Non-statistical 13C Fractionation Distinguishes Co-incident and Divergent Steps in the Biosynthesis of the Alkaloids Nicotine and Tropine*

PubMed Central

Romek, Katarzyna M.; Remaud, Gérald S.; Silvestre, Virginie; Paneth, Piotr; Robins, Richard J.

2016-01-01

During the biosynthesis of natural products, isotopic fractionation occurs due to the selectivity of enzymes for the heavier or lighter isotopomers. As only some of the positions in the molecule are implicated in a given reaction mechanism, position-specific fractionation occurs, leading to a non-statistical distribution of isotopes. This can be accessed by isotope ratio monitoring 13C NMR spectrometry. The solanaceous alkaloids S-(−)-nicotine and hyoscyamine (atropine) are related in having a common intermediate, but downstream enzymatic steps diverge, providing a relevant test case to: (a) elucidate the isotopic affiliation between carbon atoms in the alkaloids and those in the precursors; (b) obtain information about the kinetic isotope effects of as yet undescribed enzymes, thus to make predictions as to their possible mechanism(s). We show that the position-specific 13C/12C ratios in the different moieties of these compounds can satisfactorily be related to their known precursors and to the known kinetic isotope effects of enzymes involved in their biosynthesis, or to similar reaction mechanisms. Thus, the pathway to the common intermediate, N-methyl-Δ1-pyrrolinium, is seen to introduce similar isotope distribution patterns in the two alkaloids independent of plant species, whereas the remaining atoms of each target compound, which are of different origins, reflect their specific metabolic ancestry. We further demonstrate that the measured 13C distribution pattern can be used to deduce aspects of the reaction mechanism of enzymes still to be identified. PMID:27288405

The carbon isotopic composition of ecosystem breath

NASA Astrophysics Data System (ADS)

Ehleringer, J.

2008-05-01

At the global scale, there are repeatable annual fluctuations in the concentration and isotopic composition of atmospheric carbon dioxide, sometimes referred to as the "breathing of the planet". Vegetation components within ecosystems fix carbon dioxide through photosynthesis into stable organic compounds; simultaneously both vegetation and heterotrophic components of the ecosystem release previously fixed carbon as respiration. These two-way fluxes influencing carbon dioxide exchange between the biosphere and the atmosphere impact both the concentration and isotopic composition of carbon dioxide within the convective boundary layer. Over space, the compounding effects of gas exchange activities from ecosystems become reflected in both regional and global changes in the concentration and isotopic composition of atmospheric carbon dioxide. When these two parameters are plotted against each other, there are significant linear relationships between the carbon isotopic composition and inverse concentration of atmospheric carbon dioxide. At the ecosystem scale, these "Keeling plots" intercepts of C3-dominated ecosystems describe the carbon isotope ratio of biospheric gas exchange. Using Farquhar's model, these carbon isotope values can be translated into quantitative measures of the drought-dependent control of photosynthesis by stomata as water availability changes through time. This approach is useful in aggregating the influences of drought across regional landscapes as it provides a quantitative measure of stomatal influence on photosynthetic gas exchange at the ecosystem-to-region scales. Multi-year analyses of the drought-dependent trends across terrestrial ecosystems show a repeated pattern with water stress in all but one C3-ecosystem type. Ecosystems that are dominated by ring-porous trees appear not to exhibit a dynamic stomatal response to water stress and therefore, there is little dependence of the carbon isotope ratio of gas exchange on site water balance. The mechanistic basis for this pattern is defined; the implications of climate change on ring-porous versus diffuse-porous vegetation and therefore on future atmospheric carbon dioxide isotope-concentration patterns is discussed.

A Triple-Isotope Approach to Predict the Breeding Origins of European Bats

PubMed Central

Popa-Lisseanu, Ana G.; Sörgel, Karin; Luckner, Anja; Wassenaar, Leonard I.; Ibáñez, Carlos; Kramer-Schadt, Stephanie; Ciechanowski, Mateusz; Görföl, Tamás; Niermann, Ivo; Beuneux, Grégory; Mysłajek, Robert W.; Juste, Javier; Fonderflick, Jocelyn; Kelm, Detlev H.; Voigt, Christian C.

2012-01-01

Despite a commitment by the European Union to protect its migratory bat populations, conservation efforts are hindered by a poor understanding of bat migratory strategies and connectivity between breeding and wintering grounds. Traditional methods like mark-recapture are ineffective to study broad-scale bat migratory patterns. Stable hydrogen isotopes (δD) have been proven useful in establishing spatial migratory connectivity of animal populations. Before applying this tool, the method was calibrated using bat samples of known origin. Here we established the potential of δD as a robust geographical tracer of breeding origins of European bats by measuring δD in hair of five sedentary bat species from 45 locations throughout Europe. The δD of bat hair strongly correlated with well-established spatial isotopic patterns in mean annual precipitation in Europe, and therefore was highly correlated with latitude. We calculated a linear mixed-effects model, with species as random effect, linking δD of bat hair to precipitation δD of the areas of hair growth. This model can be used to predict breeding origins of European migrating bats. We used δ13C and δ15N to discriminate among potential origins of bats, and found that these isotopes can be used as variables to further refine origin predictions. A triple-isotope approach could thereby pinpoint populations or subpopulations that have distinct origins. Our results further corroborated stable isotope analysis as a powerful method to delineate animal migrations in Europe. PMID:22291947

Global patterns of foliar nitrogen isotopes and their relationships with climate, mycorrhizal fungi, foliar nutrient concentrations, and nitrogen availability

Treesearch

Joseph M. Craine; Andrew J. Elmore; Marcos P. M. Aidar; Mercedes Bustamante; Todd E. Dawson; Erik A. Hobbie; Ansgar Kahmen; Michelle C. Mack; Kendra K. McLauchlan; Anders Michelsen; Gabriela Nardoto; Linda H. Pardo; Josep Penuelas; Peter B. Reich; Edward A.G. Schuur; William D. Stock; Pamela H. Templer; Ross A. Virginia; Jeffrey M. Welker; Ian J. Wright

2009-01-01

Ratios of nitrogen (N) isotopes in leaves could elucidate underlying patterns of N cycling across ecological gradients. To better understand global-scale patterns of N cycling, we compiled data on foliar N isotope ratios, foliar N concentrations, mycorrhizal type and climate for over 11 000 plants worldwide. Global-scale comparisons of other components of the N cycle...

Variation in catchment areas of Indiana bat (Myotis sodalis) hibernacula inferred from stable hydrogen (δ2H) isotope analysis.

Treesearch

E.R. Britzke; S.C. Loeb; C.S. Romanek; K.A. Hobson; M.J. Vonhof

2013-01-01

Understanding seasonal movements of bats is important for effective conservation efforts. Although female Indiana bats (Myotis sodalis Miller and Allen, 1928) have been documented to migrate >500 km, knowledge of their migratory patterns is still extremely limited. We used the relationship between latitude and stable hydrogen isotope ratio in bat hair (δ...

The Steady State Great Ape? Long Term Isotopic Records Reveal the Effects of Season, Social Rank and Reproductive Status on Bonobo Feeding Behavior

PubMed Central

Oelze, Vicky M.; Douglas, Pamela Heidi; Stephens, Colleen R.; Surbeck, Martin; Behringer, Verena; Richards, Michael P.; Fruth, Barbara; Hohmann, Gottfried

2016-01-01

Dietary ecology of extant great apes is known to respond to environmental conditions such as climate and food availability, but also to vary depending on social status and life history characteristics. Bonobos (Pan paniscus) live under comparatively steady ecological conditions in the evergreen rainforests of the Congo Basin. Bonobos are an ideal species for investigating influences of sociodemographic and physiological factors, such as female reproductive status, on diet. We investigate the long term dietary pattern in wild but fully habituated bonobos by stable isotope analysis in hair and integrating a variety of long-term sociodemographic information obtained through observations. We analyzed carbon and nitrogen stable isotopes in 432 hair sections obtained from 101 non-invasively collected hair samples. These samples represented the dietary behavior of 23 adult bonobos from 2008 through 2010. By including isotope and crude protein data from plants we could establish an isotope baseline and interpret the results of several general linear mixed models using the predictors climate, sex, social rank, reproductive state of females, adult age and age of infants. We found that low canopy foliage is a useful isotopic tracer for tropical rainforest settings, and consumption of terrestrial herbs best explains the temporal isotope patterns we found in carbon isotope values of bonobo hair. Only the diet of male bonobos was affected by social rank, with lower nitrogen isotope values in low-ranking young males. Female isotope values mainly differed between different stages of reproduction (cycling, pregnancy, lactation). These isotopic differences appear to be related to changes in dietary preference during pregnancy (high protein diet) and lactation (high energy diet), which allow to compensate for different nutritional needs during maternal investment. PMID:27626279

High-resolution (SIMS) versus bulk sulfur isotope patterns of pyrite in Proterozoic microbialites with diverse mat textures

NASA Astrophysics Data System (ADS)

Gomes, M. L.; Fike, D. A.; Bergmann, K.; Knoll, A. H.

2015-12-01

Sulfur (S) isotope signatures of sedimentary pyrite preserved in marine rocks provide a rich suite of information about changes in biogeochemical cycling associated with the evolution of microbial metabolisms and oxygenation of Earth surface environments. Conventionally, these S isotope records are based on bulk rock measurements. Yet, in modern microbial mat environments, S isotope compositions of sulfide can vary by up to 40‰ over a spatial range of ~ 1 mm. Similar ranges of S isotope variability have been found in Archean pyrite grains using both Secondary Ion Mass Spectrometry and other micro-analytical techniques. These micron-scale patterns have been linked to changes in rates of microbial sulfate reduction and/or sulfide oxidation, isotopic distillation of the sulfate reservoir due to microbial sulfate reduction, and post-depositional alteration. Fine-scale mapping of S isotope compositions of pyrite can thus be used to differentiate primary environmental signals from post-depositional overprinting - improving our understanding of both. Here, we examine micron-scale S isotope patterns of pyrite in microbialites from the Mesoproterozoic-Neoproterozoic Sukhaya Tunguska Formation and Neoproterozoic Draken Formation in order to explore S isotope variability associated with different mat textures and pyrite grain morphologies. A primary goal is to link modern observations of how sulfide spatial isotope distributions reflect active microbial communities present at given depths in the mats to ancient processes driving fine-sale pyrite variability in microbialites. We find large (up to 60‰) S isotope variability within a spatial range of less than 2.5cm. The micron-scale S isotope measurements converge around the S isotope composition of pyrite extracted from bulk samples of the same microbialites. These micron-scale pyrite S isotope patterns have the potential to reveal important information about ancient biogeochemical cycling in Proterozoic mat environments with implications for interpreting S isotope signatures from the geological record.

Secular variations of iron isotopes in ferromanganese crusts: evidences for deeply sourced iron in the Pacific Ocean?

NASA Astrophysics Data System (ADS)

Rouxel, O. J.; Gueguen, B.

2016-12-01

Ferromanganese (Fe-Mn) crusts are potential archive of the Fe isotope composition of deep seawater through time. Here, we report Fe isotope composition of two pairs of Fe-Mn crusts collected on two volcanic seamounts from the Northern Pacific Ocean (Apuupuu Seamount, Hawaii) and the Southern Pacific Ocean (near Rurutu Island, Austral archipelago of French Polynesia). This approach allows (a) a direct comparison of the Fe isotope record in Fe-Mn crusts from the same seamount in order to address local effects, and (b) a comparison of geochemical composition of crusts between North and South Pacific in order to address the effect of more global geochemical processes. The results show that, despite different growth rates, diagenetic history, textures and geochemical patterns, Fe-Mn crusts from both North and South Pacific Oceans have fairly homogenous Fe isotope compositions over the last 17 Ma, yielding average δ56Fe values of -0.22 ± 0.20‰ (1sd, n = 54). The results also show striking correlations between Fe and Pb isotope ratios, indicating that local mixing between water masses is the main factor controlling Fe isotope composition in FeMn crusts. Recently, Horner et al. (2015) reported a range of δ56Fe values from -1.12‰ to 1.54‰ along a 76 Ma-old FeMn crust from the central pacific. However, secular variations of Fe isotopes inferred from other FeMn crusts in the Central North Pacific and Western Pacific (Yang and Rouxel, unpublished) show different patterns over the last 40 Ma, with δ56Fe ranging from -0.07 to -0.61‰ (n=81). Hence, the application of Fe isotopes as paleoceanographic proxies to trace deeply sourced iron at the scale of oceanic basins should be used with caution, prompting for an integrative approach combining diverse yet complimentary geochemical proxies.

Tracking Cats: Problems with Placing Feline Carnivores on δ18O, δD Isoscapes

PubMed Central

Pietsch, Stephanie J.; Hobson, Keith A.; Wassenaar, Leonard I.; Tütken, Thomas

2011-01-01

Background Several felids are endangered and threatened by the illegal wildlife trade. Establishing geographic origin of tissues of endangered species is thus crucial for wildlife crime investigations and effective conservation strategies. As shown in other species, stable isotope analysis of hydrogen and oxygen in hair (δDh, δ18Oh) can be used as a tool for provenance determination. However, reliably predicting the spatial distribution of δDh and δ18Oh requires confirmation from animal tissues of known origin and a detailed understanding of the isotopic routing of dietary nutrients into felid hair. Methodology/Findings We used coupled δDh and δ18Oh measurements from the North American bobcat (Lynx rufus) and puma (Puma concolor) with precipitation-based assignment isoscapes to test the feasibility of isotopic geo-location of felidae. Hairs of felid and rabbit museum specimens from 75 sites across the United States and Canada were analyzed. Bobcat and puma lacked a significant correlation between H/O isotopes in hair and local waters, and also exhibited an isotopic decoupling of δ18Oh and δDh. Conversely, strong δD and δ18O coupling was found for key prey, eastern cottontail rabbit (Sylvilagus floridanus; hair) and white-tailed deer (Odocoileus virginianus; collagen, bone phosphate). Conclusions/Significance Puma and bobcat hairs do not adhere to expected pattern of H and O isotopic variation predicted by precipitation isoscapes for North America. Thus, using bulk hair, felids cannot be placed on δ18O and δD isoscapes for use in forensic investigations. The effective application of isotopes to trace the provenance of feline carnivores is likely compromised by major controls of their diet, physiology and metabolism on hair δ18O and δD related to body water budgets. Controlled feeding experiments, combined with single amino acid isotope analysis of diets and hair, are needed to reveal mechanisms and physiological traits explaining why felid hair does not follow isotopic patterns demonstrated in many other taxa. PMID:21931770

Inverse methods for estimating primary input signals from time-averaged isotope profiles

NASA Astrophysics Data System (ADS)

Passey, Benjamin H.; Cerling, Thure E.; Schuster, Gerard T.; Robinson, Todd F.; Roeder, Beverly L.; Krueger, Stephen K.

2005-08-01

Mammalian teeth are invaluable archives of ancient seasonality because they record along their growth axes an isotopic record of temporal change in environment, plant diet, and animal behavior. A major problem with the intra-tooth method is that intra-tooth isotope profiles can be extremely time-averaged compared to the actual pattern of isotopic variation experienced by the animal during tooth formation. This time-averaging is a result of the temporal and spatial characteristics of amelogenesis (tooth enamel formation), and also results from laboratory sampling. This paper develops and evaluates an inverse method for reconstructing original input signals from time-averaged intra-tooth isotope profiles. The method requires that the temporal and spatial patterns of amelogenesis are known for the specific tooth and uses a minimum length solution of the linear system Am = d, where d is the measured isotopic profile, A is a matrix describing temporal and spatial averaging during amelogenesis and sampling, and m is the input vector that is sought. Accuracy is dependent on several factors, including the total measurement error and the isotopic structure of the measured profile. The method is shown to accurately reconstruct known input signals for synthetic tooth enamel profiles and the known input signal for a rabbit that underwent controlled dietary changes. Application to carbon isotope profiles of modern hippopotamus canines reveals detailed dietary histories that are not apparent from the measured data alone. Inverse methods show promise as an effective means of dealing with the time-averaging problem in studies of intra-tooth isotopic variation.

Isotope pattern deconvolution as a tool to study iron metabolism in plants.

PubMed

Rodríguez-Castrillón, José Angel; Moldovan, Mariella; García Alonso, J Ignacio; Lucena, Juan José; García-Tomé, Maria Luisa; Hernández-Apaolaza, Lourdes

2008-01-01

Isotope pattern deconvolution is a mathematical technique for isolating distinct isotope signatures from mixtures of natural abundance and enriched tracers. In iron metabolism studies measurement of all four isotopes of the element by high-resolution multicollector or collision cell ICP-MS allows the determination of the tracer/tracee ratio with simultaneous internal mass bias correction and lower uncertainties. This technique was applied here for the first time to study iron uptake by cucumber plants using 57Fe-enriched iron chelates of the o,o and o,p isomers of ethylenediaminedi(o-hydroxyphenylacetic) acid (EDDHA) and ethylenediamine tetraacetic acid (EDTA). Samples of root, stem, leaves, and xylem sap, after exposure of the cucumber plants to the mentioned 57Fe chelates, were collected, dried, and digested using nitric acid. The isotopic composition of iron in the samples was measured by ICP-MS using a high-resolution multicollector instrument. Mass bias correction was computed using both a natural abundance iron standard and by internal correction using isotope pattern deconvolution. It was observed that, for plants with low 57Fe enrichment, isotope pattern deconvolution provided lower tracer/tracee ratio uncertainties than the traditional method applying external mass bias correction. The total amount of the element in the plants was determined by isotope dilution analysis, using a collision cell quadrupole ICP-MS instrument, after addition of 57Fe or natural abundance Fe in a known amount which depended on the isotopic composition of the sample.

Analysing the isotopic life history of the alpine ungulates Capra ibex and Rupicapra rupicapra rupicapra through their horns.

PubMed

Barbosa, Inês C R; Kley, Maximiliane; Schäufele, Rudi; Auerswald, Karl; Schröder, Wolf; Filli, Flurin; Hertwig, Stefan; Schnyder, Hans

2009-08-01

The horn of ungulate grazers offers a valuable isotopic record of their diet and environment. However, there have been no reports of the spatio-temporal variation of the isotopic composition of horns. We investigated patterns of carbon (delta(13)C) and nitrogen (delta(15)N) isotopic composition along and perpendicular to the horn axis in Capra ibex and Rupicapra rupicapra rupicapra to assess the effects of animal age, within-year (seasonal) and inter-annual variation, natural contamination and sampling position on horn isotope composition. Horns of male C. ibex (n = 23) and R. r. rupicapra (n = 1) were sampled longitudinally on the front (only R. r. rupicapra) and back side and on the surface and sub-surface. The sides of the R. r. rupicapra horn did not differ in delta(13)C. In both species, the horn surface had a 0.15 per thousand lower delta(13)C and a higher carbon-to-nitrogen (C/N) ratio than the sub-surface. Washing the horn with water and organic solvents removed material that caused these differences. With age, the delta(15)N of C. ibex horns increased (+0.1 per thousand year(-1)), C/N ratio increased, and (13)C discrimination relative to atmospheric CO(2) ((13)Delta) increased slightly (+0.03 per thousand year(-1)). Geostatistical analysis of one C. ibex horn revealed systematic patterns of inter-annual and seasonal (13)C changes, but (15)N changed only seasonally. The work demonstrates that isotopic signals in horns are influenced by natural contamination (delta(13)C), age effects ((13)Delta and delta(15)N), and seasonal (delta(13)C and delta(15)N) and inter-annual variation (delta(13)C). The methods presented allow us to distinguish between these effects and thus allow the use of horns as isotopic archives of the ecology of these species and their habitat. Copyright (c) 2009 John Wiley & Sons, Ltd.

Measurement of Enzyme Isotope Effects.

PubMed

Kholodar, Svetlana A; Ghosh, Ananda K; Kohen, Amnon

2017-01-01

Enzyme isotope effects, or the kinetic effects of "heavy" enzymes, refer to the effect of isotopically labeled protein residues on the enzyme's activity or physical properties. These effects are increasingly employed in the examination of the possible contributions of protein dynamics to enzyme catalysis. One hypothesis assumed that isotopic substitution of all 12 C, 14 N, and nonexchangeable 1 H by 13 C, 15 N, and 2 H, would slow down protein picosecond to femtosecond dynamics without any effect on the system's electrostatics following the Born-Oppenheimer approximation. It was suggested that reduced reaction rates reported for several "heavy" enzymes accords with that hypothesis. However, numerous deviations from the predictions of that hypothesis were also reported. Current studies also attempt to test the role of individual residues by site-specific labeling or by labeling a pattern of residues on activity. It appears that in several systems the protein's fast dynamics are indeed reduced in "heavy" enzymes in a way that reduces the probability of barrier crossing of its chemical step. Other observations, however, indicated that slower protein dynamics are electrostatically altered in isotopically labeled enzymes. Interestingly, these effects appear to be system dependent, thus it might be premature to suggest a general role of "heavy" enzymes' effect on catalysis. © 2017 Elsevier Inc. All rights reserved.

Patterns of local and nonlocal water resource use across the western U.S. determined via stable isotope intercomparisons

USDA-ARS?s Scientific Manuscript database

The stable isotope ratios of hydrogen (H) and oxygen (O) are valuable tracers of the origin of biological materials and water sources. Application of these environmental tracers is largely based on the distinct and pervasive spatial patterns of precipitation isotopes, which are preserved in many hy...

Zinc isotopic fractionation in Phragmites australis in response to toxic levels of zinc

PubMed Central

Caldelas, Cristina; Dong, Shuofei; Araus, José Luis; Jakob Weiss, Dominik

2011-01-01

Stable isotope signatures of Zn have shown great promise in elucidating changes in uptake and translocation mechanisms of this metal in plants during environmental changes. Here this potential was tested by investigating the effect of high Zn concentrations on the isotopic fractionation patterns of Phragmites australis (Cav.) Trin. ex Steud. Plants were grown for 40 d in a nutritive solution containing 3.2 μM (sufficient) or 2 mM (toxic) Zn. The Zn isotopic composition of roots, rhizomes, shoots, and leaves was analysed. Stems and leaves were sampled at different heights to evaluate the effect of long-distance transport on Zn fractionation. During Zn sufficiency, roots, rhizomes, and shoots were isotopically heavy (δ66ZnJMC Lyon=0.2‰) while the youngest leaves were isotopically light (–0.5‰). During Zn excess, roots were still isotopically heavier (δ66Zn=0.5‰) and the rest of the plant was isotopically light (up to –0.5‰). The enrichment of heavy isotopes at the roots was attributed to Zn uptake mediated by transporter proteins under Zn-sufficient conditions and to chelation and compartmentation in Zn excess. The isotopically lighter Zn in shoots and leaves is consistent with long-distance root to shoot transport. The tolerance response of P. australis increased the range of Zn fractionation within the plant and with respect to the environment. PMID:21193582

Isotope fractionation during the anaerobic consumption of acetate by methanogenic and sulfate-reducing microorganisms

NASA Astrophysics Data System (ADS)

Gövert, D.; Conrad, R.

2009-04-01

During the anaerobic degradation of organic matter in anoxic sediments and soils acetate is the most important substrate for the final step in production of CO2 and/or CH4. Sulfate-reducing bacteria (SRB) and methane-producing archaea both compete for the available acetate. Knowledge about the fractionation of 13C/12C of acetate carbon by these microbial groups is still limited. Therefore, we determined carbon isotope fractionation in different cultures of acetate-utilizing SRB (Desulfobacter postgatei, D. hydrogenophilus, Desulfobacca acetoxidans) and methanogens (Methanosarcina barkeri, M. acetivorans). Including literature values (e.g., Methanosaeta concilii), isotopic enrichment factors (epsilon) ranged between -35 and +2 permil, possibly involving equilibrium isotope effects besides kinetic isotope effects. The values of epsilon were dependent on the acetate-catabolic pathway of the particular microorganism, the methyl or carboxyl position of acetate, and the relative availability or limitation of the substrate acetate. Patterns of isotope fractionation in anoxic lake sediments and rice field soil seem to reflect the characteristics of the microorganisms actively involved in acetate catabolism. Hence, it might be possible using environmental isotopic information to determine the type of microbial metabolism converting acetate to CO2 and/or CH4.

First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi.

PubMed

Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass ( Equus hemionus ) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi.

Relation of Phanerozoic stable isotope excursions to climate, bacterial metabolism, and major extinctions

PubMed Central

Stanley, Steven M.

2010-01-01

Conspicuous global stable carbon isotope excursions that are recorded in marine sedimentary rocks of Phanerozoic age and were associated with major extinctions have generally paralleled global stable oxygen isotope excursions. All of these phenomena are therefore likely to share a common origin through global climate change. Exceptional patterns for carbon isotope excursions resulted from massive carbon burial during warm intervals of widespread marine anoxic conditions. The many carbon isotope excursions that parallel those for oxygen isotopes can to a large degree be accounted for by the Q10 pattern of respiration for bacteria: As temperature changed along continental margins, where ∼90% of marine carbon burial occurs today, rates of remineralization of isotopically light carbon must have changed exponentially. This would have reduced organic carbon burial during global warming and increased it during global cooling. Also contributing to the δ13C excursions have been release and uptake of methane by clathrates, the positive correlation between temperature and degree of fractionation of carbon isotopes by phytoplankton at temperatures below ∼15°, and increased phytoplankton productivity during “icehouse” conditions. The Q10 pattern for bacteria and climate-related changes in clathrate volume represent positive feedbacks for climate change. PMID:21041682

Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

NASA Astrophysics Data System (ADS)

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

2006-12-01

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

Multiple isotope analyses of the pike tapeworm Triaenophorus nodulosus reveal peculiarities in consumer-diet discrimination patterns.

PubMed

Behrmann-Godel, J; Yohannes, E

2015-03-01

Previous studies of dietary isotope discrimination have led to the general expectation that a consumer will exhibit enriched stable isotope levels relative to its diet. Parasite-host systems are specific consumer-diet pairs in which the consumer (parasite) feeds exclusively on one dietary source: host tissue. However, the small numbers of studies previously carried out on isotopic discrimination in parasite-host (ΔXP-HT) systems have yielded controversial results, showing some parasites to be isotopically depleted relative to their food source, while others are enriched or in equilibrium with their hosts. Although the mechanism for these deviations from expectations remains to be understood, possible influences of specific feeding niche or selection for only a few nutritional components by the parasite are discussed. ΔXP-HT for multiple isotopes (δ13C, δ15N, δ34S) were measured in the pike tapeworm Triaenophorus nodulosus and two of its life-cycle fish hosts, perch Perca fluviatilis and pike Esox lucius, within which T. nodulosus occupies different feeding locations. Variability in the value of ΔXP-HT calculated for the parasite and its different hosts indicates an influence of feeding location on isotopic discrimination. In perch liver ΔXP-HT was relatively more negative for all three stable isotopes. In pike gut ΔXP-HT was more positive for δ13C, as expected in conventional consumer-diet systems. For parasites feeding on pike gut, however, the δ15N and δ34S isotope values were comparable with those of the host. We discuss potential causes of these deviations from expectations, including the effect of specific parasite feeding niches, and conclude that ΔXP-HT should be critically evaluated for trophic interactions between parasite and host before general patterns are assumed.

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.

Carbon isotopic patterns of amino acids associated with various microbial metabolic pathways and physiological conditions

NASA Astrophysics Data System (ADS)

Wang, P. L.; Hsiao, K. T.; Lin, L. H.

2017-12-01

Amino acids represent one of the most important categories of biomolecule. Their abundance and isotopic patterns have been broadly used to address issues related to biochemical processes and elemental cycling in natural environments. Previous studies have shown that various carbon assimilative pathways of microorganisms (e.g. autotrophy, heterotrophy and acetotrophy) could be distinguished by carbon isotopic patterns of amino acids. However, the taxonomic and catabolic coverage are limited in previous examination. This study aims to uncover the carbon isotopic patterns of amino acids for microorganisms remaining uncharacterized but bearing biogeochemical and ecological significance in anoxic environments. To fulfill the purpose, two anaerobic strains were isolated from riverine wetland and mud volcano in Taiwan. One strain is a sulfate reducing bacterium (related to Desulfovibrio marrakechensis), which is capable of utilizing either H2 or lactate, and the other is a methanogen (related to Methanolobus profundi), which grows solely with methyl-group compounds. Carbon isotope analyses of amino acids were performed on cells grown in exponential and stationary phase. The isotopic patterns were similar for all examined cultures, showing successive 13C depletion along synthetic pathways. No significant difference was observed for the methanogen and lactate-utilizing sulfate reducer harvested in exponential and stationary phases. In contrast, the H2-utilizing sulfate reducer harvested in stationary phase depleted and enriched 13C in aspartic acid and glycine, respectively when compared with that harvested in exponential phase. Such variations might infer the change of carbon flux during synthesis of these two amino acids in the reverse TCA cycle. In addition, the discriminant function analysis for all available data from culture studies further attests the capability of using carbon isotope patterns of amino acids in identifying microbial metabolisms.

Ecological differences in three autochthonous equid species in Mongolian Gobi inferred from stable isotopes in tail hair

NASA Astrophysics Data System (ADS)

Burnik Šturm, Martina; Voigt, Christian C.; Oyunsaikhan, Ganbaatar; Kaczensky, Petra

2014-05-01

In the Dzungarian Gobi of Mongolia three equid species, Asiatic wild ass (Equus hemionus), domestic horse (Equus caballus), and re-introduced Przewalski's horse (Equus ferus przewalskii) share the same habitat and thus provide a unique opportunity for comparative ecological studies. In our project we use the stable isotope analysis of tail hair as a tool to study feeding ecology, water use and movement pattern of the three extant sympatric equid species to reveal species specific differences and thus strengthen our understanding of the ecological adaptations of the three species to the harsh environment of the Gobi desert. Since tail hair grow continuously and is isotopically inert after formation, when sampled and analysed longitudinally, provides temporary explicit information on dietary regime and movement pattern. We use the carbon isotopes in the tail hair to determine the quantitative dependence of each animal on isotopically distinct C3 (grasses) and C4 (multitude of annuals and perennials) diet. Nitrogen isotopes reflect the isotopic composition of the diet and hydrogen isotopes reflect the isotopic composition of the water that animals utilize, while both elements have been reported to also give information on the physical status of the animal. Combined isotope data will be used to describe the movement patterns and habitat use of the three equid species. We will present the methodology and first preliminary results of carbon and nitrogen isotope analysis of potential forage plants of the study area and of the tail hair analysis. Among the analysed plants, collected in the pilot sampling campaign in 2012 (n = 192), we identified 14 C3 and two C4species and found no general trend that could explain the effect of altitude on carbon isotopic composition in C3 plants and no correlation between carbon isotopic composition and longitude or latitude. We performed additional, more detailed plant sampling in 2013. The first results obtained from the tail hair analysis indicate differences in feeding preferences between extant wild asses (n = 6) and Przewalski's (n = 6) and domestic horses (n = 6). While wild asses switch regularly between periods with predominantly feeding on C3 diet with low incorporation of C4 diet (wet season) and periods with high incorporation of C4 (dry season) diet, Przewalski's and domestic horses predominantly feed on C3 plant diet but seem to also include C4plants in their diet during extreme conditions (i.e. extremely harsh winters).

Periodicity analysis of δ18O in precipitation over Central Europe: Time-frequency considerations of the isotopic 'temperature' effect

NASA Astrophysics Data System (ADS)

Salamalikis, V.; Argiriou, A. A.; Dotsika, E.

2016-03-01

In this paper the periodic patterns of the isotopic composition of precipitation (δ18O) for 22 stations located around Central Europe are investigated through sinusoidal models and wavelet analysis over a 23 years period (1980/01-2002/12). The seasonal distribution of δ18O follows the temporal variability of air temperature providing seasonal amplitudes ranging from 0.94‰ to 4.47‰; the monthly isotopic maximum is observed in July. The isotopic amplitude reflects the geographical dependencies of the isotopic composition of precipitation providing higher values when moving inland. In order to describe the dominant oscillation modes included in δ18O time series, the Morlet Continuous Wavelet Transform is evaluated. The main periodicity is represented at 12-months (annual periodicity) where the wavelet power is mainly concentrated. Stations (i.e. Cuxhaven, Trier, etc.) with limited seasonal isotopic effect provide sparse wavelet power areas at the annual periodicity mode explaining the fact that precipitation has a complex isotopic fingerprint that cannot be examined solely by the seasonality effect. Since temperature is the main contributor of the isotopic variability in mid-latitudes, the isotope-temperature effect is also investigated. The isotope-temperature slope ranges from 0.11‰/°C to 0.47‰/°C with steeper values observed at the southernmost stations of the study area. Bivariate wavelet analysis is applied in order to determine the correlation and the slope of the δ18O - temperature relationship over the time-frequency plane. High coherencies are detected at the annual periodicity mode. The time-frequency slope is calculated at the annual periodicity mode ranging from 0.45‰/°C to 0.83‰/°C with higher values at stations that show a more distinguishable seasonal isotopic behavior. Generally the slope fluctuates around a mean value but in certain cases (sites with low seasonal effect) abrupt slope changes are derived and the slope becomes strongly unstable.

First stable isotope analysis of Asiatic wild ass tail hair from the Mongolian Gobi

PubMed Central

Horacek, Micha; Sturm, Martina Burnik; Kaczensky, Petra

2015-01-01

Stable isotope analysis has become a powerful tool to study feeding ecology, water use or movement pattern in contemporary, historic and ancient species. Certain hair and teeth grow continuously, and when sampled longitudinally can provide temporally explicit information on dietary regime and movement pattern. In an initial trial, we analysed a tail sample of an Asiatic wild ass (Equus hemionus) from the Mongolian Gobi. We found seasonal variations in H, C and N isotope patterns, likely being the result of temporal variations in available feeds, water supply and possibly physiological status. Thus stable isotope analysis shows promise to study the comparative ecology of the three autochthonous equid species in the Mongolian Gobi. PMID:26339116

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.

Isotope pattern deconvolution for peptide mass spectrometry by non-negative least squares/least absolute deviation template matching

PubMed Central

2012-01-01

Background The robust identification of isotope patterns originating from peptides being analyzed through mass spectrometry (MS) is often significantly hampered by noise artifacts and the interference of overlapping patterns arising e.g. from post-translational modifications. As the classification of the recorded data points into either ‘noise’ or ‘signal’ lies at the very root of essentially every proteomic application, the quality of the automated processing of mass spectra can significantly influence the way the data might be interpreted within a given biological context. Results We propose non-negative least squares/non-negative least absolute deviation regression to fit a raw spectrum by templates imitating isotope patterns. In a carefully designed validation scheme, we show that the method exhibits excellent performance in pattern picking. It is demonstrated that the method is able to disentangle complicated overlaps of patterns. Conclusions We find that regularization is not necessary to prevent overfitting and that thresholding is an effective and user-friendly way to perform feature selection. The proposed method avoids problems inherent in regularization-based approaches, comes with a set of well-interpretable parameters whose default configuration is shown to generalize well without the need for fine-tuning, and is applicable to spectra of different platforms. The R package IPPD implements the method and is available from the Bioconductor platform (http://bioconductor.fhcrc.org/help/bioc-views/devel/bioc/html/IPPD.html). PMID:23137144

Clumped Isotope Composition of Cold-Water Corals: A Role for Vital Effects?

NASA Astrophysics Data System (ADS)

Spooner, P.; Guo, W.; Robinson, L. F.

2014-12-01

Measurements on a set of cold-water corals (mainly Desmophyllum dianthus) have suggested that their clumped isotope composition could serve as a promising proxy for reconstructing paleocean temperatures. Such measurements have also offered support for certain isotope models of coral calcification. However, there are differences in the clumped isotope compositions between warm-water and cold-water corals, suggesting that different kinds of corals could have differences in their biocalcification processes. In order to understand the systematics of clumped isotope variations in cold-water corals more fully, we present clumped isotope data from a range of cold-water coral species from the tropical Atlantic and the Southern Ocean.Our samples were either collected live or recently dead (14C ages < 1,000 yrs) with associated temperature data. They include a total of 11 solitary corals and 1 colonial coral from the Atlantic, and 8 solitary corals from the Southern Ocean. The data indicate that coral clumped isotope systematics may be more complicated than previously thought. For example, for the genus Caryophyllia we observe significant variations in clumped isotope compositions for corals which grew at the same temperature with an apparent negative correlation between Δ47 and δ18O, different to patterns previously observed in Desmophyllum. These results indicate that existing isotope models of biocalcification may not apply equally well to all corals. Clumped isotope vital effects may be present in certain cold-water corals as they are in warm-water corals, complicating the use of this paleoclimate proxy.

Isotopic incorporation rates for shark tissues from a long-term captive feeding study.

PubMed

Kim, Sora Lee; del Rio, Carlos Martínez; Casper, Dave; Koch, Paul L

2012-07-15

Stable isotope analysis has provided insight into the dietary and habitat patterns of many birds, mammals and teleost fish. A crucial biological parameter to interpret field stable isotope data is tissue incorporation rate, which has not been well studied in large ectotherms. We report the incorporation of carbon and nitrogen into the tissues of leopard sharks (Triakis semifasciata). Because sharks have relatively slow metabolic rates and are difficult to maintain in captivity, no long-term feeding study has been conducted until the point of isotopic steady state with a diet. We kept six leopard sharks in captivity for 1250 days, measured their growth, and serially sampled plasma, red blood cells and muscle for stable carbon and nitrogen isotope analysis. A single-compartment model with first-order kinetics adequately described the incorporation patterns of carbon and nitrogen isotopes for these three tissues. Both carbon and nitrogen were incorporated faster in plasma than in muscle and red blood cells. The rate of incorporation of carbon into muscle was similar to that predicted by an allometric equation relating isotopic incorporation rate to body mass that was developed previously for teleosts. In spite of their large size and unusual physiology, the rates of isotopic incorporation in sharks seem to follow the same patterns found in other aquatic ectotherms.

Nitrogen isotope fractionation during N uptake via arbuscular mycorrhizal and ectomycorrhizal fungi into grey alder.

PubMed

Schweiger, Peter F

2016-10-20

Arbuscular mycorrhizal (AM) and ectomycorrhizal (ECM) fungi affect plant nitrogen (N) dynamics. Plant N isotope patterns have been used to characterise the contribution of ECM fungi to plant N uptake. By quantifying and comparing the effects of an AM and an ECM fungus on growth, N uptake and isotopic composition of one host plant grown at different relative N supply levels, the aim of this study was to improve the mechanistic understanding of natural 15 N abundance patterns in mycorrhizal plants and their underlying causes. Grey alders were inoculated with one ECM fungus or one AM fungus or left non-mycorrhizal. Plants were grown under semi-hydroponic conditions and were supplied with three rates of relative N supply ranging from deficient to luxurious. Neither mycorrhizal fungus increased plant growth or N uptake. AM root colonisation had no effect on whole plant δ 15 N and decreased foliar δ 15 N only under N deficiency. The roots of these plants were 15 N-enriched. ECM root colonisation consistently decreased foliar and whole plant δ 15 N. It is concluded, that both mycorrhizal fungi contributed to plant N uptake into the shoot. Nitrogen isotope fractionation during N assimilation and transformations in fungal mycelia is suggested to have resulted in plants receiving 15 N-depleted N via the mycorrhizal uptake pathways. Negative mycorrhizal growth effects are explained by symbiotic resource trade on carbon and N and decreased direct plant N uptake. Copyright © 2016 Elsevier GmbH. All rights reserved.

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake. Comparing carbon isotope fractionation between CO2 and CH4 with clumped isotope data suggests the temporal variability may result from changes in methane oxidation.

Sea surface salinity of the Eocene Arctic Azolla event using innovative isotope modeling

NASA Astrophysics Data System (ADS)

Speelman, E. N.; Sewall, J. O.; Noone, D.; Huber, M.; Sinninghe Damste, J. S.; Reichart, G. J.

2009-04-01

With the realization that the Eocene Arctic Ocean was covered with enormous quantities of the free floating freshwater fern Azolla, new questions regarding Eocene conditions facilitating these blooms arose. Our present research focuses on constraining the actual salinity of, and water sources for, the Eocene Arctic basin through the application of stable water isotope tracers. Precipitation pathways potentially strongly affect the final isotopic composition of water entering the Arctic Basin. Therefore we use the Community Atmosphere Model (CAM3), developed by NCAR, combined with a recently developed integrated isotope tracer code to reconstruct the isotopic composition of global Eocene precipitation and run-off patterns. We further addressed the sensitivity of the modeled hydrological cycle to changes in boundary conditions, such as pCO2, sea surface temperatures (SSTs) and sea ice formation. In this way it is possible to assess the effect of uncertainties in proxy estimates of these parameters. Overall, results of all runs with Eocene boundary conditions, including Eocene topography, bathymetry, vegetation patterns, TEX86 derived SSTs and pCO2 estimates, show the presence of an intensified hydrological cycle with precipitation exceeding evaporation in the Arctic region. Enriched, precipitation weighted, isotopic values of around -120‰ are reported for the Arctic region. Combining new results obtained from compound specific isotope analyses (δD) on terrestrially derived n-alkanes extracted from Eocene sediments, and model outcomes make it possible to verify climate reconstructions for the middle Eocene Arctic. Furthermore, recently, characteristic long-chain mid-chain ω20 hydroxy wax constituents of Azolla were found in ACEX sediments. δD values of these C32 - C36 diols provide insight into the isotopic composition of the Eocene Arctic surface water. As the isotopic signature of the runoff entering the Arctic is modelled, and the final isotopic composition of the surface waters can be deduced from the isotopic composition of the diols, we can calculate the degree of mixing between freshwater (isotopically light) and seawater (isotopically heavy) in the surface waters. This way we quantify Eocene Arctic surface water salinity, which in turn will shed light on the degree of (seasonal) mixing and stratification.

Characterization of phenol and cresol biodegradation by compound-specific stable isotope analysis.

PubMed

Wei, Xi; Gilevska, Tetyana; Wetzig, Felix; Dorer, Conrad; Richnow, Hans-Hermann; Vogt, Carsten

2016-03-01

Microbial degradation of phenol and cresols can occur under oxic and anoxic conditions by different degradation pathways. One recent technique to take insight into reaction mechanisms is compound-specific isotope analysis (CSIA). While enzymes and reaction mechanisms of several degradation pathways have been characterized in (bio)chemical studies, associated isotope fractionation patterns have been rarely reported, possibly due to constraints in current analytical methods. In this study, carbon enrichment factors and apparent kinetic isotope effects (AKIEc) of the initial steps of different aerobic and anaerobic phenol and cresols degradation pathways were analyzed by isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). Significant isotope fractionation was detected for aerobic ring hydroxylation, anoxic side chain hydroxylation, and anoxic fumarate addition, while anoxic carboxylation reactions produced small and inconsistent fractionation. The results suggest that several microbial degradation pathways of phenol and cresols are detectable in the environment by CSIA. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biologically mediated isotope fractionations - Biochemistry, geochemical significance and preservation in the earth's oldest sediments

NASA Technical Reports Server (NTRS)

Schidlowski, M.

1983-01-01

Preferential metabolization of isotopically light carbon and sulfur has resulted in a fractionation of the stable isotopes of these elements on a global scale, with the light species (C-12, S-32) markedly concentrated in biogenic materials. Since the biological effects are basically retained when carbon and sulfur are incorporated in sediments, the respective fractionations are propagated into the rock section of the geochemical cycle, this having consequently caused a characteristic bipartition of both elements between 'light' and 'heavy' crustal reservoirs. Preservation of the biological isotope effects in sedimentary rocks makes it possible to trace the underlying biochemical processes back over most of the geological record. According to the available evidence, biological (autotrophic) carbon fixation arose prior to 3.5(if not 3.8) billion years ago, while the emergence of dissimilatory sulfate reduction antedates the appearance of the oldest presumably bacteriogenic sulfur isotope patterns in rocks between 2.7 and 2.8 billion years old. Hence, biological control of the terrestrial carbon and sulfur cycles has been established very early in the earth's history.

Envelope: interactive software for modeling and fitting complex isotope distributions.

PubMed

Sykes, Michael T; Williamson, James R

2008-10-20

An important aspect of proteomic mass spectrometry involves quantifying and interpreting the isotope distributions arising from mixtures of macromolecules with different isotope labeling patterns. These patterns can be quite complex, in particular with in vivo metabolic labeling experiments producing fractional atomic labeling or fractional residue labeling of peptides or other macromolecules. In general, it can be difficult to distinguish the contributions of species with different labeling patterns to an experimental spectrum and difficult to calculate a theoretical isotope distribution to fit such data. There is a need for interactive and user-friendly software that can calculate and fit the entire isotope distribution of a complex mixture while comparing these calculations with experimental data and extracting the contributions from the differently labeled species. Envelope has been developed to be user-friendly while still being as flexible and powerful as possible. Envelope can simultaneously calculate the isotope distributions for any number of different labeling patterns for a given peptide or oligonucleotide, while automatically summing these into a single overall isotope distribution. Envelope can handle fractional or complete atom or residue-based labeling, and the contribution from each different user-defined labeling pattern is clearly illustrated in the interactive display and is individually adjustable. At present, Envelope supports labeling with 2H, 13C, and 15N, and supports adjustments for baseline correction, an instrument accuracy offset in the m/z domain, and peak width. Furthermore, Envelope can display experimental data superimposed on calculated isotope distributions, and calculate a least-squares goodness of fit between the two. All of this information is displayed on the screen in a single graphical user interface. Envelope supports high-quality output of experimental and calculated distributions in PNG or PDF format. Beyond simply comparing calculated distributions to experimental data, Envelope is useful for planning or designing metabolic labeling experiments, by visualizing hypothetical isotope distributions in order to evaluate the feasibility of a labeling strategy. Envelope is also useful as a teaching tool, with its real-time display capabilities providing a straightforward way to illustrate the key variable factors that contribute to an observed isotope distribution. Envelope is a powerful tool for the interactive calculation and visualization of complex isotope distributions for comparison to experimental data. It is available under the GNU General Public License from http://williamson.scripps.edu/envelope/.

Iron and nickel isotope fractionation by diffusion, with applications to iron meteorites

NASA Astrophysics Data System (ADS)

Watson, Heather C.; Richter, Frank; Liu, Ankun; Huss, Gary R.

2016-10-01

Mass-dependent, kinetic fractionation of isotopes through processes such as diffusion can result in measurable isotopic signatures. When these signatures are retained in geologic materials, they can be used to help interpret their thermal histories. The mass dependence of the diffusion coefficient of isotopes 1 and 2 can be written as (D1 /D2) =(m2 /m1) β, where D1 and D2 are the diffusion coefficients of m1 and m2 respectively, and β is an empirical coefficient that relates the two ratios. Experiments have been performed to measure β in the Fe-Ni alloy system. Diffusion couple experiments between pure Fe and Ni metals were run in a piston cylinder at 1300-1400 °C and 1 GPa. Concentration and isotopic profiles were measured by electron microprobe and ion microprobe respectively. We find that a single β coefficient of β = 0.32 ± 0.04 can describe the isotopic effect in all experiments. This result is comparable to the isotope effect determined in many other similar alloy systems. The new β coefficient is used in a model of the isotopic profiles to be expected during the Widmanstätten pattern formation in iron meteorites. The results are consistent with previous estimates of the cooling rate of the iron meteorite Toluca. The application of isotopic constraints based on these results in addition to conventional cooling rate models could provide a more robust picture of the thermal history of these early planetary bodies.

0.1 Trend analysis of δ18O composition of precipitation in Germany: Combining Mann-Kendall trend test and ARIMA models to correct for higher order serial correlation

NASA Astrophysics Data System (ADS)

Klaus, Julian; Pan Chun, Kwok; Stumpp, Christine

2015-04-01

Spatio-temporal dynamics of stable oxygen (18O) and hydrogen (2H) isotopes in precipitation can be used as proxies for changing hydro-meteorological and regional and global climate patterns. While spatial patterns and distributions gained much attention in recent years the temporal trends in stable isotope time series are rarely investigated and our understanding of them is still limited. These might be a result of a lack of proper trend detection tools and effort for exploring trend processes. Here we make use of an extensive data set of stable isotope in German precipitation. In this study we investigate temporal trends of δ18O in precipitation at 17 observation station in Germany between 1978 and 2009. For that we test different approaches for proper trend detection, accounting for first and higher order serial correlation. We test if significant trends in the isotope time series based on different models can be observed. We apply the Mann-Kendall trend tests on the isotope series, using general multiplicative seasonal autoregressive integrate moving average (ARIMA) models which account for first and higher order serial correlations. With the approach we can also account for the effects of temperature, precipitation amount on the trend. Further we investigate the role of geographic parameters on isotope trends. To benchmark our proposed approach, the ARIMA results are compared to a trend-free prewhiting (TFPW) procedure, the state of the art method for removing the first order autocorrelation in environmental trend studies. Moreover, we explore whether higher order serial correlations in isotope series affects our trend results. The results show that three out of the 17 stations have significant changes when higher order autocorrelation are adjusted, and four stations show a significant trend when temperature and precipitation effects are considered. Significant trends in the isotope time series are generally observed at low elevation stations (≤315 m a.s.l.). Higher order autoregressive processes are important in the isotope time series analysis. Our results show that the widely used trend analysis with only the first order autocorrelation adjustment may not adequately take account of the high order autocorrelated processes in the stable isotope series. The investigated time series analysis method including higher autocorrelation and external climate variable adjustments is shown to be a better alternative.

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.

Characterizing isotopic compositions of TC-C, NO3--N, and NH4+-N in PM2.5 in South Korea: Impact of China's winter heating.

PubMed

Park, Yu-Mi; Park, Kwang-Su; Kim, Hyuk; Yu, Seok-Min; Noh, Seam; Kim, Min-Seob; Kim, Jee-Young; Ahn, Joon-Young; Lee, Min-do; Seok, Kwang-Seol; Kim, Young-Hee

2018-02-01

The origin of PM 2.5 has long been the subject of debate and stable isotopic tools have been applied to decipher. In this study, weekly PM 2.5 samples were simultaneously collected at an urban (Seoul) and rural (Baengnyeong Island) site in Korea from January 2014 through February 2016. The seasonal variation of isotopic species showed significant seasonal differences with sinusoidal variation. The isotopic results implied that isotope species from Baengnyeong were mostly originated from coal combustion during China's winter heating seasons, whereas in summer, the isotopic patterns observed that were more likely to be from marine. In Seoul, coal combustion related isotopic patterns increased during China's winter heating period while vehicle related isotopic patterns were dominated whole seasons by default. Therefore, aerosol formation was originated from long-range transported coal combustion-related NO x by vehicle-related NH 3 in Seoul. δN-NH 4 + in Seoul showed highly enriched 15 N compositions in all seasons, indicating that NH 3 from vehicle emission is the important source of NH 4 + in PM 2.5 in Seoul. In addition, Baengnyeong should be consistently considered as a key region for observing the changes of isotopic features depend on the contribution of individual emissions to the atmospheric as a result of the reduction of coal consumption in China. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of land-use patterns on in-stream nitrogen in a highly-polluted river basin in Northeast China.

PubMed

Bu, Hongmei; Zhang, Yuan; Meng, Wei; Song, Xianfang

2016-05-15

This study investigated the effects of land-use patterns on nitrogen pollution in the Haicheng River basin in Northeast China during 2010 by conducting statistical and spatial analyses and by analyzing the isotopic composition of nitrate. Correlation and stepwise regressions indicated that land-use types and landscape metrics were correlated well with most river nitrogen variables and significantly predicted them during different sampling seasons. Built-up land use and shape metrics dominated in predicting nitrogen variables over seasons. According to the isotopic compositions of river nitrate in different zones, the nitrogen sources of the river principally originated from synthetic fertilizer, domestic sewage/manure, soil organic matter, and atmospheric deposition. Isotope mixing models indicated that source contributions of river nitrogen significantly varied from forested headwaters to densely populated towns of the river basin. Domestic sewage/manure was a major contributor to river nitrogen with the proportions of 76.4 ± 6.0% and 62.8 ± 2.1% in residence and farmland-residence zones, respectively. This research suggested that regulating built-up land uses and reducing discharges of domestic sewage and industrial wastewater would be effective methods for river nitrogen control. Copyright © 2016 Elsevier B.V. All rights reserved.

'Trophic' and 'source' amino acids in trophic estimation: a likely metabolic explanation.

PubMed

O'Connell, T C

2017-06-01

Amino acid nitrogen isotopic analysis is a relatively new method for estimating trophic position. It uses the isotopic difference between an individual's 'trophic' and 'source' amino acids to determine its trophic position. So far, there is no accepted explanation for the mechanism by which the isotopic signals in 'trophic' and 'source' amino acids arise. Yet without a metabolic understanding, the utility of nitrogen isotopic analyses as a method for probing trophic relations, at either bulk tissue or amino acid level, is limited. I draw on isotopic tracer studies of protein metabolism, together with a consideration of amino acid metabolic pathways, to suggest that the 'trophic'/'source' groupings have a fundamental metabolic origin, to do with the cycling of amino-nitrogen between amino acids. 'Trophic' amino acids are those whose amino-nitrogens are interchangeable, part of a metabolic amino-nitrogen pool, and 'source' amino acids are those whose amino-nitrogens are not interchangeable with the metabolic pool. Nitrogen isotopic values of 'trophic' amino acids will reflect an averaged isotopic signal of all such dietary amino acids, offset by the integrated effect of isotopic fractionation from nitrogen cycling, and modulated by metabolic and physiological effects. Isotopic values of 'source' amino acids will be more closely linked to those of equivalent dietary amino acids, but also modulated by metabolism and physiology. The complexity of nitrogen cycling suggests that a single identifiable value for 'trophic discrimination factors' is unlikely to exist. Greater consideration of physiology and metabolism should help in better understanding observed patterns in nitrogen isotopic values.

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.

Product ion isotopologue pattern: A tool to improve the reliability of elemental composition elucidations of unknown compounds in complex matrices.

PubMed

Kaufmann, A; Walker, S; Mol, G

2016-04-15

Elucidation of the elemental compositions of unknown compounds (e.g., in metabolomics) generally relies on the availability of accurate masses and isotopic ratios. This study focuses on the information provided by the abundance ratio within a product ion pair (monoisotopic versus the first isotopic peak) when isolating and fragmenting the first isotopic ion (first isotopic mass spectrum) of the precursor. This process relies on the capability of the quadrupole within the Q Orbitrap instrument to isolate a very narrow mass window. Selecting only the first isotopic peak (first isotopic mass spectrum) leads to the observation of a unique product ion pair. The lighter ion within such an isotopologue pair is monoisotopic, while the heavier ion contains a single carbon isotope. The observed abundance ratio is governed by the percentage of carbon atoms lost during the fragmentation and can be described by a hypergeometric distribution. The observed carbon isotopologue abundance ratio (product ion isotopologue pattern) gives reliable information regarding the percentage of carbon atoms lost in the fragmentation process. It therefore facilitates the elucidation of the involved precursor and product ions. Unlike conventional isotopic abundances, the product ion isotopologue pattern is hardly affected by isobaric interferences. Furthermore, the appearance of these pairs greatly aids in cleaning up a 'matrix-contaminated' product ion spectrum. The product ion isotopologue pattern is a valuable tool for structural elucidation. It increases confidence in results and permits structural elucidations for heavier ions. This tool is also very useful in elucidating the elemental composition of product ions. Such information is highly valued in the field of multi-residue analysis, where the accurate mass of product ions is required for the confirmation process. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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.

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.

The Relative Importance of Convective and Trade-wind Orographic Precipitation to Streamflow in the Luquillo Mountains, Eastern Puerto Rico

NASA Astrophysics Data System (ADS)

Scholl, M. A.; Shanley, J. B.; Occhi, M.; Scatena, F. N.

2012-12-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of Puerto Rico (18.3° N) have abundant rainfall and stream discharge, but relatively little storage capacity. Therefore, the water supply is vulnerable to drought and water availability may be affected by projected changes in regional temperature and atmospheric dynamics due to global warming. To help determine the links between climate and water availability, precipitation patterns were analyzed, and stable-isotope signatures of precipitation from different seasonal weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Stable isotope data include cloud water, rainfall, throughfall, streamflow, and groundwater from the Rio Mameyes and Rio Icacos/ Rio Blanco watersheds. Precipitation inputs have a wide range of stable isotope values, from fog/cloud water with δ2H and δ18O averaging +3.2‰, -1.74‰ respectively, to tropical storm rain with values as low as -154‰, -20.4‰. Spatial and temporal patterns of water isotopic values on this Caribbean island are different than higher latitude, continental watersheds. The data exhibit a 'reverse seasonality', with higher isotopic values in winter and lower values in summer; and stable isotope values of stream water do not decrease as expected with increasing altitude, because of cloud water input. Rain isotopic values vary predictably with local and mesoscale weather patterns and correlate strongly with cloud altitude. This correlation allows us to assign isotopic signatures to different sources of precipitation, and to investigate which climate patterns contribute to streamflow and groundwater recharge. At a measurement site at 615 m in the Luquillo Mountains, the average length of time between rain events was 15 h, and 45% of the rain events were <2 mm, reflecting the frequent small rain events of the trade-wind orographic rainfall weather pattern. Long-term average streamflow isotopic composition indicates a disproportionately large contribution of this trade-wind precipitation to streamflow, highlighting the importance of this climate pattern to the hydrology of the watersheds. Isotopic composition of groundwater suggests a slightly higher proportion of convective precipitation, but still smaller than in total rainfall. Hydrograph separation experiments yielded information on stormflow characteristics, with quantification of contributing sources determined from water isotopes and solute chemistry. The evidence that intense convective rain events run off and light trade-wind showers appear to contribute much of the baseflow indicates that the area may undergo a change in water supply if the trade-wind orographic precipitation dynamics in the Caribbean are affected by future climate change.

Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation

NASA Astrophysics Data System (ADS)

Tesmer, M.; Möller, P.; Wieland, S.; Jahnke, C.; Voigt, H.; Pekdeger, A.

2007-11-01

Major element chemistry, rare-earth element distribution, and H and O isotopes are conjointly used to study the sources of salinisation and interaquifer flow of saline groundwater in the North East German Basin. Chemical analyses from hydrocarbon exploration campaigns showed evidence of the existence of two different groups of brines: halite and halite Ca-Cl brines. Residual brines and leachates are identified by Br-/Cl- ratios. Most of the brines are dissolution brines of Permian evaporites. New analyses show that the pattern of rare-earth elements and yttrium (REY) are closely linked to H and O isotope distribution. Thermal brines from deep wells and artesian wells indicate isotopically evaporated brines, which chemically interacted with their aquifer environment. Isotopes and rare-earth element patterns prove that cross flow exists, especially in the post-Rupelian aquifer. However, even at depths exceeding 2,000 m, interaquifer flow takes place. The rare-earth element pattern and H and O isotopes identify locally ascending brines. A large-scale lateral groundwater flow has to be assumed because all pre-Rupelian aquifer systems to a depth of at least 500 m are isotopically characterised by Recent or Pleistocene recharge conditions.

Isotopic Randomness and Maxwell's Demon

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2005-03-01

Isotopic disorder in crystals can lead to suppression of thermal conductivity, mobility variations and (weak) Anderson localization on isotopic fluctuations. The latter (AAB, J.ChemPhys.1984) is akin to polaron effect (self-localization due polarization). Possibility of isotopic patterning (IP) increases near melting point (thermally activated isotopic hopping swaps). Crystal near melting threshold become “informationally sensitive” as if its IP is operated by some external Maxwell’s Demon, MD (AAB, URAM J, 2002). At this state short range (e.g. electrostatic inverse square) forces evolve into long-range interactions (due to divergence of order parameter) and information sensitivity can be further amplified by (say) a single fast electron (e.g. beta-particle from decay of 14-C or other radioactive isotope) which may result in cascade of impact ionization events and (short time-scale) enhancement of screening by impact-generated non-equilibrium (non-thermal) electrons. In this state informationally driven (MD-controlled) IP (Eccles effect) can result in decrease of positional entropy signifying emergence of physical complexity out of pure information, similar to peculiar “jinni effect” on closed time loops in relativistic cosmology (R.J.Gott, 2001) or Wheeler’s “it from bit” metaphor. By selecting special IP, MD modifies ergodicity principle in favor of info rich states.

Isotopes in North American Rocky Mountain Snowpack 1993-2014

NASA Astrophysics Data System (ADS)

Anderson, Lesleigh; Berkelhammer, Max; Mast, M. Alisa

2016-01-01

We present ∼1300 new isotopic measurements (δ18O and δ2H) from a network of snowpack sites in the Rocky Mountains that have been sampled since 1993. The network includes 177 locations where depth-integrated snow samples are collected each spring near peak accumulation. At 57 of these locations snowpack samples were obtained for 10-21 years and their isotopic measurements provide unprecedented spatial and temporal documentation of snowpack isotope values at mid-latitudes. For environments where snowfall accounts for the majority of annual precipitation, snowmelt is likely to have the strongest influence on isotope values retained in proxy archives. In this first presentation of the dataset we (1) describe the basic features of the isotope values in relation to the Global Meteoric Water Line (GMWL), (2) evaluate space for time substitutions traditionally used to establish δ18O-temperature relations, (3) evaluate site-to-site similarities across the network and identify those that are the most regionally representative, (4) examine atmospheric circulation patterns for several years with spatially coherent isotope patterns, and (5) provide examples of the implications this new dataset has for interpreting paleoclimate records (Bison Lake, Colorado and Minnetonka Cave, Idaho). Results indicate that snowpack δ18O is rarely a simple proxy of temperature. Instead, it exhibits a high degree of spatial heterogeneity and temporal variance that reflect additional processes such as vapor transport and post-depositional modification. Despite these complexities we identify consistent climate-isotope patterns and regionally representative locations that serve to better define Holocene hydroclimate estimates and their uncertainty. Climate change has and will affect western U.S. snowpack and we suggest these changes can be better understood and anticipated by oxygen and hydrogen isotope-based reconstructions of Holocene hydroclimate using a process-based understanding of the controls on snowpack isotope ratios.

Geochemically distinct carbon isotope distributions in Allochromatium vinosum DSM 180T grown photoautotrophically and photoheterotrophically.

PubMed

Tang, T; Mohr, W; Sattin, S R; Rogers, D R; Girguis, P R; Pearson, A

2017-03-01

Anoxygenic, photosynthetic bacteria are common at redox boundaries. They are of interest in microbial ecology and geosciences through their role in linking the carbon, sulfur, and iron cycles, yet much remains unknown about how their flexible carbon metabolism-permitting either autotrophic or heterotrophic growth-is recorded in the bulk sedimentary and lipid biomarker records. Here, we investigated patterns of carbon isotope fractionation in a model photosynthetic sulfur-oxidizing bacterium, Allochromatium vinosum DSM180 T . In one treatment, A. vinosum was grown with CO 2 as the sole carbon source, while in a second treatment, it was grown on acetate. Different intracellular isotope patterns were observed for fatty acids, phytol, individual amino acids, intact proteins, and total RNA between the two experiments. Photoautotrophic CO 2 fixation yielded typical isotopic ordering for the lipid biomarkers: δ 13 C values of phytol > n-alkyl lipids. In contrast, growth on acetate greatly suppressed intracellular isotopic heterogeneity across all molecular classes, except for a marked 13 C-depletion in phytol. This caused isotopic "inversion" in the lipids (δ 13 C values of phytol < n-alkyl lipids). The finding suggests that inverse δ 13 C patterns of n-alkanes and pristane/phytane in the geologic record may be at least in part a signal for photoheterotrophy. In both experimental scenarios, the relative isotope distributions could be predicted from an isotope flux-balance model, demonstrating that microbial carbon metabolisms can be interrogated by combining compound-specific stable isotope analysis with metabolic modeling. Isotopic differences among molecular classes may be a means of fingerprinting microbial carbon metabolism, both in the modern environment and the geologic record. © 2017 John Wiley & Sons Ltd.

Influence of Terrain and Land Cover on the Isotopic Composition of Seasonal Snowpack in Rocky Mountain Headwater Catchments Affected by Bark Beetle Induced Tree Mortality

NASA Astrophysics Data System (ADS)

Kipnis, E. L.; Murphy, M.; Klatt, A. L.; Miller, S. N.; Williams, D. G.

2015-12-01

Session H103: The Hydrology-Vegetation-Climate Nexus: Identifying Process Interactions and Environmental Shifts in Mountain Catchments Influence of Terrain and Land Cover on the Isotopic Composition of Seasonal Snowpack in Rocky Mountain Headwater Catchments Affected by Bark Beetle Induced Tree Mortality Evan L Kipnis, Melanie A Murphey, Alan Klatt, Scott N Miller, David G Williams Snowpack accumulation and ablation remain difficult to estimate in forested headwater catchments. How physical terrain and forest cover separately and interactively influence spatial patterns of snow accumulation and ablation largely shapes the hydrologic response to land cover disturbances. Analysis of water isotopes in snowpack provides a powerful tool for examining integrated effects of water vapor exchange, selective redistribution, and melt. Snow water equivalence (SWE), δ2H, δ18O and deuterium excess (D-excess) of snowpack were examined throughout winter 2013-2014 across two headwater catchments impacted by bark beetle induced tree mortality. A USGS 10m DEM and a derived land cover product from 1m NAIP imagery were used to examine the effects of terrain features (e.g., elevation, slope, aspect) and canopy disturbance (e.g., live, bark-beetle killed) as predictors of D-excess, an expression of kinetic isotope effects, in snowpack. A weighting of Akaike's Information Criterion (AIC) values from multiple spatially lagged regression models describing D-excess variation for peak snowpack revealed strong effects of elevation and canopy mortality, and weaker, but significant effects of aspect and slope. Snowpack D-excess was lower in beetle-killed canopy patches compared to live green canopy patches, and at lower compared to high elevation locations, suggesting that integrated isotopic effects of vapor exchange, vertical advection of melted snow, and selective accumulation and redistribution varied systematically across the two catchments. The observed patterns illustrate the potential for using D-excess to identify origins and timing of snowmelt runoff in streams and assessing the relative magnitude of different accumulation and ablation processes in snowpack evolution.

Preliminary Study: Application of Off-Axis ICOS to Determine Stable Carbon Isotope in Dissolved Inorganic Carbon

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Lee, J. M.; Hwang, J. H.; Piao, J.; Woo, N. C.

2015-12-01

CO2 is one of the major causes for global climate change. Because stable carbon isotope ratio is used to trace carbon source, several analytical techniques likes IRMS (Isotope Ratio Mass Spectrometry) and LAS (Laser Absorption Spectrometry) were extensively used. Off-axis ICOS, a kind of LAS, has merits on long-term stability and field application, therefore it is widely being used in CCS (Carbon Capture and Storage) field. The aim of this study is to extend the application scope of OA-ICOS to determine dissolved inorganic carbon (DIC). Because OA-ICOS showed dependence of δ13C on CO2 concentration, data processing is required. We tested CO2 Carbon Isotope Analyzer (CCIA-36-EP, Los Gatos Research) with both reference gas (δ13C= -28.28‰) and aqueous solutions prepared by dissolving sodium bicarbonate standards (δ13C= -12.26‰ and +3.96‰). The differences of δ13C between reference and measurement values are plotted by CO2 concentrations, then compared. At first, we checked the similarity between our curve pattern for reference gas and Guillon's research (δ13C= -43.99‰) by other Analyzer. To analyze aqueous samples, more errors can be caused than gas analysis. The carbon isotope fractionation occurs during dissolving standard reagents and extracting DIC as CO2 gas form. This effect is mixed with CO2 concentration dependence effect, therefore the curve patterns are different with that for reference gas. Our experiments are done for various δ13C values. It could be an important point to use OA-ICOS to analyze DIC, too.

Temperature effects on the fractionation of multiple sulfur isotopes by Thermodesulfobacterium and Desulfovibrio strains

NASA Astrophysics Data System (ADS)

Wang, P.; Sun, C.; Ono, S.; Lin, L.

2012-12-01

Microbial dissimilatory sulfate reduction is one of the major mechanisms driving anaerobic mineralization of organic matter in global ocean. While sulfate-reducing prokaryotes are well known to fractionate sulfur isotopes during dissimilatory sulfate reduction, unraveling the isotopic compositions of sulfur-bearing minerals preserved in sedimentary records could provide invaluable constraints on the evolution of seawater chemistry and metabolic pathways. Variations in the sulfur isotope fractionations are partly due to inherent differences among species and also affected by environmental conditions. The isotope fractionations caused by microbial sulfate reduction have been interpreted to be a sequence of enzyme-catalyzed isotope fractionation steps. Therefore, the fractionation factor depends on (1) the sulfate flux into and out of the cell, and (2) the flux of sulfur transformation between the internal pools. Whether the multiple sulfur isotope effect could be quantitatively predicted using such a metabolic flux model would provide insights into the cellular machinery catalyzing with sulfate reduction. This study examined the multiple sulfur isotope fractionation patterns associated with a thermophilic Thermodesulfobacterium-related strain and a mesophilic Desulfovibrio gigas over a wide temperature range. The Thermodesulfobacterium-related strain grew between 34 and 79°C with an optimal temperature at 72°C and the highest cell-specific sulfate reduction rate at 77°C. The 34ɛ values ranged between 8.2 and 31.6‰ with a maximum at 68°C. The D. gigas grew between 10 and 45 °C with an optimal temperature at 30°C and the highest cell-specific sulfate reduction rate at 41°C. The 34ɛ values ranged between 10.3 and 29.7‰ with higher magnitude at both lower and higher temperatures. The results of multiple sulfur isotope measurements expand the previously reported range and cannot be described by a solution field of the metabolic flux model, which calculates the Δ33S and 34ɛ values assuming equilibrium fractionation among internal steps. Either larger isotope effects or kinetic fractionation has to be considered in the metabolic flux model to explain the multiple sulfur isotope effect produced by these two strains. Overall, the metabolic flux model warrants further revision and further studies regarding physiological responses to growth conditions may probably offer a linkage between multiple sulfur isotope effects and environmental factors for microbial dissimilatory sulfate reduction.

Investigations of interhydrogen bond dynamical coupling effects in the polarized IR spectra of acetanilide crystals.

PubMed

Flakus, Henryk T; Michta, Anna

2010-02-04

This Article presents the investigation results of the polarized IR spectra of the hydrogen bond in acetanilide (ACN) crystals measured in the frequency range of the proton and deuteron stretching vibration bands, nu(N-H) and nu(N-D). The basic spectral properties of the crystals were interpreted quantitatively in terms of the "strong-coupling" theory. The model of the centrosymmetric dimer of hydrogen bonds postulated by us facilitated the explanation of the well-developed, two-branch structure of the nu(N-H) and nu(N-D) bands as well as the isotopic dilution effects in the spectra. On the basis of the linear dichroic and temperature effects in the polarized IR spectra of ACN crystals, the H/D isotopic "self-organization" effects were revealed. A nonrandom distribution of hydrogen isotope atoms (H or D) in the lattice was deduced from the spectra of isotopically diluted ACN crystals. It was also determined that identical hydrogen isotope atoms occupy both hydrogen bonds in the dimeric systems, where each hydrogen bond belongs to a different chain. A more complex fine structure pattern of nu(N-H) and nu(N-D) bands in ACN spectra in comparison with the spectra of other secondary amides (e.g., N-methylacetamide) can be explained in terms of the "relaxation" theory of the IR spectra of hydrogen-bonded systems.

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.

Global Patterns of the Isotopic Composition of Soil and Plant Nitrogen

NASA Astrophysics Data System (ADS)

Amundson, R.; Yoo, K.

2014-12-01

From a societal perspective, soil N follows only soil C in the importance of soil to 21st century environmental issues. Amundson et al (2003) developed a mass balance model for soil N and the ratio of 15N/14N, and provided the first global projections of the spatial patterns of soil and plant δ15N values. It was hypothesized that state factors, particularly climate, should drive broad patterns of soil and plant δ15N values in a manner analogous to the known patterns of total soil N (e.g. Post et al., 1984). At that time, the N isotope data available to explore the effect of individual factors was modest. In the past decade, numerous papers from a broad spectrum of locations have created a rich database that can be used to further refine the initial projections made more than a decade ago. In this paper, hundreds of published measurements will be used to more deeply examine the climatic impacts on soil and plant δ15N values. Additionally, we will focus on the local controls of topography on ecosystem N cycling, which can create local isotopic variation that is similar in magnitude to the global effects of climate. The adoption of process-based models from the hillslope geomorphology community appears to be a powerful tool for explaining some existing data from toposequences, designing new studies of topographic controls on biogeochemistry, and particularly for parameterization in global models. Amundson, R., A.T. Austin, E.A.G. Schuur, K. Yoo, V. Matzek, C. Kendall, A. Uebersax, D. Brenner, and W.T. Baisden. 2003. Global Biogeochemical Cycles 17(1):1031.

C, N, and H isotope fractionation of the herbicide isoproturon reflects different microbial transformation pathways.

PubMed

Penning, Holger; Sørensen, Sebastian R; Meyer, Armin H; Aamand, Jens; Elsner, Martin

2010-04-01

The fate of pesticides in the subsurface is of great interest to the public, industry, and regulatory authorities. Compound-specific isotope analysis (CSIA) is a promising tool complementary to existing methods for elucidating pesticide degradation reactions. Here, we address three different initial biotransformation reactions of the phenylurea herbicide isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea) in pure culture experiments with bacterial and fungal strains. When analyzing isotopic changes in different parts of the isoproturon molecule, hydroxylation of the isopropyl group by fungi was found to be associated with C and H isotope fractionation. In contrast, hydrolysis by Arthrobacter globiformis D47 caused strong C and N isotope fractionation, albeit in a different manner than abiotic hydrolysis so that isotope measurements can distinguish between both modes of transformation. No significant isotope fractionation was observed during N-demethylation by Sphingomonas sp. SRS2. The observed isotope fractionation patterns were in agreement with the type of reactions and elements involved. Moreover, their substantially different nature suggests that isotope changes in natural samples may be uniquely attributed to either pathway, allowing even to distinguish the abiotic versus biotic nature of hydrolysis. Our investigations show how characteristic isotope patterns may significantly add to the present understanding of the environmental fate of pesticides.

Population variation in isotopic composition of shorebird feathers: Implications for determining molting grounds

USGS Publications Warehouse

Torres-Dowdall, J.; Farmer, A.H.; Bucher, E.H.; Rye, R.O.; Landis, G.

2009-01-01

Stable isotope analyses have revolutionized the study of migratory connectivity. However, as with all tools, their limitations must be understood in order to derive the maximum benefit of a particular application. The goal of this study was to evaluate the efficacy of stable isotopes of C, N, H, O and S for assigning known-origin feathers to the molting sites of migrant shorebird species wintering and breeding in Argentina. Specific objectives were to: 1) compare the efficacy of the technique for studying shorebird species with different migration patterns, life histories and habitat-use patterns; 2) evaluate the grouping of species with similar migration and habitat use patterns in a single analysis to potentially improve prediction accuracy; and 3) evaluate the potential gains in prediction accuracy that might be achieved from using multiple stable isotopes. The efficacy of stable isotope ratios to determine origin was found to vary with species. While one species (White-rumped Sandpiper, Calidris fuscicollis) had high levels of accuracy assigning samples to known origin (91% of samples correctly assigned), another (Collared Plover, Charadrius collaris) showed low levels of accuracy (52% of samples correctly assigned). Intra-individual variability may account for this difference in efficacy. The prediction model for three species with similar migration and habitat-use patterns performed poorly compared with the model for just one of the species (71% versus 91% of samples correctly assigned). Thus, combining multiple sympatric species may not improve model prediction accuracy. Increasing the number of stable isotopes in the analyses increased the accuracy of assigning shorebirds to their molting origin, but the best combination - involving a subset of all the isotopes analyzed - varied among species.

Environmental forcing of terrestrial carbon isotope excursion amplification across five Eocene hyperthermals

NASA Astrophysics Data System (ADS)

Bowen, G. J.; Abels, H.

2015-12-01

Abrupt changes in the isotope composition of exogenic carbon pools accompany many major episodes of global change in the geologic record. The global expression of this change in substrates that reflect multiple carbon pools provides important evidence that many events reflect persistent, global redistribution of carbon between reduced and oxidized stocks. As the diversity of records documenting any event grows, however, discrepancies in the expression of carbon isotope change among substrates are almost always revealed. These differences in magnitude, pace, and pattern of change can complicate interpretations of global carbon redistribution, but under ideal circumstances can also provide additional information on changes in specific environmental and biogeochemical systems that accompanied the global events. Here we evaluate possible environmental influences on new terrestrial records of the negative carbon isotope excursions (CIEs) associated with multiple hyperthermals of the Early Eocene, which show a common pattern of amplified carbon isotope change in terrestrial paleosol carbonate records relative to that recorded in marine substrates. Scaling relationships between climate and carbon-cycle proxies suggest that that the climatic (temperature) impact of each event scaled proportionally with the magnitude of its marine CIE, likely implying that all events involved release of reduced carbon with a similar isotopic composition. Amplification of the terrestrial CIEs, however, does not scale with event magnitude, being proportionally less for the first, largest event (the PETM). We conduct a sensitivity test of a coupled plant-soil carbon isotope model to identify conditions that could account for the observed CIE scaling. At least two possibilities consistent with independent lines of evidence emerge: first, varying effects of pCO2 change on photosynthetic carbon isotope discrimination under changing background pCO2, and second, contrasting changes in regional hydroclimate during the PETM and subsequent hyperthermals. These mechanisms have very different implications for the reconstruction of environmental conditions, and resolving the correct interpretation will require new, complimentary records of plant and soil conditions associated with the Early Eocene hyperthermals.

ESTIMATING THE TIMING OF DIET SHIFTS USING STABLE ISOTOPES

EPA Science Inventory

Stable isotope analysis has become an important tool in studies of trophic food webs and animal feeding patterns. When animals undergo rapid dietary shifts due to migration, metamorphosis, or other reasons, the isotopic composition of their tissues begins changing to reflect tha...

Comparing spatial and temporal patterns of river water isotopes across networks

EPA Science Inventory

A detailed understanding of the spatial and temporal dynamics of water sources across river networks is central to managing the impacts of climate change. Because the stable isotope composition of precipitation varies geographically, variation in surface-water isotope signatures ...

The Isotopic Record of Elevation Thresholds in Continental Plateaus to Atmospheric Circulation

NASA Astrophysics Data System (ADS)

Mulch, A.; Chamberlain, C. P.; Graham, S. A.; Teyssier, C.; Cosca, M. A.

2011-12-01

High-elevation orogenic plateaus and mountain ranges exert a strong control on global climate and precipitation patterns and interact with lithospheric and upper mantle tectonic processes as well as atmospheric circulation. Reconstructing the history of surface elevation thus not only provides a critical link between erosional and tectonic processes but also ties Earth surface processes to the long-term climate history of our planet. This interaction, however, has important implications when using stable isotopes (O, H) as proxies for landscape and terrestrial climate evolution as interacting land surface properties (elevation, relief, vegetation cover) and atmospheric circulation patterns (upstream moisture path) may attain threshold conditions that can cloak or amplify the impact of topography on isotopes in precipitation. A large number of stable isotope studies in lacustrine and pedogenic environments of intermontane basins record the isotopic and sedimentologic fingerprint of the evolving landscape of the Cenozoic western North American Cordillera. In general we observe the onset of strong oxygen isotope in precipitation gradients along the eastward and westward flanks of the Cordilleran orogen and associated 18O-depleted moisture within the Cordilleran hinterland to develop no later than 50-55 Ma in British Columbia and Washington, 49 Ma in Montana, and 39-40 Ma in Nevada. However, some of these shifts to very low oxygen isotope compositions in meteoric water occur at rates that by far exceed those that could be attributed to tectonic surface uplift alone. Here we present a multi-proxy approach from the Elko Basin (NV) that ties stable and radiogenic tracers of landscape evolution with high resolution Ar-Ar geochronology. In pedogenic and lacustrine deposits of the Elko basin we observe a change in oxygen isotope ratios that is far too large (6-8 %) and rapid (<200 000 a) to be solely due to changes in elevation. Rather we suggest that the combined effects of developing topography and relief and changing global climate conditions during the Mid Eocene climatic optimum interacted to change atmospheric moisture transport. We suggest that such rapid changes in rainfall composition may be relatively common in evolving plateau regions once critical relief and elevation conditions are attained and caution against using stable isotope paleoaltimetry in regions with relatively poor age control where such effects may easily be mistaken as changes in absolute paleoelevation of the plateau region. On the other hand, such highly resolved terrestrial isotope records provide extremely valuable information when trying to recover how landscape evolution interacted with atmospheric moisture transport across the continents and the terrestrial biosphere during times of paleoclimate change.

Divergence of stable isotopes in tap water across China

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

Zhao, Sihan; Hu, Hongchang; Tian, Fuqiang

Stable isotopes in water (e.g., δ2H and δ18O) are important indicators of hydrological and ecological patterns and processes. Tap water can reflect integrated features of regional hydrological processes and human activities. China is a large country with significant meteorological and geographical variations. This report presents the first national-scale survey of Stable Isotopes in Tap Water (SITW) across China. 780 tap water samples have been collected from 95 cities across China from December 2014 to December 2015. (1) Results yielded the Tap Water Line in China is δ2H = 7.72 δ18O + 6.57 (r2 = 0.95). (2) SITW spatial distribution presentsmore » typical "continental effect". (3) SITW seasonal variations indicate clearly regional patterns but no trends at the national level. (4) SITW can be correlated in some parts with geographic or meteorological factors. This work presents the first SITW map in China, which sets up a benchmark for further stable isotopes research across China. This is a critical step toward monitoring and investigating water resources in climate-sensitive regions, so the human-hydrological system. These findings could be used in the future to establish water management strategies at a national or regional scale. Title: Divergence of stable isotopes in tap water across China Authors: Zhao, SH; Hu, HC; Tian, FQ; Tie, Q; Wang, LX; Liu, YL; Shi, CX Source: SCIENTIFIC REPORTS, 7 10.1038/srep43653 MAR 2 2017« less

Late Pleistocene/Early Holocene Migratory Behavior of Ungulates Using Isotopic Analysis of Tooth Enamel and Its Effects on Forager Mobility.

PubMed

Pilaar Birch, Suzanne E; Miracle, Preston T; Stevens, Rhiannon E; O'Connell, Tamsin C

2016-01-01

Zooarchaeological and paleoecological investigations have traditionally been unable to reconstruct the ethology of herd animals, which likely had a significant influence on the mobility and subsistence strategies of prehistoric humans. In this paper, we reconstruct the migratory behavior of red deer (Cervus elaphus) and caprids at the Pleistocene-Holocene transition in the northeastern Adriatic region using stable oxygen isotope analysis of tooth enamel. The data show a significant change in δ18O values from the Pleistocene into the Holocene, as well as isotopic variation between taxa, the case study sites, and through time. We then discuss the implications of seasonal faunal availability as determining factors in human mobility patterns.

Nitrogen isotope patterns in Alaskan black spruce reflect organic nitrogen sources and the activity of ectomycorrihizal fungi

Treesearch

Jordan R. Mayor; Edward A.G. Schuur; Michelle C. Mack; Teresa N. Hollingsworth; Erland Bääth

2012-01-01

Global patterns in soil, plant, and fungal stable isotopes of N (15N) show promise as integrated metrics of N cycling, particularly the activity of ectomycorrhizal (ECM) fungi. At small spatial scales, however, it remains difficult to differentiate the underlying causes of plant 15N variability and this limits the...

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Non-linear mixing effects on mass-47 CO2 clumped isotope thermometry: Patterns and implications.

PubMed

Defliese, William F; Lohmann, Kyger C

2015-05-15

Mass-47 CO(2) clumped isotope thermometry requires relatively large (~20 mg) samples of carbonate minerals due to detection limits and shot noise in gas source isotope ratio mass spectrometry (IRMS). However, it is unreasonable to assume that natural geologic materials are homogenous on the scale required for sampling. We show that sample heterogeneities can cause offsets from equilibrium Δ(47) values that are controlled solely by end member mixing and are independent of equilibrium temperatures. A numerical model was built to simulate and quantify the effects of end member mixing on Δ(47). The model was run in multiple possible configurations to produce a dataset of mixing effects. We verified that the model accurately simulated real phenomena by comparing two artificial laboratory mixtures measured using IRMS to model output. Mixing effects were found to be dependent on end member isotopic composition in δ(13)C and δ(18)O values, and independent of end member Δ(47) values. Both positive and negative offsets from equilibrium Δ(47) can occur, and the sign is dependent on the interaction between end member isotopic compositions. The overall magnitude of mixing offsets is controlled by the amount of variability within a sample; the larger the disparity between end member compositions, the larger the mixing offset. Samples varying by less than 2 ‰ in both δ(13)C and δ(18)O values have mixing offsets below current IRMS detection limits. We recommend the use of isotopic subsampling for δ(13)C and δ(18)O values to determine sample heterogeneity, and to evaluate any potential mixing effects in samples suspected of being heterogonous. Copyright © 2015 John Wiley & Sons, Ltd.

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.

Evaluating the cave carbonate chemical signal as a proxy for rain patterns in Mallorca Island

NASA Astrophysics Data System (ADS)

Cacho, Isabel; Cisneros, Mercé; Torner, Judit; Català, Albert; Moreno, Ana; Stoll, Heather; Iglesias, Miguel; Bladé, Ileana; Fornos, Joan

2017-04-01

Mallorca's climate is marked by a strong seasonal cycle in both temperatures and precipitations which is likely to be recorded in the carbonate precipitates formed in its extended karst systems. Here we present isotopes and trace elements measured in dripwaters collected at weakly and/or seasonal bases since spring 2013 in three caves from Mallorca that represent the eastern and S-eastern sector of the island. This information is complemented with isotopic composition of rain events in the same region, other cave environmental parameters and chemistry of seasonal farmed carbonates in the same caves. Drip water results are very consistent between the different studied caves and indicate an important attenuation of the rainfall isotopic signal in the epikarst and only extreme climate conditions such as the severe dry conditions in summer 2015. Farmed carbonates present a clear seasonal cycle with low values, in both carbon and oxygen isotopes, in summer and autumn and high values in winter and spring. This cyclicity can not be attributed to amount effect or rain composition and we propose a close relation to cave environmental conditions. High CO2 concentrations in summer and autumn would avoid degasification reducing the PCP process and resulting in more negative isotopic relationships in both oxygen and carbon isotopes. Coherently, this CO2 cycles are in phase with those of temperature since both reflect ventilation rates in the cave. Nevertheless, ultra-high resolution profiles of Mg/Ca ratios measured by laser ablation on last century carbonate precipitates in the same caves, reveal a inter-annual variability with a persistent cyclicity which show coherent patterns with the instrumental rain records from Mallorca. This comparison reveals the potential of the Mallorca carbonates to reveal the long-term precipitation evolution of the island.

Quantification and isotopic analysis of intracellular sulfur metabolites in the dissimilatory sulfate reduction pathway

NASA Astrophysics Data System (ADS)

Sim, Min Sub; Paris, Guillaume; Adkins, Jess F.; Orphan, Victoria J.; Sessions, Alex L.

2017-06-01

Microbial sulfate reduction exhibits a normal isotope effect, leaving unreacted sulfate enriched in 34S and producing sulfide that is depleted in 34S. However, the magnitude of sulfur isotope fractionation is quite variable. The resulting changes in sulfur isotope abundance have been used to trace microbial sulfate reduction in modern and ancient ecosystems, but the intracellular mechanism(s) underlying the wide range of fractionations remains unclear. Here we report the concentrations and isotopic ratios of sulfur metabolites in the dissimilatory sulfate reduction pathway of Desulfovibrio alaskensis. Intracellular sulfate and APS levels change depending on the growth phase, peaking at the end of exponential phase, while sulfite accumulates in the cell during stationary phase. During exponential growth, intracellular sulfate and APS are strongly enriched in 34S. The fractionation between internal and external sulfate is up to 49‰, while at the same time that between external sulfate and sulfide is just a few permil. We interpret this pattern to indicate that enzymatic fractionations remain large but the net fractionation between sulfate and sulfide is muted by the closed-system limitation of intracellular sulfate. This 'reservoir effect' diminishes upon cessation of exponential phase growth, allowing the expression of larger net sulfur isotope fractionations. Thus, the relative rates of sulfate exchange across the membrane versus intracellular sulfate reduction should govern the overall (net) fractionation that is expressed. A strong reservoir effect due to vigorous sulfate reduction might be responsible for the well-established inverse correlation between sulfur isotope fractionation and the cell-specific rate of sulfate reduction, while at the same time intraspecies differences in sulfate uptake and/or exchange rates could account for the significant scatter in this relationship. Our approach, together with ongoing investigations of the kinetic isotope fractionation by key enzymes in the sulfate reduction pathway, should provide an empirical basis for a quantitative model relating the magnitude of microbial isotope fractionation to their environmental and physiological controls.

Isotopes in North American Rocky Mountain snowpack 1993–2014

USGS Publications Warehouse

Anderson, Lesleigh; Max Berkelhammer,; Mast, M. Alisa

2015-01-01

We present ∼1300 new isotopic measurements (δ18O and δ2H) from a network of snowpack sites in the Rocky Mountains that have been sampled since 1993. The network includes 177 locations where depth-integrated snow samples are collected each spring near peak accumulation. At 57 of these locations snowpack samples were obtained for 10–21 years and their isotopic measurements provide unprecedented spatial and temporal documentation of snowpack isotope values at mid-latitudes. For environments where snowfall accounts for the majority of annual precipitation, snowmelt is likely to have the strongest influence on isotope values retained in proxy archives. In this first presentation of the dataset we (1) describe the basic features of the isotope values in relation to the Global Meteoric Water Line (GMWL), (2) evaluate space for time substitutions traditionally used to establish δ18O-temperature relations, (3) evaluate site-to-site similarities across the network and identify those that are the most regionally representative, (4) examine atmospheric circulation patterns for several years with spatially coherent isotope patterns, and (5) provide examples of the implications this new dataset has for interpreting paleoclimate records (Bison Lake, Colorado and Minnetonka Cave, Idaho). Results indicate that snowpack δ18O is rarely a simple proxy of temperature. Instead, it exhibits a high degree of spatial heterogeneity and temporal variance that reflect additional processes such as vapor transport and post-depositional modification. Despite these complexities we identify consistent climate-isotope patterns and regionally representative locations that serve to better define Holocene hydroclimate estimates and their uncertainty. Climate change has and will affect western U.S. snowpack and we suggest these changes can be better understood and anticipated by oxygen and hydrogen isotope-based reconstructions of Holocene hydroclimate using a process-based understanding of the controls on snowpack isotope ratios.

Isotopic characteristics of simulated meteoritic organic matter. I - Kerogen-like material

NASA Technical Reports Server (NTRS)

Kerridge, John F.; Mariner, Ruth; Flores, Jose; Chang, Sherwood

1989-01-01

Carbonaceous residues from a variety of laboratory syntheses yield release patterns for C and H isotopes during stepwise combustion that fail to mimic the striking patterns characteristic of meteoritic kerogen-like residues that otherwise superficially resemble them. It seems likely that the meteoritic material comprises a complex mixture of substances having different origins and/or synthesis conditions.

Stable isotope variations (δ18O and δD) in modern waters across the Andean Plateau

NASA Astrophysics Data System (ADS)

Bershaw, John; Saylor, Joel E.; Garzione, Carmala N.; Leier, Andrew; Sundell, Kurt E.

2016-12-01

Environmental parameters that influence the isotopic composition of meteoric water (δ18O and δD) are well characterized up the windward side of mountains, where orographic precipitation results in a predictable relationship between the isotopic composition of precipitation and elevation. The topographic and climatic evolution of the Andean Plateau and surrounding regions has been studied extensively by exploiting this relationship through the use of paleowater proxies. However, interpretation on the plateau itself is challenged by a poor understanding of processes that fractionate isotopes during vapor transport and rainout, and by the relative contribution of unique moisture sources. Here, we present an extensive dataset of modern surface water samples for the northern Andean Plateau and surrounding regions to elucidate patterns and causes of isotope fractionation in this continental environment. These data show a progressive increase in δ18O of stream water west of the Eastern Cordillera (∼1‰/70 km), almost identical to the rate observed across the Tibetan Plateau, attributed to a larger fraction of recycled water in precipitation and/or increased evaporative enrichment downwind. This may lead to underestimates of paleoelevation, particularly for sites deep into the rainshadow of the Eastern Cordilleran crest. That said, elevation is a primary control on the isotopic composition of surface waters across the entire Andean Plateau and its flanks when considering the most negative δ18O values, highlighting the need for sufficiently large datasets to distinguish minimally evaporated samples. There is a general increase in δ18O on the plateau from north to south, concomitant with an increase in aridity and decrease in convective moistening (amount effect). Lastly, stable isotope and seasonal precipitation patterns suggest easterlies provide the vast majority of moisture that falls as precipitation across the Andean Plateau and Western Cordillera, from Peru to northern Bolivia (-13° to -20° latitude), with Pacific-derived moisture contributing a minor amount at low elevations near the coast.

Does upwelling intensity influence feeding habits and trophic position of planktivorous fish?

NASA Astrophysics Data System (ADS)

Lopez-Lopez, Lucia; Preciado, Izaskun; Muñoz, Isabel; Decima, Moira; Molinero, Juan Carlos; Tel, Elena

2017-04-01

Food web configuration is shaped by many factors, including primary production patterns and oceanographic features, such as upwelling events. In this study, we investigate variability in the trophic position, food web interlinks and energy pathways of four planktivorous demersal fish in the Southern Bay of Biscay- NE Atlantic. The study area is exposed to upwelling events of varying intensity and shows a significant spatial gradient along the coast. The two sampling years were characterized by markedly different conditions, with weak summer upwelling in 2012 and an intense upwelling season in 2013. We used a complementary approach based on stomach content analysis (SCA) and stable isotope analysis (SIA) to test the effects of upwelling intensity and persistence on the food-web. In particular we investigated whether different intensities shift the main flow of energy between the pelagic and benthic energy pathways. We found conspicuous interannual changes in the isotopic POM, whose δ15N was 2.5‰ lower during the productive 2013 season. Interannual changes in the isotopic signature of the fish species were also detected, although their values did not mirror variability at the basal level. The SCA results did not match the isotopic changes, which likely reflected dietary adjustments of the species during summer. The upwelling intensity gradient along the coast did not affect the nitrogen isotopic ratio of any group, however there was a significant effect of such gradient on the carbon isotopic ratio of the fish and euphausiid species. This effect was likely related to the higher primary production associated with intense upwelling conditions.

Mass fractionation of noble gases in synthetic methane hydrate: Implications for naturally occurring gas hydrate dissociation

USGS Publications Warehouse

Hunt, Andrew G.; Stern, Laura; Pohlman, John W.; Ruppel, Carolyn; Moscati, Richard J.; Landis, Gary P.

2013-01-01

As a consequence of contemporary or longer term (since 15 ka) climate warming, gas hydrates in some settings may presently be dissociating and releasing methane and other gases to the ocean-atmosphere system. A key challenge in assessing the impact of dissociating gas hydrates on global atmospheric methane is the lack of a technique able to distinguish between methane recently released from gas hydrates and methane emitted from leaky thermogenic reservoirs, shallow sediments (some newly thawed), coal beds, and other sources. Carbon and deuterium stable isotopic fractionation during methane formation provides a first-order constraint on the processes (microbial or thermogenic) of methane generation. However, because gas hydrate formation and dissociation do not cause significant isotopic fractionation, a stable isotope-based hydrate-source determination is not possible. Here, we investigate patterns of mass-dependent noble gas fractionation within the gas hydrate lattice to fingerprint methane released from gas hydrates. Starting with synthetic gas hydrate formed under laboratory conditions, we document complex noble gas fractionation patterns in the gases liberated during dissociation and explore the effects of aging and storage (e.g., in liquid nitrogen), as well as sampling and preservation procedures. The laboratory results confirm a unique noble gas fractionation pattern for gas hydrates, one that shows promise in evaluating modern natural gas seeps for a signature associated with gas hydrate dissociation.

Mono-isotope Prediction for Mass Spectra Using Bayes Network.

PubMed

Li, Hui; Liu, Chunmei; Rwebangira, Mugizi Robert; Burge, Legand

2014-12-01

Mass spectrometry is one of the widely utilized important methods to study protein functions and components. The challenge of mono-isotope pattern recognition from large scale protein mass spectral data needs computational algorithms and tools to speed up the analysis and improve the analytic results. We utilized naïve Bayes network as the classifier with the assumption that the selected features are independent to predict mono-isotope pattern from mass spectrometry. Mono-isotopes detected from validated theoretical spectra were used as prior information in the Bayes method. Three main features extracted from the dataset were employed as independent variables in our model. The application of the proposed algorithm to publicMo dataset demonstrates that our naïve Bayes classifier is advantageous over existing methods in both accuracy and 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.

Estimates of lake trout (Salvelinus namaycush) diet in Lake Ontario using two and three isotope mixing models

USGS Publications Warehouse

Colborne, Scott F.; Rush, Scott A.; Paterson, Gordon; Johnson, Timothy B.; Lantry, Brian F.; Fisk, Aaron T.

2016-01-01

Recent development of multi-dimensional stable isotope models for estimating both foraging patterns and niches have presented the analytical tools to further assess the food webs of freshwater populations. One approach to refine predictions from these analyses is to include a third isotope to the more common two-isotope carbon and nitrogen mixing models to increase the power to resolve different prey sources. We compared predictions made with two-isotope carbon and nitrogen mixing models and three-isotope models that also included sulphur (δ34S) for the diets of Lake Ontario lake trout (Salvelinus namaycush). We determined the isotopic compositions of lake trout and potential prey fishes sampled from Lake Ontario and then used quantitative estimates of resource use generated by two- and three-isotope Bayesian mixing models (SIAR) to infer feeding patterns of lake trout. Both two- and three-isotope models indicated that alewife (Alosa pseudoharengus) and round goby (Neogobius melanostomus) were the primary prey items, but the three-isotope models were more consistent with recent measures of prey fish abundances and lake trout diets. The lake trout sampled directly from the hatcheries had isotopic compositions derived from the hatchery food which were distinctively different from those derived from the natural prey sources. Those hatchery signals were retained for months after release, raising the possibility to distinguish hatchery-reared yearlings and similarly sized naturally reproduced lake trout based on isotopic compositions. Addition of a third-isotope resulted in mixing model results that confirmed round goby have become an important component of lake trout diet and may be overtaking alewife as a prey resource.

Connection between ENSO and Asian Summer Monsoon Precipitation Oxygen Isotope

NASA Astrophysics Data System (ADS)

Cai, Z.; Tian, L.

2016-12-01

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

Precipitation isotopes link regional climate patterns to water supply in a tropical mountain forest, eastern Puerto Rico

USGS Publications Warehouse

Scholl, Martha A.; Murphy, Sheila F.

2014-01-01

Like many mountainous areas in the tropics, watersheds in the Luquillo Mountains of eastern Puerto Rico have abundant rainfall and stream discharge and provide much of the water supply for the densely populated metropolitan areas nearby. Projected changes in regional temperature and atmospheric dynamics as a result of global warming suggest that water availability will be affected by changes in rainfall patterns. It is essential to understand the relative importance of different weather systems to water supply to determine how changes in rainfall patterns, interacting with geology and vegetation, will affect the water balance. To help determine the links between climate and water availability, stable isotope signatures of precipitation from different weather systems were established to identify those that are most important in maintaining streamflow and groundwater recharge. Precipitation stable isotope values in the Luquillo Mountains had a large range, from fog/cloud water with δ2H, δ18O values as high as +12 ‰, −0.73 ‰ to tropical storm rain with values as low as −127 ‰, −16.8 ‰. Temporal isotope values exhibit a reverse seasonality from those observed in higher latitude continental watersheds, with higher isotopic values in the winter and lower values in the summer. Despite the higher volume of convective and low-pressure system rainfall, stable isotope analyses indicated that under the current rainfall regime, frequent trade -wind orographic showers contribute much of the groundwater recharge and stream base flow. Analysis of rain events using 20 years of 15 -minute resolution data at a mountain station (643 m) showed an increasing trend in rainfall amount, in agreement with increased precipitable water in the atmosphere, but differing from climate model projections of drying in the region. The mean intensity of rain events also showed an increasing trend. The determination of recharge sources from stable isotope tracers indicates that water supply will be affected if regional atmospheric dynamics change trade- wind orographic rainfall patterns in the Caribbean.

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

Treesearch

Scott T. Allen; Richard F. Keim; Jeffrey J. McDonnell

2015-01-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability...

Isotope analysis of diamond-surface passivation effect of high-temperature H{sub 2}O-grown atomic layer deposition-Al{sub 2}O{sub 3} films

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

Hiraiwa, Atsushi, E-mail: hiraiwa@aoni.waseda.jp, E-mail: qs4a-hriw@asahi-net.or.jp; Saito, Tatsuya; Matsumura, Daisuke

2015-06-07

The Al{sub 2}O{sub 3} film formed using an atomic layer deposition (ALD) method with trimethylaluminum as Al precursor and H{sub 2}O as oxidant at a high temperature (450 °C) effectively passivates the p-type surface conduction (SC) layer specific to a hydrogen-terminated diamond surface, leading to a successful operation of diamond SC field-effect transistors at 400 °C. In order to investigate this excellent passivation effect, we carried out an isotope analysis using D{sub 2}O instead of H{sub 2}O in the ALD and found that the Al{sub 2}O{sub 3} film formed at a conventional temperature (100 °C) incorporates 50 times more CH{sub 3} groups thanmore » the high-temperature film. This CH{sub 3} is supposed to dissociate from the film when heated afterwards at a higher temperature (550 °C) and causes peeling patterns on the H-terminated surface. The high-temperature film is free from this problem and has the largest mass density and dielectric constant among those investigated in this study. The isotope analysis also unveiled a relatively active H-exchange reaction between the diamond H-termination and H{sub 2}O oxidant during the high-temperature ALD, the SC still being kept intact. This dynamic and yet steady H termination is realized by the suppressed oxidation due to the endothermic reaction with H{sub 2}O. Additionally, we not only observed the kinetic isotope effect in the form of reduced growth rate of D{sub 2}O-oxidant ALD but found that the mass density and dielectric constant of D{sub 2}O-grown Al{sub 2}O{sub 3} films are smaller than those of H{sub 2}O-grown films. This is a new type of isotope effect, which is not caused by the presence of isotopes in the films unlike the traditional isotope effects that originate from the presence of isotopes itself. Hence, the high-temperature ALD is very effective in forming Al{sub 2}O{sub 3} films as a passivation and/or gate-insulation layer of high-temperature-operation diamond SC devices, and the knowledge of the aforementioned new isotope effect will be a basis for further enhancing ALD technologies in general.« less

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

USGS Publications Warehouse

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

2009-01-01

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

Isotope pattern deconvolution as rising tool for isotope tracer studies in environmental research

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Zitek, Andreas; Prohaska, Thomas

2014-05-01

During the last decade stable isotope tracers have emerged as versatile tool in ecological research. Besides 'intrinsic' isotope tracers caused by the natural variation of isotopes, the intentional introduction of 'extrinsic' enriched stable isotope tracers into biological systems has gained significant interest. Hereby the induced change in the natural isotopic composition of an element allows amongst others for studying the fate and fluxes of metals, trace elements and species in organisms or provides an intrinsic marker or tag of particular biological samples. Due to the shoreless potential of this methodology, the number of publications dealing with applications of isotope (double) spikes as tracers to address research questions in 'real world systems' is constantly increasing. However, some isotope systems like the natural Sr isotopic system, although potentially very powerful for this type of application, are still rarely used, mainly because their adequate measurement/determination poses major analytical challenges; as e.g. Sr is available in significant amounts in natural samples. In addition, biological systems underlie complex processes such as metabolism, adsorption/desorption or oxidation/reduction. As a consequence, classic evaluation approaches such as the isotope dilution mass spectrometry equation are often not applicable because of the unknown amount of tracer finally present in the sample. Isotope pattern deconvolution (IPD), based on multiple linear regression, serves as simplified alternative data processing strategy to double spike isotope dilution calculations. The outstanding advantage of this mathematical tool lies in the possibility of deconvolving the isotope pattern in a spiked sample without knowing the quantities of enriched isotope tracer being incorporated into the natural sample matrix as well as the degree of impurities and species-interconversion (e.g. from sample preparation). Here, the potential of IPD for environmental tracer studies is critically discussed, where special emphasis is set on evaluating different data processing strategies on the example of enriched stable Sr isotopes.1 The analytical key parameters such as blank (Kr, Sr and Rb), variation of the natural Sr isotopic composition in the sample, mass bias, interferences (Rb) and total combined uncertainty are considered. A full metrological protocol for data processing using IPD is presented based on data gained during two transgenerational marking studies of fish, where the transfer of a Sr isotope double spike (84Sr and 86Sr) from female spawners of common carp (Cyprinus carpio L.) and brown trout (Salmo trutta f.f.)2 to the centre of the otoliths of their offspring was studied by (LA)-MC-ICP-MS. 1J. Irrgeher, A. Zitek, M. Cervicek and T. Prohaska, J. Anal. At. Spectrom., 2014, 29, 193-200. 2A. Zitek, J. Irrgeher, M. Kletzl, T. Weismann and T. Prohaska, Fish. Manage. Ecol., 2013, 20, 654-361.

Position-specific 13C distributions within propane from experiments and natural gas samples

NASA Astrophysics Data System (ADS)

Piasecki, Alison; Sessions, Alex; Lawson, Michael; Ferreira, A. A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael D.; Eiler, John M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, 'bulk' isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

Position-specific 13C distributions within propane from experiments and natural gas samples

USGS Publications Warehouse

Piasecki, Alison; Sessions, Alex L.; Lawson, Michael; Ferreira, A.A.; Santos Neto, E. V.; Ellis, Geoffrey S.; Lewan, Michael; Eilers, J.M.

2018-01-01

Site-specific carbon isotope measurements of organic compounds potentially recover information that is lost in a conventional, ‘bulk’ isotopic analysis. Such measurements are useful because isotopically fractionating processes may have distinct effects at different molecular sites, and thermodynamically equilibrated populations of molecules tend to concentrate heavy isotopes in one molecular site versus another. Most recent studies of site-specific 13C in organics use specialized Nuclear Magnetic Resonance (NMR) techniques or complex chemical degradations prior to mass spectrometric measurements. Herein we present the first application of a new mass spectrometric technique that reconstructs the site-specific carbon isotope composition of propane based on measurements of the 13C/12C ratios of two or more fragment ions that sample different proportions of the terminal and central carbon sites. We apply this method to propane from laboratory experiments and natural gas samples to explore the relationships between site-specific carbon isotope composition, full-molecular δ13C, thermal maturity, and variation in organic matter precursors. Our goal is to advance the understanding of the sources and histories of short-chain alkanes within geologic systems. Our findings suggest that propane varies in its site-specific carbon isotope structure, which is correlated with increasing thermal maturity, first increasing in terminal position δ13C and then increasing in both center and terminal position δ13C. This pattern is observed in both experimental and natural samples, and is plausibly explained by a combination of site-specific, temperature-dependent isotope effects associated with conversion of different precursor molecules (kerogen, bitumen, and/or oil) to propane, differences in site-specific isotopic contents of those precursors, and possibly distillation of reactive components of those precursors with increasing maturity. We hypothesize that the largest changes in site-specific isotopic content of propane occur when bitumen and/or oil replace kerogen as the dominant precursors. If correct, this phenomenon could have significant utility for understanding gas generation in thermogenic petroleum systems.

A Distinct Magnetic Isotope Effect Measured in Atmospheric Mercury in Epiphytes

NASA Astrophysics Data System (ADS)

Ghosh, S.; Odom, A. L.

2007-12-01

Due to the importance of Mercury as an environmental contaminant, mercury cycling in the atmosphere has been extensively studied. However, there still remain uncertainties in the relative amounts of natural and anthropogenic emissions, atmospheric deposition rates as well as the spatial variation of atmospheric mercury. Part of a study to determine the isotopic composition of mercury deposited from the atmosphere has involved the use of epiphytes as monitors. The greatest advantage of such natural monitors is that a widespread, high-density network is possible at low cost. One of the disadvantages at present is that these monitors likely contain different mercury species (for example both gaseous, elemental mercury trapped by adsorption and Hg (II) by wet deposition). The project began with the understanding that biochemical reactions involving metallothioneins within the epiphytes might have produced an isotopic effect. One such regional network was composed of samples of Tillandsia usenoides (common name: Spanish moss) collected along the eastern Coastal Plain of the U.S. from northern Florida to North Carolina. The isotopic composition of a sample is expressed as permil deviations from a standard. The deviations are defined as δAHg = \\left(\\frac{Rsample}{Rstd}-1 \\right)1000 ‰ , where A represents the atomic mass number. R=\\frac{AHg}{202Hg} were measured for the isotopes 198Hg, 199Hg, 200Hg, 201Hg, 202Hg and 204Hg relative to the mercury standard SRM NIST 3133, by a standard-sample bracketing technique. For all samples, the delta values of the even-N plotted against atomic mass numbers define a linear curve. For the odd-N isotopes, δ199Hg and δ201Hg deviate from this mass-dependent fractionation (MDF) relationship and indicate a mass-independent fractionation (MIF) effect and a negative anomaly, i.e. a depletion in 199Hg and 201Hg relative to the even-N isotopes. These deviations are expressed as Δ199Hg = δ199Hgtotal - δ199HgMDF. A Δ201Hg/Δ199Hg ratio of 1.11 is predicted by isotope fractionation due to the Magnetic Isotope Effect (MIE), because 1.11 is the ratio of the magnetic moments of the two odd-N isotopes. A plot of Δ199Hg versus Δ201Hg values obtained reveals a striking pattern. All samples plot well within analytical uncertainly along a straight line passing through zero and having a slope of 1.11. Based on thermodynamic principles, some have argued that nuclear spin effects are quite insignificant in producing isotopic fractionation. However the MIE is a kinetic one in which those isotopes with non-zero magnetic moments effect the rates of recombination of free radical pairs by nuclear-electron hyperfine interaction and can become enriched or depleted in either reactants or products. In the samples studied here, the nuclear spin is far more important than either nuclear mass or nuclear volume in effecting isotopic fractionation of Mercury.

Agricultural Nutrient Cycling at the Strawberry Creek Watershed: Insights Into Processes Using Stable Isotope Analysis

NASA Astrophysics Data System (ADS)

Thuss, E.; English, M. C.; Spoelstra, J.

2009-05-01

When nitrogen availability exceeds biological demand, excess nitrogen, especially nitrate, may subsequently pollute ground and surface water. Agricultural practices in Southern Ontario typically supplement soils with organic and inorganic nutrients to aid in crop development, and employ various management techniques to limit nutrient loss. Excess nitrogen has several potential fates, which are controlled by the net effects of numerous nitrogen cycling reactions in the soil that are often difficult to measure directly. Nitrogen cycling in soils is controlled in large part by soil moisture, as it affects microbial activity and soil redox conditions. Stable isotope geochemistry is a powerful tool that provides information on nitrogen sources and processes. This study uses crop nitrogen and carbon isotope ratios to provide insights into the net effects of soil nitrogen cycling and nitrogen fate. This research was conducted at the Strawberry Creek Watershed (SCW), an agricultural research watershed located between Kitchener-Waterloo and Guelph, Ontario. The SCW exhibits elevated nitrate concentrations in groundwater, tile discharge, and the stream itself. Previous isotopic work revealed that this nitrate is largely derived from chemical fertilizer and manure applications. Field-scale hydrological processes lead to areas where the fate of applied nitrogen differs, which has an isotopic effect on the residual nitrogen that is available to plants. Results of this study indicate significant patterns in the isotopic signature of plant tissue, in both temporal and spatial scales. At the plot-scale where soil conditions are similar, there is little to no variation in foliar isotope values, but at the field-scale there appears to be a significant amount of variability related to soil moisture and nitrogen loss. This relationship can potentially provide insight into ideal conditions for nitrogen uptake efficiency. Reducing agricultural nitrogen leaching to ground and surface water requires a better understanding of nitrogen fate in the soil zone, and will result in more effective agricultural nutrient management.

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

Yogodzinski, Gene; Vervoort, Jeffery; Brown, Shaun Tyler

The Hf and Nd isotopic compositions of 71 Quaternary lavas collected from locations along the full length of the Aleutian island arc are used to constrain the sources of Aleutian magmas and to provide insight into the geochemical behavior of Nd and Hf and related elements in the Aleutian subduction-magmatic system. Isotopic compositions of Aleutian lavas fall approximately at the center of, and form a trend parallel to, the terrestrial Hf-Nd isotopic array with {var_epsilon}{sub Hf} of +12.0 to +15.5 and {var_epsilon}{sub Nd} of +6.5 to +10.5. Basalts, andesites, and dacites within volcanic centers or in nearby volcanoes generally allmore » have similar isotopic compositions, indicating that there is little measurable effect of crustal or other lithospheric assimilation within the volcanic plumbing systems of Aleutian volcanoes. Hafnium isotopic compositions have a clear pattern of along-arc increase that is continuous from the eastern-most locations near Cold Bay to Piip Seamount in the western-most part of the arc. This pattern is interpreted to reflect a westward decrease in the subducted sediment component present in Aleutian lavas, reflecting progressively lower rates of subduction westward as well as decreasing availability of trench sediment. Binary bulk mixing models (sediment + peridotite) demonstrate that 1-2% of the Hf in Aleutian lavas is derived from subducted sediment, indicating that Hf is mobilized out of the subducted sediment with an efficiency that is similar to that of Sr, Pb and Nd. Low published solubility for Hf and Nd in aqueous subduction fluids lead us to conclude that these elements are mobilized out of the subducted component and transferred to the mantle wedge as bulk sediment or as a silicate melt. Neodymium isotopes also generally increase from east to west, but the pattern is absent in the eastern third of the arc, where the sediment flux is high and increases from east to west, due to the presence of abundant terrigenous sediment in the trench east of the Amlia Fracture Zone, which is being subducting beneath the arc at Seguam Island. Mixing trends between mantle wedge and sediment end members become flatter in Hf-Nd isotope space at locations further west along the arc, indicating that the sediment end member in the west has either higher Nd/Hf or is more radiogenic in Hf compared to Nd. This pattern is interpreted to reflect an increase in pelagic clay relative to the terrigenous subducted sedimentary component westward along the arc. Results of this study imply that Hf does not behave as a conservative element in the Aleutian subduction system, as has been proposed for some other arcs.« less

The effect of drainage reorganization on paleoaltimetry studies: An example from the Paleogene Laramide foreland

NASA Astrophysics Data System (ADS)

Davis, Steven J.; Wiegand, Bettina A.; Carroll, Alan R.; Chamberlain, C. Page

2008-11-01

Using multiple isotope systems, we examine the complex effects of drainage reorganization in the Laramide Foreland in the context of stable isotope paleoaltimetry. Strontium, oxygen and carbon isotopic data from lacustrine carbonates formed in the southwestern Uinta Basin, Utah between the Late Cretaceous and late Middle Eocene reveal a two stage expansion in the drainage basin of Lake Uinta beginning at ~ 53 Ma culminating in the Mahogany highstand at 48.6 Ma. A marked increase in 87Sr/ 86Sr ratios of samples from the Main Body of the Green River Formation is interpreted as the result of water overflowing the Greater Green River Basin in Wyoming and entering Lake Uinta from the east via the Piceance Creek Basin of northwestern Colorado. This large new source of water caused a rapid expansion of Lake Uinta and was accompanied by a significant and rapid increase in the O isotope record of carbonate samples by ~ 6‰. The periodic overspilling of Lake Gosiute probably became continuous at ~ 49 Ma, when the lake captured low- δ18O water from the Challis and Absaroka Volcanic Fields to the north. However, evaporation in the Greater Green River and Piceance Creek Basins meant that the waters entering Lake Uinta were still enriched in 18O. By ~ 46 Ma, inflows from the Greater Green River Basin ceased, resulting in a lowstand of Lake Uinta and the deposition of bedded evaporites in the Saline Facies of the Green River Formation. We thus show that basin development and lake hydrology in the Laramide foreland were characterized by large-scale changes in Cordilleran drainage patterns, capable of confounding paleoaltimetry studies premised on too few isotopic systems, samples or localities. In the case of the North American Cordillera of the Paleogene, we further demonstrate the likelihood that (1) topographic evolution of distal source areas strongly influenced the isotopic records of intraforeland basins and (2) a pattern of drainage integration between the hinterland and foreland may correlate in space and time with the southward sweep of hinterland magmatism.

Stable isotopic compositions in Australian precipitation

NASA Astrophysics Data System (ADS)

Liu, Jianrong; Fu, Guobin; Song, Xianfang; Charles, Stephen P.; Zhang, Yinghua; Han, Dongmei; Wang, Shiqin

2010-12-01

Stable deuterium (δD) and oxygen-18 (δ18O) isotopes in 1962 to 2002 precipitation from the seven Australian stations of the Global Network of Isotopes in Precipitation (GNIP) were used to investigate isotope characteristics including temporal and spatial distributions across different regions of Australia. On the basis of 1534 samples, the local meteoric water line (LMWL) was established as δD = 7.10δ18O + 8.21. δ18O showed a depletion trend from north and south to central Australia (a continental effect) and from west to east. Precipitation amount effects were generally greater than temperature effects, with quadratic or logarithmic correlations describing δ/T and δ/P better than linear relationships. Nonlinear stepwise regression was used to determine the significant meteorological control factors for each station, explaining about 50% or more of the δ18O variations. Geographical control factors for δ18O were given by the relationship δ18O (‰) = -0.005 longitude (°) - 0.034 latitude (°)-0.003 altitude (m) - 4.753. Four different types of d-excess patterns demonstrated particular precipitation formation conditions for four major seasonal rainfall zones. Finally, wavelet coherence (WTC) between δ18O and SOI confirmed that the influence of ENSO decreased from east and north to west Australia.

Effect-directed analysis to explore the polar bear exposome: identification of thyroid hormone disrupting compounds in plasma.

PubMed

Simon, Eszter; van Velzen, Martin; Brandsma, Sicco H; Lie, Elisabeth; Løken, Katharina; de Boer, Jacob; Bytingsvik, Jenny; Jenssen, Bjørn M; Aars, Jon; Hamers, Timo; Lamoree, Marja H

2013-08-06

Compounds with transthyretin (TTR)-binding potency in the blood plasma of polar bear cubs were identified with effect-directed analysis (EDA). This approach contributes to the understanding of the thyroid disrupting exposome of polar bears. The selection of these samples for in-depth EDA was based on the difference between the observed TTR-binding potency on the one hand and the calculated potency (based on known concentrations of TTR-binding compounds and their relative potencies) on the other. A library-based identification was applied to the liquid chromatography-time-of-flight-mass spectrometry (LC-ToF-MS) data by screening for matches between compound lists and the LC-ToF-MS data regarding accurate mass and isotope pattern. Then, isotope cluster analysis (ICA) was applied to the LC-ToF-MS data allowing specific screening for halogen isotope patterns. The presence of linear and branched nonylphenol (NP) was observed for the first time in polar bears. Furthermore, the presence of one di- and two monohydroxylated octachlorinated biphenyls (octaCBs) was revealed in the extracts. Linear and branched NP, 4'-OH-CB201 and 4,4'-OH-CB202 could be successfully confirmed with respect to their retention time in the analytical system. In addition, branched NP, mono- and dihydroxylated-octaCBs showed TTR-binding potencies and could explain another 32 ± 2% of the total measured activities in the extracts.

Isotope Identification

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

Karpius, Peter Joseph

2017-09-18

The objective of this training modules is to examine the process of using gamma spectroscopy for radionuclide identification; apply pattern recognition to gamma spectra; identify methods of verifying energy calibration; and discuss potential causes of isotope misidentification.

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.

Forensic Stable Isotope Biogeochemistry

NASA Astrophysics Data System (ADS)

Cerling, Thure E.; Barnette, Janet E.; Bowen, Gabriel J.; Chesson, Lesley A.; Ehleringer, James R.; Remien, Christopher H.; Shea, Patrick; Tipple, Brett J.; West, Jason B.

2016-06-01

Stable isotopes are being used for forensic science studies, with applications to both natural and manufactured products. In this review we discuss how scientific evidence can be used in the legal context and where the scientific progress of hypothesis revisions can be in tension with the legal expectations of widely used methods for measurements. Although this review is written in the context of US law, many of the considerations of scientific reproducibility and acceptance of relevant scientific data span other legal systems that might apply different legal principles and therefore reach different conclusions. Stable isotopes are used in legal situations for comparing samples for authenticity or evidentiary considerations, in understanding trade patterns of illegal materials, and in understanding the origins of unknown decedents. Isotope evidence is particularly useful when considered in the broad framework of physiochemical processes and in recognizing regional to global patterns found in many materials, including foods and food products, drugs, and humans. Stable isotopes considered in the larger spatial context add an important dimension to forensic science.

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean).

PubMed

van Geldern, Robert; Kuhlemann, Joachim; Schiebel, Ralf; Taubald, Heinrich; Barth, Johannes A C

2014-06-01

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δP) with values of-8.6(± 0.2) ‰ for δ(18)O and-58(± 2) ‰ for δ(2)H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of-0.17(± 0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.

Tracing Carbon Sources through Aquatic and Terrestrial Food Webs Using Amino Acid Stable Isotope Fingerprinting

PubMed Central

Larsen, Thomas; Ventura, Marc; Andersen, Nils; O’Brien, Diane M.; Piatkowski, Uwe; McCarthy, Matthew D.

2013-01-01

Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ13C patterns among amino acids (δ13CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ13CAA patterns in contrast to bulk δ13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs. PMID:24069196

Tracing carbon sources through aquatic and terrestrial food webs using amino acid stable isotope fingerprinting.

PubMed

Larsen, Thomas; Ventura, Marc; Andersen, Nils; O'Brien, Diane M; Piatkowski, Uwe; McCarthy, Matthew D

2013-01-01

Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ(13)C patterns among amino acids (δ(13)CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ(13)CAA patterns in contrast to bulk δ(13)C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ(13)CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ(13)C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ(13)C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

Quantifying dispersal rates and distances in North American martens: a test of enriched isotope labeling

Treesearch

Jonathan N. Pauli; Winston P. Smith; Merav Ben-David

2012-01-01

Advances in the application of stable isotopes have allowed the quantitative evaluation of previously cryptic ecological processes. In particular, researchers have utilized the predictable spatial patterning in natural abundance of isotopes to better understand animal dispersal and migration. However, quantifying dispersal via natural abundance alone has proven to be...

Mapping "Vital Effects": Unlocking the Archive of Deep Sea Stylasterid δ18O and δ13C

NASA Astrophysics Data System (ADS)

King, T. M.; Rosenheim, B. E.

2017-12-01

Deep sea coral skeletons are able to incorporate chemical and isotopic signals from the dissolved inorganic pool of the surrounding water mass, attributing them with continuous, high-resolution records that span centuries to millennia. Most importantly, they are sessile organisms and remain fixed to the seafloor with respect to fluctuating water mass boundaries. Stylasterid corals (order Anthoathecata) are abundant in the Southern Ocean but not as commonly used for paleoceanographic reconstructions as corals of the order Scleractinia. Little is known about stylasterid growth rate, skeletal structure, or their effects on chemical and isotopic signals from the surrounding environment. Here, we present stable isotope "heat maps" over cross sections of stylasterid corals (genus Errina) from the western Ross Sea and eastern Wilkes Land, Antarctica. Isotope heat maps are used to illustrate isotope variability over small spatial scales within different sections of the coral skeletons. These maps indicate that the central growth axis of the coral stem is subject to kinetic effects, whereas, the outer coral skeleton is precipitated nearer to equilibrium with the surrounding water mass. We present several maps of both live and dead-collected corals (spanning 40,000 years from present) in order to examine natural variability through time and to identify possible diagenetic effects. Our results begin to clarify stylasterid growth patterns so that we are able to optimize sampling plans of these corals. These results also provide us with a context in which to interpret radiocarbon records, and potentially independent radio chronologies, compiled from the same coral collection (King et al., in review; GRL).

Controls of precipitation δ18O on the northwestern Tibetan Plateau: A case study at Ngari station

NASA Astrophysics Data System (ADS)

Guo, Xiaoyu; Tian, Lide; Wen, Rong; Yu, Wusheng; Qu, Dongmei

2017-06-01

The shifting atmospheric circulation between the Indian monsoon and the westerlies on the northwestern Tibetan Plateau (TP) influences precipitation as well as precipitation isotopes. Isotopic records will therefore show historical fluctuations. To understand better the factors controlling present day precipitation δ18O values on the northwestern TP, we made continuous observations of precipitation isotopes at Ngari station from 2010 to 2013. The drivers of precipitation δ18O were investigated using analyses of their statistical relations with temperature, precipitation amount, relative humidity, and convective activities based on outgoing longwave radiation (OLR) data from NOAA satellites, and downward shortwave radiation (DSR) data collected at the Ngari automatic weather station. Atmospheric circulation patterns from NCAR reanalysis, and moisture transport paths of individual events derived from the HYSPLIT model using NCEP data, were also used to trace moisture sources. The results of our study include: (1) The slope and intercept of the Local Meteoric Water Line (LMWL) at Ngari (δD = 8.51 δ18O + 11.57 (R2 = 0.97, p < 0.01)) were higher than for the Global Meteoric Water Line (GMWL), indicating drier local climatic conditions; (2) Precipitation δ18O values showed a weak ;temperature effect; and a weak ;precipitation amount effect; at Ngari; and (3) Convection (or temperature patterns) integrated over several days (0-20) preceding each event were determined to be the main driver of precipitation isotopic values in monsoon (or non-monsoon) season. The longer (shorter) periods of τm days when correlation coefficients between precipitation δ18O and OLR were at their maxima (minima) indicate deep convective activities (shorter moisture transportation pathways) in August (June, July, and September).

15N investigation into the effect of a pollutant on the nitrogen metabolism of Tetrahymena pyriformis as a model for environmental medical research.

PubMed Central

Arndt, K; Hofmann, D; Gehre, M; Krumbiegel, P

1998-01-01

A pilot study was performed to examine the potential of stable isotope techniques for monitoring the impact of a harmful substance on the cellular nitrogen metabolism in the ciliate species Tetrahymena pyriformis. After identical cultivation periods of control cells and toluene-exposed cells in a defined culture medium enriched with [guanidino-15N2]l-arginine, a number of nitrogen-containing pools were analyzed: 1) quantity and 15N abundance of ammonia as the end product of nitrogen metabolism in the system; 2) pattern and 15N abundances of the protein-bound amino acids in the cells; 3) pattern and 15N abundances of free amino acids in the cells; and 4) pattern and 15N abundances of the amino acids in the culture medium. In addition to 15N emission spectrometry, a new gas chromatography/combustion interface-isotope ratio mass spectrometry/mass spectrometry analytical system was used. The production and 15N content of ammonia were higher in the toluene-exposed system by 30% and 43%, respectively, indicating higher deamination rates and greater arginine consumption. The toluene-exposed cells exhibited increased 15N abundances of protein-bound amino acids in alanine, aspartic acid, glutamic acid, and tyrosine. Furthermore, structural analyses revealed the presence of N[Omega]-acetylarginine and pyrrolidonecarboxylic acid--compounds that had not previously been detected in Tetrahymena pyriformis. Differences in the 15N-enrichment of free amino acids were also evident. This new effect-monitoring system designed to investigate the impact of a pollutant on protein metabolism by using a stable isotope-labeled cell culture is a powerful tool for environmental medical research. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 PMID:9681977

Dietary heterogeneity among Western industrialized countries reflected in the stable isotope ratios of human hair.

PubMed

Valenzuela, Luciano O; Chesson, Lesley A; Bowen, Gabriel J; Cerling, Thure E; Ehleringer, James R

2012-01-01

Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization). Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ(13)C values (-22.7 to -18.3‰), and significantly higher δ(15)N (7.8 to 10.3‰) and δ(34)S (4.8 to 8.3‰) values than samples from the USA (δ(13)C: -21.9 to -15.0‰, δ(15)N: 6.7 to 9.9‰, δ(34)S: -1.2 to 9.9‰). Within Europe, we detected differences in hair δ(13)C and δ(34)S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments.

Dietary Heterogeneity among Western Industrialized Countries Reflected in the Stable Isotope Ratios of Human Hair

PubMed Central

Valenzuela, Luciano O.; Chesson, Lesley A.; Bowen, Gabriel J.; Cerling, Thure E.; Ehleringer, James R.

2012-01-01

Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization). Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ13C values (−22.7 to −18.3‰), and significantly higher δ15N (7.8 to 10.3‰) and δ34S (4.8 to 8.3‰) values than samples from the USA (δ13C: −21.9 to −15.0‰, δ15N: 6.7 to 9.9‰, δ34S: −1.2 to 9.9‰). Within Europe, we detected differences in hair δ13C and δ34S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments. PMID:22479574

Isotopic Ordering in Atmospheric O2 as a Tracer of Ozone Photochemistry and the Tropical Atmosphere

NASA Technical Reports Server (NTRS)

Yeung, Laurence Y.; Murray, Lee T.; Ash, Jeanine L.; Young, Edward D.; Boering, Kristie A.; Atlas, Elliot L.; Schauffler, Sue M.; Lueb, Richard A.; Langenfelds, Ray L.; Krummel, Paul B.;

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

NASA Astrophysics Data System (ADS)

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

2009-01-01

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

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

PubMed Central

Antler, Gilad; Pellerin, André

2018-01-01

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

Water balance model for mean annual hydrogen and oxygen isotope distributions in surface waters of the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Kennedy, Casey D.; Liu, Zhongfang; Stalker, Jeremy

2011-12-01

The stable H and O isotope composition of river and stream water records information on runoff sources and land-atmosphere water fluxes within the catchment and is a potentially powerful tool for network-based monitoring of ecohydrological systems. Process-based hydrological models, however, have thus far shown limited power to replicate observed large-scale variation in U.S. surface water isotope ratios. Here we develop a geographic information system-based model to predict long-term annual average surface water isotope ratios across the contiguous United States. We use elevation-explicit, gridded precipitation isotope maps as model input and data from a U.S. Geological Survey monitoring program for validation. We find that models incorporating monthly variation in precipitation-evapotranspiration (P-E) amounts account for the majority (>89%) of isotopic variation and have reduced regional bias relative to models that do not consider intra-annual P-E effects on catchment water balance. Residuals from the water balance model exhibit strong spatial patterning and correlations that suggest model residuals isolate additional hydrological signal. We use interpolated model residuals to generate optimized prediction maps for U.S. surface water δ2H and δ18O values. We show that the modeled surface water values represent a relatively accurate and unbiased proxy for drinking water isotope ratios across the United States, making these data products useful in ecological and criminal forensics applications that require estimates of the local environmental water isotope variation across large geographic regions.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

NASA Astrophysics Data System (ADS)

Li, Weiqiang; Jackson, Simon E.; Pearson, Norman J.; Graham, Stuart

2010-07-01

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ 65Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1 σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ˜-0.4‰ (-0.25 ± 0.36‰, 1 σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1 σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ 65Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.

Clinical experience with the radioisotope varicocele scan as a screening method for the detection of subclinical varicoceles

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

Wheatley, J.K.; Fajman, W.A.; Witten, F.R.

1982-07-01

The association of varicoceles and subfertility has been well documented. Although varicoceles remain the most common surgically correctable cause of male infertility the diagnosis of small varicoceles remains a challenge. We evaluated 40 men with an isotope blood pooling scan. Seven volunteers served as either positive or negative controls. Complete correlation between physical findings and the isotope scan was found. The 6 patients with obvious clinical varicoceles and a stress pattern on semen analysis all had positive scans. The 18 patients with a stress pattern and who were clinically suspected of having a varicocele all had positive scans. Of 9more » patients evaluated for infertility with a stress pattern but no clinical evidence of varicocele 6 had positive scans. We believe that the isotope scan will prove to be a useful procedure in the detection of nonpalpable varicoceles in selected subfertile men.« less

Oceans Apart: Using Stable Isotopes to Assess the Role of Fog in Two Semi-Arid Island Ecosystems

NASA Astrophysics Data System (ADS)

Schmitt, S.; Riveros-Iregui, D.; Hu, J.

2017-12-01

Fog is a significant hydrologic input in many tropical island systems, and is a water source particularly susceptible to the effects of global climate change. To better understand the role of fog as a hydrological input in two oceanic islands, we address two principal questions: 1) Do seasonal or extreme precipitation events lead to distinguishable differences in stable isotopic signatures of water inputs within and between sites and islands? 2) Does microclimatic zonation lead to distinguishable differences in isotopic signatures of meteoric inputs between different sites on a given island? To perform this analysis, meteoric water samples (fog, rain and throughfall) were collected over three sites (one windward and two leeward) and three field seasons in San Cristobal, Galapagos to ascertain the isotopic signature of each water balance input during different times of year. An additional field season of data in Ascension Island, UK, was also used to perform a comparative analysis between islands. A stable isotope mixing model was used to determine the relative proportion of surface water and groundwater that is composed of fog, and to demonstrate spatiotemporal patterns of recharge dynamics in each island system. Local meteoric water lines were generated for each site and over each field season to determine the source of hydrologic inputs (trade wind-generated orographic precipitation versus storm precipitation) and the role of locally recycled water in the overall water balance of each site. Our results will approximate potential changes in water inputs to San Cristobal and Ascension, respectively, that could be impacted by an increase in cloud base height or a change in weather patterns brought about by climate change.

Understanding Extreme Precipitation Behaviour in British Columbia's Lower Mainland Using Historical and Proxy Records

NASA Astrophysics Data System (ADS)

Spry, Christina

In British Columbia, Pineapple Express storms can lead to flooding, slope failures and negative impacts to water quality. Mitigating the impacts of extreme weather events in a changing climate requires an understanding of how local climate responds to regional-toglobal climate forcing patterns. In this study, I use historical and proxy data to identify the distinguishing characteristics of Pineapple Express storms and to develop a tree ring oxygen isotope record (1960--1995) of local climate conditions in the Lower Mainland of British Columbia. I found that high magnitude Pineapple Express storms have significantly higher precipitation and streamflow than other storms types, which result in relatively high contributions of Pineapple Express storms to the annual water budget. As well, Pineapple Express precipitation is characterized by an enriched delta18O isotopic signature when compared to precipitation originating from the North Pacific Ocean. However, differences in source water do not appear to be driving the variability in tree ring delta18O ratios. Instead, tree ring isotopic values exhibit a regional climate pattern that is strongly driven by latitudinal temperature gradients and the Rayleigh distillation effect. Therefore, future warmer conditions may decrease the temperature gradient between the equator and the poles, which can be recorded in the tree ring isotope record. The results also suggest that warmer temperatures due to climate change could result in more active Pineapple Express storm seasons, with multiple PE storms happening over a short period of time. Concurrent storms significantly increase the risk to society because the resulting antecedent saturated soil conditions can trigger precipitationinduced natural hazards. Keywords: extreme weather; stable isotopes; Pineapple Express; British Columbia; climate change; tree rings.

Patterns in Stable Isotope Values of Nitrogen and Carbon in Particulate Matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras

EPA Science Inventory

Stable isotope measurements of nitrogen and carbon (15N, 13ddC) are often used to characterize estuarine, nearshore, and open ocean ecosystems. Reliable information about the spatial distribution of base-level stable isotope values, often represented by primary producers, is crit...

Development and validation of a liquid chromatography isotope dilution mass spectrometry method for the reliable quantification of alkylphenols in environmental water samples by isotope pattern deconvolution.

PubMed

Fabregat-Cabello, Neus; Sancho, Juan V; Vidal, Andreu; González, Florenci V; Roig-Navarro, Antoni Francesc

2014-02-07

We present here a new measurement method for the rapid extraction and accurate quantification of technical nonylphenol (NP) and 4-t-octylphenol (OP) in complex matrix water samples by UHPLC-ESI-MS/MS. The extraction of both compounds is achieved in 30min by means of hollow fiber liquid phase microextraction (HF-LPME) using 1-octanol as acceptor phase, which provides an enrichment (preconcentration) factor of 800. On the other hand we have developed a quantification method based on isotope dilution mass spectrometry (IDMS) and singly (13)C1-labeled compounds. To this end the minimal labeled (13)C1-4-(3,6-dimethyl-3-heptyl)-phenol and (13)C1-t-octylphenol isomers were synthesized, which coelute with the natural compounds and allows the compensation of the matrix effect. The quantification was carried out by using isotope pattern deconvolution (IPD), which permits to obtain the concentration of both compounds without the need to build any calibration graph, reducing the total analysis time. The combination of both extraction and determination techniques have allowed to validate for the first time a HF-LPME methodology at the required levels by legislation achieving limits of quantification of 0.1ngmL(-1) and recoveries within 97-109%. Due to the low cost of HF-LPME and total time consumption, this methodology is ready for implementation in routine analytical laboratories. Copyright © 2013 Elsevier B.V. All rights reserved.

Evaporative fractionation of marine water isotopes in the Arctic Ocean help understand a changing Arctic water cycle

NASA Astrophysics Data System (ADS)

Klein, E. S.; Welker, J. M.

2017-12-01

Most of the global hydrologic cycle occurs in oceanic waters. This oceanic derived moisture is critical to the precipitation and evapotranspiration regimes that influence terrestrial Earth systems. Thus understanding oceanic water processes has important global implications for our knowledge of modern and past hydrologic cycles. As they are influenced by environmental variables such as sea surface temperature and atmospheric humidity, water isotope ratios (e.g., δ18O, δ2H) can help understand the patterns driving the water cycle. However, our knowledge of marine isotopes is relatively limited. In particular, the fractionation of water isotopes during evaporation of oceanic water, essentially the start of the hydrologic cycle, is largely based on theoretical relationships derived from spatially and temporally limited data sets. This constrained understanding of oceanic evaporation fractionation patterns is especially pronounced in the rapidly changing Arctic Ocean. These changes are associated with reduced sea ice coverage, which is increasing the amount of local Artic Ocean sourced moisture in atmospheric and terrestrial systems and amplifying the Arctic hydrologic cycle. Here we present new data revealing the nuances of evaporative fractionation of Arctic Ocean water isotopes with the first collection of continuous, contemporaneous sea water and vapor isotopes. These data, collected in situ aboard the icebreaker Healy, show that the difference between actual ocean vapor isotope values and vapor values estimated by the closure equation increases progressively with latitude (especially beyond 70°) and varies between δ18O and δ2H. These differences are likely due to more isotopic mixing in the troposphere and/or closure equation assumptions inapplicable to Arctic regions. Moreover, we find: 1) a positive relationship between fractionation magnitude and latitude; and 2) the influence of evaporative fractionation from environmental variables such as wind and relative humidity reverses with the presence of sea ice. These new data increase our understanding of the patterns and processes governing past, present, and future changes to the Arctic hydrologic cycle.

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.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails

USGS Publications Warehouse

Nardoto, G.B.; Silva, S.; Kendall, C.; Ehleringer, J.R.; Chesson, L.A.; Ferraz, E.S.B.; Moreira, M.Z.; Ometto, Jean P. H. B.; Martinelli, L.A.

2006-01-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail ??13C values (mean ?? standard deviation) were -15.4 ?? 1.0 and -18.8 ?? 0.8??? and ??15N values were 10.4 ?? 0.7 and 9.4 ?? 0.6??? for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. ?? 2006 Wiley-Liss, Inc.

Geographical patterns of human diet derived from stable-isotope analysis of fingernails.

PubMed

Nardoto, Gabriela B; Silva, Steven; Kendall, Carol; Ehleringer, James R; Chesson, Lesley A; Ferraz, Epaminondas S B; Moreira, Marcelo Z; Ometto, Jean P H B; Martinelli, Luiz A

2006-09-01

Carbon and nitrogen isotope ratios of human fingernails were measured in 490 individuals in the western US and 273 individuals in southeastern Brazil living in urban areas, and 53 individuals living in a moderately isolated area in the central Amazon region of Brazil and consuming mostly locally grown foods. In addition, we measured the carbon and nitrogen isotope ratios of common food items to assess the extent to which these isotopic signatures remain distinct for people eating both omnivorous and vegetarian diets and living in different parts of the world, and the extent to which dietary information can be interpreted from these analyses. Fingernail delta13C values (mean +/- standard deviation) were -15.4 +/- 1.0 and -18.8 +/- 0.8 per thousand and delta15N values were 10.4 +/- 0.7 and 9.4 +/- 0.6 per thousand for southeastern Brazil and western US populations, respectively. Despite opportunities for a "global supermarket" effect to swamp out carbon and nitrogen isotope ratios in these two urbanized regions of the world, differences in the fingernail isotope ratios between southeastern Brazil and western US populations persisted, and appeared to be more associated with regional agricultural and animal production practices. Omnivores and vegetarians from Brazil and the US were isotopically distinct, both within and between regions. In a comparison of fingernails of individuals from an urban city and isolated communities in the Amazonian region, the urban region was similar to southeastern Brazil, whereas individuals from isolated nonurban communities showed distinctive isotopic values consistent with their diets and with the isotopic values of local foods. Although there is a tendency for a "global supermarket" diet, carbon and nitrogen isotopes of human fingernails hold dietary information directly related to both food sources and dietary practices in a region. 2006 Wiley-Liss, Inc.

Measurement of the Isotopic Signature of Soil Carbon Dioxide: Methods Development and Initial Field Results

NASA Astrophysics Data System (ADS)

Kayler, Z.; Rugh, W.; Mix, A. C.; Bond, B. J.; Sulzman, E. W.

2005-12-01

Soil respiration is a significant component of ecosystem respiration and its isotopic composition is likely to lend insight into ecosystem processes. We have designed probes to determine the isotopic signature of soil-respired CO2 using a two end-member mixing model approach (i.e., Keeling plot). Each probe consists of three 35 ml PVC chambers cased in fiberglass mesh and connected to the soil surface via stainless steel tubing with a septa-lined swagelok fitting. Chambers are vertically connected such that they sample gases at depth intervals centered on 5, 15, and 30 cm. Gases are sampled via a hand vacuum pump equipped with a two-way valve, which allows vials pre-filled with N2 gas in the laboratory to be evacuated and re-filled with only a single septa puncture in the field. Data indicate samples can be stored reliably for up to three days if punctured septa are coated in silicone sealant. To test whether this field sampling method was robust, we constructed a carbon-free sand column out of PVC pipe into which we plumbed a tank of known CO2 concentration and isotopic composition. We have tested the effects of wetting and flow rate on our ability to reproduce tank values. A linear model (geometric mean regression) yielded a more negative isotopic value than the actual gas, but a simple polynomial curve fit the tank value. After laboratory testing, the probes were established in a steep drainage in the H.J. Andrews LTER site in the Cascade Mountains of western Oregon (as part of the Andrews Airshed project). We established a transect of five 10 m2 plots with four soil probes and a companion respiration collar and measured soil CO2 efflux and soil δ13CO2 values biweekly from June-Sept. Results indicate there is a clear difference in isotopic and respiration flux patterns between the north- and south-facing slopes, with the north facing slope exhibiting higher fluxes and more 13C enriched respiration. The temporal pattern of respiration correlates well with decreasing soil moisture over the summer. In addition, flux and isotopic samples collected every 4 hours over a 24 hour period suggested strong diel patterns in both measures, with more enriched δ13C respired from soils in early morning and more δ13C depleted values during the day, suggesting that photosynthetic uptake and CO2 recycling by the aboveground vegetation influence soil-respired CO2 values.

Uncovering patterns of spring migration in the monarch butterfly using stable isotopes and demographic models

NASA Astrophysics Data System (ADS)

Norris, R.; Miller, N.; Wassenaar, L.; Hobson, K.

2010-12-01

Each spring, millions of monarch butterflies (Danaus plexippus) migrate up to 3000 km from central Mexico to re-colonize eastern North America. However, despite centuries of research, the patterns of re-colonization are not well understood. We combined stable-hydrogen (δD) and -carbon (δ13C) isotope measurements with demographic models to test (1) whether individuals sampled in the northern part of the breeding range in the Great Lakes originate directly from Mexico or are second generation individuals born in the southern US and (2) to estimate whether populations on the eastern seaboard migrate longitudinally over the Appalachians or originate directly from the Gulf Coast. In the Great Lakes, we found that the majority of individuals were second-generation monarchs born in the Gulf Coast and Central regions of the US. However, 25% individuals originated directly from Mexico and we estimated that these individuals produced the majority of offspring born in the Great Lakes region during June. On the eastern seaboard, we found the majority of monarchs (88%) originated in the mid-west and Great Lakes regions, providing the first direct evidence that second generation monarchs born in June complete a (trans-) longitudinal migration across the Appalachian mountains. The remaining individuals (12%) originated from parents that migrated directly from the Gulf coast during early spring. Our results demonstrate how stable isotopes, when combined with ecological data, can provide insights into patterns of connectivity in migratory insects that have been impossible to test using conventional techniques. The migration patterns presented here have important implications for predicting future changes in population size and for developing effective conservation plans for this species.

A 115-year δ15N record of cumulative nitrogen pollution in California serpentine grasslands

NASA Astrophysics Data System (ADS)

Vallano, D.; Zavaleta, E. S.

2010-12-01

Until the 1980s, California’s biodiverse serpentine grasslands were threatened primarily by development and protected by reserve creation. However, nitrogen (N) fertilization due to increasing fossil fuel emissions in the expanding Bay Area is thought to be contributing to rapid, recent invasion of these ecosystems by exotic annual grasses that are displacing rare and endemic serpentine species. Documenting the cumulative effects of N deposition in this ecosystem can direct policy and management actions to mitigate the role of N deposition in its transformation. Natural abundance stable isotopes of N in vegetation have been increasingly used as bio-indicators of N deposition patterns and subsequent changes to plant N cycling and assimilation. However, the long-term record of atmospheric reactive N enrichment and the resulting changes in ecosystem N dynamics have yet to be adequately reconstructed in many ecosystems. Museum archives of vascular plant tissue are valuable sources of materials to reconstruct temporal and spatial isotopic patterns of N inputs to ecosystems. Here, we present N stable isotope data from archived and current specimens of an endemic California serpentine grassland species, leather oak (Quercus durata), since 1895 across the greater San Francisco Bay region. We measured spatial and temporal trends in stable isotope composition (δ15N and δ13C) and concentration (%N and %C) of historical and current samples of leather oak leaves from sites within the Bay Area, impacted by increasing development, and sites northeast of the Bay Area, with significantly lower rates of urbanization and industrialization. Specifically, we sampled dry museum and fresh leaf specimens from serpentine sites within Lake (n=27) and Santa Clara (n=30) counties dating from 1895 to 2010. Leaf δ15N values were stable from 1895 to the 1950s and then decreased strongly throughout the last 50 years as fossil fuel emissions rapidly increased in the Bay Area, indicating that N pollution is being retained in serpentine grassland ecosystems. Leaf δ15N values in the high-deposition region declined at a rate of -0.041‰ yr-1, while leaf δ15N values in the low-deposition region did not show a strong pattern. In both regions, leaf δ13C values declined through time as atmospheric CO2 concentrations increased in response to fossil fuel combustion (the Suess effect). Leaf %N and %C values did not present any clear patterns at sites within or outside of the Bay Area. We conclude that using natural abundance stable isotope values in leaves can indicate variation in N pollution inputs across wide spatial and temporal scales and that archived plant samples can provide valuable baselines against which to assess changes in regional N cycling and subsequent ecological impacts on vegetation.

IsoMark - a comprehensive assessment of the potential of isotopes in hard parts of freshwater fish to determine origin and migratory patterns using LA-(MC)-ICP-MS

NASA Astrophysics Data System (ADS)

Zitek, Andreas; Irrgeher, Johanna; Sturm, Monika; Brunner, Marion; Dillinger, Benno; Prohaska, Thomas

2010-05-01

The ‘IsoMark' project focuses for the first time on the comprehensive investigation of microchemical information (elemental fingerprint of Ca, Sr, Na, Ba, Mg; isotopic fingerprint of Sr, Ca, and additionally of C and O) in different hard parts of several typical European freshwater fish species like brown trout (Salmo trutta f.f., L.), European grayling (Thymallus thymallus, L.) or nase (Chondrostoma nasus, L.) and the barbel (Barbus barbus, L.). Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is used as major technique for the direct in situ analysis of trace elements and isotopes, whereby the employment of a multiple collector - inductively coupled plasma - mass spectrometer (MC-ICP-MS) enables high precise isotope ratio analysis of such sample matrices due to its simultaneous detection capabilities. Microchemical patterns in hard parts of farmed and wild fish are analysed resulting in natural site specific elemental and isotopic signatures. Within a pilot study the potential to discriminate between wild and hatchery trout by chronological microchemical patterns of different otolith regions in relation to site specific water chemistry was documented. 100% accuracy of classification of fish to life stage specific habitats and therefore to their origin was achieved by the elemental ratios 88Sr/43Ca, 23Na/43Ca and the isotope ratio of 87Sr/86Sr. Clear differences in otolith chemistry were found, when fish experienced different geological units or specific environmental situations (e.g. groundwater) in hatcheries during a certain period of their life. These results proved the concept that natural microchemical patterns in hard parts linked to specific life stages of fish represent a valuable tool for a wide variety of ecological questions, e.g. discriminating wild and hatchery fish without the necessity of inducing any other artificial mark, or studying natural migration phenomena on small spatial scales in freshwater systems within geologically diverse river catchments.

Paleo-oceanography of the Norwegian Sea during the past 130,000 years: Coccolithophorid and foraminferal data

USGS Publications Warehouse

Belanger, P.E.

1982-01-01

Faunal, floral and sedimentological properties of Norwegian Sea core V27-86 were examined in order to reconstruct the paleo-oceanographic history of this region. Downcore variations in the relative abundance of three microfossil groups and several sediment properties exhibit three different climate response patterns (CRP). Each pattern is judged to represent the response of a different part of the climate system. The covariance patterns among coccoliths, henthic foraminifera, and other properties suggest that the Norwegian Sea has been ice-free and productive during the present interhlacial. the penultimate interglacial (isotopic-stage se) and at least partially ice-free during an intermediate climatic regime (stages sa-d). A maximum change in these measures occurs at the boundary between isotopic stage 5a (an intermediate climatic regime)and isotopic stage 4 (a glacial climatic regime). In contrast, planktic foraminiferal assemblages and oxygen isotope measurements on planktic foraminifera show a major change at the end of stage 5e (the penultimate interglacial). The contrasting behavior of these two sets of observations is explained by a model which postulates a low-salinity surface layer 115,000 to 75,000 years ago (stages 5a-d).

Spatial evolution of Zn-Fe-Pb isotopes of sphalerite within a single ore body: A case study from the Dongshengmiao ore deposit, Inner Mongolia, China

NASA Astrophysics Data System (ADS)

Gao, Zhaofu; Zhu, Xiangkun; Sun, Jian; Luo, Zhaohua; Bao, Chuang; Tang, Chao; Ma, Jianxiong

2018-01-01

Analyses of sphalerite minerals from the characteristic brecciated Zn-Pb ores of the main ore body in the giant Dongshengmiao deposit have revealed variations in δ66Zn from 0.17 to 0.40‰ and in δ56Fe from -1.78 to -0.35‰. Further, the investigated pyrrhotite samples have iron that is isotopically similar to that of associated sphalerite minerals. The most distinctive pattern revealed by the zinc and iron isotope data is the lateral trend of increasing δ66Zn and δ56Fe values from southwest to northeast within the main ore body. The lead isotopic homogeneity of ore sulfides from the main ore body suggests that there is only one significant source for metal, thus precluding the mixing of multiple metal sources as the key factor controlling spatial variations of zinc and iron isotopes. The most likely control on spatial variations is Rayleigh fractionation during hydrothermal fluid flow, with lighter Zn and Fe isotopes preferentially incorporated into the earliest sulfides to precipitate from fluids. Precipitations of sphalerite and pyrrhotite have played vital roles in the Zn and Fe isotopic variations, respectively, of the ore-forming system. Accordingly, the larger isotopic variability for Fe than Zn within the same hydrothermal system perhaps resulted from a larger proportion of precipitation for pyrrhotite than for sphalerite. The lateral trend pattern revealed by the zinc and iron isotope data is consistent with the occurrence of a cystic-shaped breccia zone, which is characterized by marked elevation in Cu. The results further confirm that Zn and Fe isotopes can be used as a vectoring tool for mineral prospecting.

Isotopic studies of metabolic systems by mass spectrometry: using Pascal's triangle to produce biological standards with fully controlled labeling patterns.

PubMed

Millard, Pierre; Massou, Stéphane; Portais, Jean-Charles; Létisse, Fabien

2014-10-21

Mass spectrometry (MS) is widely used for isotopic studies of metabolism in which detailed information about biochemical processes is obtained from the analysis of isotope incorporation into metabolites. The biological value of such experiments is dependent on the accuracy of the isotopic measurements. Using MS, isotopologue distributions are measured from the quantitative analysis of isotopic clusters. These measurements are prone to various biases, which can occur during the experimental workflow and/or MS analysis. The lack of relevant standards limits investigations of the quality of the measured isotopologue distributions. To meet that need, we developed a complete theoretical and experimental framework for the biological production of metabolites with fully controlled and predictable labeling patterns. This strategy is valid for different isotopes and different types of metabolisms and organisms, and was applied to two model microorganisms, Pichia augusta and Escherichia coli, cultivated on (13)C-labeled methanol and acetate as sole carbon source, respectively. The isotopic composition of the substrates was designed to obtain samples in which the isotopologue distribution of all the metabolites should give the binomial coefficients found in Pascal's triangle. The strategy was validated on a liquid chromatography-tandem mass spectrometry (LC-MS/MS) platform by quantifying the complete isotopologue distributions of different intracellular metabolites, which were in close agreement with predictions. This strategy can be used to evaluate entire experimental workflows (from sampling to data processing) or different analytical platforms in the context of isotope labeling experiments.

Use of precipitation and groundwater isotopes to interpret regional hydrology on a tropical volcanic island: Kilauea volcano area, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Ingebritsen, S.E.; Janik, C.J.; Kauahikaua, J.P.

1996-01-01

Isotope tracer methods were used to determine flow paths, recharge areas, and relative age for groundwater in the Kilauea volcano area of the Island of Hawaii. A network of up to 66 precipitation collectors was emplaced in the study area and sampled twice yearly for a 3-year period. Stable isotopes in rainfall show three distinct isotopic gradients with elevation, which are correlated with trade wind, rain shadow, and highelevation climatological patterns. Temporal variations in precipitation isotopes are controlled more by the frequency of storms than by seasonal temperature fluctuations. Results from this study suggest that (1) sampling network design must take into account areal variations in rainfall patterns on islands and in continental coastal areas and (2) isotope/elevation gradients on other tropical islands may be predictable on the basis of similar climatology. Groundwater was sampled yearly in coastal springs, wells, and a few high-elevation springs. Areal contrasts in groundwater stable isotopes and tritium indicate that the volcanic rift zones compartmentalize the regional groundwater system, isolating the groundwater south of Kilauea's summit and rift zones. Part of the Southwest Rift Zone appears to act as a conduit for water from higher elevation, but there is no evidence for downrift flow in the springs and shallow wells sampled in the lower East Rift Zone.

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

Use of Precipitation and Groundwater Isotopes to Interpret Regional Hydrology on a Tropical Volcanic Island: Kilauea Volcano Area, Hawaii

NASA Astrophysics Data System (ADS)

Scholl, M. A.; Ingebritsen, S. E.; Janik, C. J.; Kauahikaua, J. P.

1996-12-01

Isotope tracer methods were used to determine flow paths, recharge areas, and relative age for groundwater in the Kilauea volcano area of the Island of Hawaii. A network of up to 66 precipitation collectors was emplaced in the study area and sampled twice yearly for a 3-year period. Stable isotopes in rainfall show three distinct isotopic gradients with elevation, which are correlated with trade wind, rain shadow, and highelevation climatological patterns. Temporal variations in precipitation isotopes are controlled more by the frequency of storms than by seasonal temperature fluctuations. Results from this study suggest that (1) sampling network design must take into account areal variations in rainfall patterns on islands and in continental coastal areas and (2) isotope/elevation gradients on other tropical islands may be predictable on the basis of similar climatology. Groundwater was sampled yearly in coastal springs, wells, and a few high-elevation springs. Areal contrasts in groundwater stable isotopes and tritium indicate that the volcanic rift zones compartmentalize the regional groundwater system, isolating the groundwater south of Kilauea's summit and rift zones. Part of the Southwest Rift Zone appears to act as a conduit for water from higher elevation, but there is no evidence for downrift flow in the springs and shallow wells sampled in the lower East Rift Zone.

Iron and zinc isotope fractionation during uptake and translocation in rice (Oryza sativa) grown in oxic and anoxic soils

NASA Astrophysics Data System (ADS)

Arnold, Tim; Markovic, Tamara; Kirk, Guy J. D.; Schönbächler, Maria; Rehkämper, Mark; Zhao, Fangjie J.; Weiss, Dominik J.

2015-11-01

Stable isotope fractionation is emerging quickly as a powerful novel technique to study metal uptake and translocation in plants. Fundamental to this development is a thorough understanding of the processes that lead to isotope fractionation under differing environmental conditions. In this study, we investigated Zn and Fe isotope fractionation in rice grown to maturity in anaerobic and aerobic soils under greenhouse conditions. The overall Zn isotope fractionation between the soil and above ground plant material was negligible in aerobic soil but significant in anaerobic soil with isotopically lighter Zn in the rice plant. The observed range of fractionation is in line with previously determined fractionations of Zn in rice grown in hydroponic solutions and submerged soils and emphasizes the effect of taking up different chemical forms of Zn, most likely free and organically complexed Zn. The Zn in the grain was isotopically lighter than in the rest of the above ground plant in rice grown in aerobic and anaerobic soils alike. This suggests that in the course of the grain loading and during the translocation within the plant important biochemical and/or biophysical processes occur. The isotope fractionation observed in the grains would be consistent with an unidirectional controlled transport from shoot to grain with a fractionation factor of α ≈ 0.9994. Iron isotopes showed an isotopic lighter signature in shoot and grain compared to the bulk soil or the leachate in aerobic and anaerobic soils alike. The negative direction of isotopic fractionation is consistent with possible changes in the redox state of Fe occurring during the uptake and translocation processes. The isotope fractionation pattern between shoots and grain material are different for Zn and Fe which finally suggests that different mechanisms operate during translocation and grain-loading in rice for these two key micronutrients.

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.

Unravelling biocultural population structure in 4th/3rd century BC Monterenzio Vecchio (Bologna, Italy) through a comparative analysis of strontium isotopes, non-metric dental evidence, and funerary practices.

PubMed

Sorrentino, Rita; Bortolini, Eugenio; Lugli, Federico; Mancuso, Giuseppe; Buti, Laura; Oxilia, Gregorio; Vazzana, Antonino; Figus, Carla; Serrangeli, Maria Cristina; Margherita, Cristiana; Penzo, Annachiara; Gruppioni, Giorgio; Gottarelli, Antonio; Jochum, Klaus Peter; Belcastro, Maria Giovanna; Cipriani, Anna; Feeney, Robin N M; Benazzi, Stefano

2018-01-01

The 4th century BC marks the main entrance of Celtic populations in northern Italy. Their arrival has been suggested based on the presence of Celtic customs in Etruscan mortuary contexts, yet up to now few bioarchaeological data have been examined to support or reject the arrival of these newcomers. Here we use strontium isotopes, non-metric dental traits and funerary patterns to unravel the biocultural structure of the necropolis of Monterenzio Vecchio (Bologna, Italy). Subsamples of our total sample of 38 individuals were analyzed based on different criteria characterizing the following analyses: 1) strontium isotope analysis to investigate migratory patterns and provenance; 2) non-metric dental traits to establish biological relationships between Monterenzio Vecchio, 13 Italian Iron age necropolises and three continental and non-continental Celtic necropolises; 3) grave goods which were statistically explored to detect possible patterns of cultural variability. The strontium isotopes results indicate the presence of local and non-local individuals, with some revealing patterns of mobility. The dental morphology reveals an affinity between Monterenzio Vecchio and Iron Age Italian samples. However, when the Monterenzio Vecchio sample is separated by isotopic results into locals and non-locals, the latter share affinity with the sample of non-continental Celts from Yorkshire (UK). Moreover, systematic analyses demonstrate that ethnic background does not retain measurable impact on the distribution of funerary elements. Our results confirm the migration of Celtic populations in Monterenzio as archaeologically hypothesized on the basis of the grave goods, followed by a high degree of cultural admixture between exogenous and endogenous traits. This contribution shows that combining different methods offers a more comprehensive perspective for the exploration of biocultural processes in past and present populations.

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

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

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

1989-12-01

Leaf water becomes enriched in the heavy isotopes of oxygen and hydrogen during evapotranspiration. The magnitude of the enrichment has been shown to be influenced by temperature and humidity, but the effects of species-specific factors on leaf water enrichment of D and {sup 18}O have not been studied for different plants growing together. To learn whether leaf water enrichment patterns and processes for D and {sup 18}O are different for individual species growing under the same environmental conditions the authors tested the proposal that leaf waters in plants with crassulacean acid metabolism (CAM) show high sloped (m in the leafmore » water equation {delta}D = m {delta}{sup 18}O + b) than in C{sub 3} plants. They determined the relationships between the stable hydrogen ({delta}D) and oxygen ({delta}{sup 18}O) isotope ratios of leaf waters collected during the diurnal cycle of evapotranspiration for Yucca schidigera, Ephedra aspera, Agave deserti, Prunus ilicifolia, Yucca whipplei, Heteromeles arbutifolia, Dyckia fosteriana, Simmondsia chinensis, and Encelia farinosa growing at two sites in southern California. The findings indicate that m in the aforementioned equation is related to the overall residence time for water in the leaf and proportions of water subjected to repeated evapotranspiration enrichments of heavy isotopes.« less

Isotope investigation on groundwater recharge and dynamics in shallow and deep alluvial aquifers of southwest Punjab.

PubMed

Keesari, Tirumalesh; Sharma, Diana A; Rishi, Madhuri S; Pant, Diksha; Mohokar, Hemant V; Jaryal, Ajay Kumar; Sinha, U K

2017-11-01

Groundwater samples collected from the alluvial aquifers of southwest Punjab, both shallow and deep zones were measured for environmental tritium ( 3 H) and stable isotopes ( 2 H and 18 O) to evaluate the source of recharge and aquifer dynamics. The shallow groundwater shows wide variation in isotopic signature (δ 18 O: -11.3 to -5.0‰) reflecting multiple sources of recharge. The average isotopic signature of shallow groundwaters (δ 18 O: -6.73 ± 1.03‰) is similar to that of local precipitation (-6.98 ± 1.66‰) indicating local precipitation contributes to a large extent compared to other sources. Other sources have isotopically distinct signatures due to either high altitude recharge (canal sources) or evaporative enrichment (irrigation return flow). Deep groundwater shows relatively depleted isotopic signature (δ 18 O: -8.6‰) and doesn't show any evaporation effect as compared to shallow zone indicating recharge from precipitation occurring at relatively higher altitudes. Environmental tritium indicates that both shallow ( 3 H: 5 - 10 T.U.) and deeper zone ( 3 H: 1.5 - 2.5 T.U.) groundwaters are modern. In general the inter-aquifer connections seem to be unlikely except a few places. Environmental isotope data suggests that shallow groundwater is dynamic, local and prone to changes in land use patterns while deep zone water is derived from distant sources, less dynamic and not impacted by surface manifestations. A conceptual groundwater flow diagram is presented. Copyright © 2017 Elsevier Ltd. All rights reserved.

Stable isotopes of captive cetaceans (killer whales and bottlenose dolphins).

PubMed

Caut, Stéphane; Laran, Sophie; Garcia-Hartmann, Emmanuel; Das, Krishna

2011-02-15

There is currently a great deal of interest in using stable isotope methods to investigate diet, trophic level and migration in wild cetaceans. In order to correctly interpret the results stemming from these methods, it is crucial to understand how diet isotopic values are reflected in consumer tissues. In this study, we investigated patterns of isotopic discrimination between diet and blood constituents of two species of cetaceans (killer whale, Orcinus orca, and bottlenose dolphin, Tursiops truncatus) fed controlled diets over 308 and 312 days, respectively. Diet discrimination factors (Δ; mean ± s.d.) for plasma were estimated to Δ(13)C=2.3±0.6‰ and Δ(15)N=1.8±0.3‰, respectively, for both species and to Δ(13)C=2.7±0.3‰ and Δ(15)N=0.5±0.1‰ for red blood cells. Delipidation did not have a significant effect on carbon and nitrogen isotopic values of blood constituents, confirming that cetacean blood does not serve as a reservoir of lipids. In contrast, carbon isotopic values were higher in delipidated samples of blubber, liver and muscle from killer whales. The potential for conflict between fisheries and cetaceans has heightened the need for trophic information about these taxa. These results provide the first published stable isotope incorporation data for cetaceans, which are essential if conclusions are to be drawn on issues concerning trophic structures, carbon sources and diet reconstruction.

Uranium disequilibrium in groundwater: An isotope dilution approach in hydrologic investigations

USGS Publications Warehouse

Osmond, J.K.; Rydell, H.S.; Kaufman, M.I.

1968-01-01

The distribution and environmental disequilibrium patterns of naturally occurring uranium isotopes (U234 and U238) in waters of the Floridan aquifer suggest that variations in the ratios of isotopic activity and concentrations can be used quantitatively to evaluate mixing proportions of waters from differing sources. Uranium is probably unique in its potential for this approach, which seems to have general usefulness in hydrologic investigations.

Compensation of matrix effects in gas chromatography-mass spectrometry analysis of pesticides using a combination of matrix matching and multiple isotopically labeled internal standards.

PubMed

Tsuchiyama, Tomoyuki; Katsuhara, Miki; Nakajima, Masahiro

2017-11-17

In the multi-residue analysis of pesticides using GC-MS, the quantitative results are adversely affected by a phenomenon known as the matrix effect. Although the use of matrix-matched standards is considered to be one of the most practical solutions to this problem, complete removal of the matrix effect is difficult in complex food matrices owing to their inconsistency. As a result, residual matrix effects can introduce analytical errors. To compensate for residual matrix effects, we have developed a novel method that employs multiple isotopically labeled internal standards (ILIS). The matrix effects of ILIS and pesticides were evaluated in spiked matrix extracts of various agricultural commodities, and the obtained data were subjected to simple statistical analysis. Based on the similarities between the patterns of variation in the analytical response, a total of 32 isotopically labeled compounds were assigned to 338 pesticides as internal standards. It was found that by utilizing multiple ILIS, residual matrix effects could be effectively compensated. The developed method exhibited superior quantitative performance compared with the common single-internal-standard method. The proposed method is more feasible for regulatory purposes than that using only predetermined correction factors and is considered to be promising for practical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Controls of Isotopic Patterns in Saprotrophic and Ectomycorrhizal Fungi

EPA Science Inventory

Isotopes of nitrogen (δ15N) and carbon (δ13C) in ectomycorrhizal and saprotrophic fungi contain important information about ecological functioning, but the complexity of physiological and ecosystem processes contributing to fungal carbon and nitrogen dynamics has limited our abil...

Discovering Mercury Protein Modifications in Whole Proteomes Using Natural Isotope Distributions Observed in Liquid Chromatography-Tandem Mass Spectrometry

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

Polacco, Benjamin J.; Purvine, Samuel O.; Zink, Erika M.

2011-08-01

The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury’s seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate,more » we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides.« less

Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

USGS Publications Warehouse

Coleman, D.D.; Risatti, J.B.; Schoell, M.

1981-01-01

Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

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.

Differing foraging strategies influence mercury (Hg) exposure in an Antarctic penguin community.

PubMed

Polito, Michael J; Brasso, Rebecka L; Trivelpiece, Wayne Z; Karnovsky, Nina; Patterson, William P; Emslie, Steven D

2016-11-01

Seabirds are ideal model organisms to track mercury (Hg) through marine food webs as they are long-lived, broadly distributed, and are susceptible to biomagnification due to foraging at relatively high trophic levels. However, using these species as biomonitors requires a solid understanding of the degree of species, sexual and age-specific variation in foraging behaviors which act to mediate their dietary exposure to Hg. We combined stomach content analysis along with Hg and stable isotope analyses of blood, feathers and common prey items to help explain inter and intra-specific patterns of dietary Hg exposure across three sympatric Pygoscelis penguin species commonly used as biomonitors of Hg availability in the Antarctic marine ecosystem. We found that penguin tissue Hg concentrations differed across species, between adults and juveniles, but not between sexes. While all three penguins species diets were dominated by Antarctic krill (Euphausia superba) and to a lesser extent fish, stable isotope based proxies of relative trophic level and krill consumption could not by itself sufficiently explain the observed patterns of inter and intra-specific variation in Hg. However, integrating isotopic approaches with stomach content analysis allowed us to identify the relatively higher risk of Hg exposure for penguins foraging on mesopelagic prey relative to congeners targeting epipelagic or benthic prey species. When possible, future seabird biomonitoring studies should seek to combine isotopic approaches with other, independent measures of foraging behavior to better account for the confounding effects of inter and intra-specific variation on dietary Hg exposure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Scale of human mobility in the southern Andes (Argentina and Chile): A new framework based on strontium isotopes.

PubMed

Barberena, Ramiro; Durán, Víctor A; Novellino, Paula; Winocur, Diego; Benítez, Anahí; Tessone, Augusto; Quiroga, María N; Marsh, Erik J; Gasco, Alejandra; Cortegoso, Valeria; Lucero, Gustavo; Llano, Carina; Knudson, Kelly J

2017-10-01

The goal of this article is to assess the scale of human paleomobility and ecological complementarity between the lowlands and highlands in the southern Andes during the last 2,300 years. By providing isotope results for human bone and teeth samples, we assess a hypothesis of "high residential mobility" suggested on the basis of oxygen isotopes from human remains. We develop an isotopic assessment of human mobility in a mountain landscape combining strontium and oxygen isotopes. We analyze bone and teeth samples as an approach to life-history changes in spatial residence. Human samples from the main geological units and periods within the last two millennia are selected. We present a framework for the analysis of bioavailable strontium based on the combination of the geological data with isotope results for rodent samples. The 87 Sr/ 86 Sr values from human samples indicate residential stability within geological regions along life history. When comparing strontium and oxygen values for the same human samples, we record a divergent pattern: while δ 18 O values for samples from distant regions overlap widely, there are important differences in 87 Sr/ 86 Sr values. Despite the large socio-economic changes recorded, 87 Sr/ 86 Sr values indicate a persisting scenario of low systematic mobility between the different geological regions. Our results suggest that strontium isotope values provide the most germane means to track patterns of human occupation of distinct regions in complex geological landscapes, offering a much higher spatial resolution than oxygen isotopes in the southern Andes. © 2017 Wiley Periodicals, Inc.

Al-26, Pu-244, Ti-50, REE, and trace element abundances in hibonite grains from CM and CV meteorites

NASA Technical Reports Server (NTRS)

Fahey, A. J.; Mckeegan, K. D.; Zinner, E.; Goswami, J. N.

1987-01-01

Hibonites from the CM meteorites Murchison, Murray, and Cold Bokkeveld, and hibonites and Ti-rich pyroxene from the CV chondrite Allende are studied. Electron microprobe measurements of major element concentrations and track and ion probe measurements of Mg and Ti isotopic ratios, rare earth elements (REEs), and trace element abundances are analyzed. Correlations between isotopic anomalies in Ti, Al-26, Pu-244, and Mg-26(asterisk) are examined. Ti isotopic anomalies are compared with REE and trace element abundance patterns. Reasons for the lack of Al-26 in the hibonites are investigated and discussed. It is observed that there is no correlation between the Ti isotopic compositions, and the presence of Mg-26(asterisk), Pu-244, and REE and trace element patterns in individual hibonite samples. The data reveal that hibonites are not interstellar dust grains but formed on a short time scale and in localized regions of the early solar system.

Evidence from stable isotopes and 10Be for solar system formation triggered by a low-mass supernova

PubMed Central

Banerjee, Projjwal; Qian, Yong-Zhong; Heger, Alexander; Haxton, W C

2016-01-01

About 4.6 billion years ago, some event disturbed a cloud of gas and dust, triggering the gravitational collapse that led to the formation of the solar system. A core-collapse supernova, whose shock wave is capable of compressing such a cloud, is an obvious candidate for the initiating event. This hypothesis can be tested because supernovae also produce telltale patterns of short-lived radionuclides, which would be preserved today as isotopic anomalies. Previous studies of the forensic evidence have been inconclusive, finding a pattern of isotopes differing from that produced in conventional supernova models. Here we argue that these difficulties either do not arise or are mitigated if the initiating supernova was a special type, low in mass and explosion energy. Key to our conclusion is the demonstration that short-lived 10Be can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed. PMID:27873999

Evidence from stable isotopes and 10Be for solar system formation triggered by a low-mass supernova

DOE PAGES

Banerjee, Projjwal; Qian, Yong -Zhong; Heger, Alexander; ...

2016-11-22

About 4.6 billion years ago, some event disturbed a cloud of gas and dust, triggering the gravitational collapse that led to the formation of the solar system. A core-collapse supernova, whose shock wave is capable of compressing such a cloud, is an obvious candidate for the initiating event. This hypothesis can be tested because supernovae also produce telltale patterns of short-lived radionuclides, which would be preserved today as isotopic anomalies. Previous studies of the forensic evidence have been inconclusive, finding a pattern of isotopes differing from that produced in conventional supernova models. Here we argue that these difficulties either domore » not arise or are mitigated if the initiating supernova was a special type, low in mass and explosion energy. Key to our conclusion is the demonstration that short-lived 10Be can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed.« less

Isotopic composition of carbonaceous-chondrite kerogen Evidence for an interstellar origin of organic matter in meteorites

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1983-01-01

Stepwise combustion has revealed systematic patterns of isotopic heterogeneity for C, H and N in the insoluble organic fraction (m-kerogen) from the Orgueil and Murray carbonaceous chondrites. Those patterns are essentially identical for both meteorites, indicating a common source of m-kerogen. The data cannot be reconciled with a single mass-fractionation process acting upon a single precursor composition. This indicates either a multi-path history of mass-dependent processing or a significant nucleogenetic contribution, or both. If mass-fractionation were the dominant process, the magnitude of the observed isotopic variability strongly suggests that ion-molecule reactions at very low temperatures, probably in interstellar clouds, were responsible. In any case, an interstellar, rather than solar nebular, origin for at least some of the meteoritic organic matter is indicated. This has interesting implications for the origin of prebiotic molecules, temperatures in the early solar system, and the isotopic compositions of volatiles accreted by the terrestrial planets.

Evidence from stable isotopes and 10Be for solar system formation triggered by a low-mass supernova

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

Banerjee, Projjwal; Qian, Yong -Zhong; Heger, Alexander

About 4.6 billion years ago, some event disturbed a cloud of gas and dust, triggering the gravitational collapse that led to the formation of the solar system. A core-collapse supernova, whose shock wave is capable of compressing such a cloud, is an obvious candidate for the initiating event. This hypothesis can be tested because supernovae also produce telltale patterns of short-lived radionuclides, which would be preserved today as isotopic anomalies. Previous studies of the forensic evidence have been inconclusive, finding a pattern of isotopes differing from that produced in conventional supernova models. Here we argue that these difficulties either domore » not arise or are mitigated if the initiating supernova was a special type, low in mass and explosion energy. Key to our conclusion is the demonstration that short-lived 10Be can be readily synthesized in such supernovae by neutrino interactions, while anomalies in stable isotopes are suppressed.« less

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

NASA Astrophysics Data System (ADS)

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

2002-05-01

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

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.

Hydrologic and environmental controls on uranium-series and strontium isotope ratios in a natural weathering environment

NASA Astrophysics Data System (ADS)

White, A. M.; Ma, L.; Moravec, B. G.; McIntosh, J. C.; Chorover, J.

2017-12-01

In a remote, volcanic headwater catchment of the Jemez River Basin Critical Zone Observatory (JRB-CZO) in NM, stable water isotopes and solute chemistry have shown that snowmelt infiltrates and is stored before later discharging into springs and streams via subsurface flowpaths that vary seasonally. Therefore, water-rock reactions are also expected to change with season as hydrologic flowpaths transport water, gases and solutes through different biogeochemical conditions, rock types and fracture networks. Uranium-series isotopes have been shown to be a novel tracer of water-rock reactions and source water contributions while strontium isotopes are frequently used as indicators of chemical weathering and bedrock geology. This study combines both isotopes to understand how U and Sr isotope signatures evolve through the Critical Zone (CZ). More specifically, this work examines the relationship between seasonality, water transit time (WTT), and U-series and Sr isotopes in stream and spring waters from three catchments within the JRB-CZO, as well as lithology, rock type and CZ structure in solid phase cores. Samples from ten springs with known WTTs were analyzed for U and Sr isotopes to determine the effect of WTT on the isotopic composition of natural waters. Results suggest that WTT alone cannot explain the variability of U and Sr isotopes in JRB-CZO springs. Stream samples were also collected across two water years to establish how seasonality controls surface water isotopic composition. U and Sr isotope values vary with season, consistent with a previous study from the La Jara catchment; however, this study revealed that these changes do not show a systematic pattern among the three catchments suggesting that differences in the mineralogy and structure of the deep CZ in individual catchments, and partitioning of water along deep vs surficial and fracture vs matrix flow paths, likely also control isotopic variability. The distribution of U-series and Sr isotopes in core samples with depth shows distinct weathering profiles with variable 234U/238U activity and Sr isotope ratios. Comparison of the isotopic composition of cores and groundwaters from similar depths, as well as surface waters in the JRB-CZO will be vital for the characterization of hydrogeologic controls on isotopic composition in this complex terrain.

[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.

Identification of volatile and semivolatile compounds in chemical ionization GC-MS using a mass-to-structure (MTS) Search Engine with integral isotope pattern ranking.

PubMed

Liao, Wenta; Draper, William M

2013-02-21

The mass-to-structure or MTS Search Engine is an Access 2010 database containing theoretical molecular mass information for 19,438 compounds assembled from common sources such as the Merck Index, pesticide and pharmaceutical compilations, and chemical catalogues. This database, which contains no experimental mass spectral data, was developed as an aid to identification of compounds in atmospheric pressure ionization (API)-LC-MS. This paper describes a powerful upgrade to this database, a fully integrated utility for filtering or ranking candidates based on isotope ratios and patterns. The new MTS Search Engine is applied here to the identification of volatile and semivolatile compounds including pesticides, nitrosoamines and other pollutants. Methane and isobutane chemical ionization (CI) GC-MS spectra were obtained from unit mass resolution mass spectrometers to determine MH(+) masses and isotope ratios. Isotopes were measured accurately with errors of <4% and <6%, respectively, for A + 1 and A + 2 peaks. Deconvolution of interfering isotope clusters (e.g., M(+) and [M - H](+)) was required for accurate determination of the A + 1 isotope in halogenated compounds. Integrating the isotope data greatly improved the speed and accuracy of the database identifications. The database accurately identified unknowns from isobutane CI spectra in 100% of cases where as many as 40 candidates satisfied the mass tolerance. The paper describes the development and basic operation of the new MTS Search Engine and details performance testing with over 50 model compounds.

Spatial patterns of throughfall isotopic composition at the event and seasonal timescales

NASA Astrophysics Data System (ADS)

Allen, Scott T.; Keim, Richard F.; McDonnell, Jeffrey J.

2015-03-01

Spatial variability of throughfall isotopic composition in forests is indicative of complex processes occurring in the canopy and remains insufficiently understood to properly characterize precipitation inputs to the catchment water balance. Here we investigate variability of throughfall isotopic composition with the objectives: (1) to quantify the spatial variability in event-scale samples, (2) to determine if there are persistent controls over the variability and how these affect variability of seasonally accumulated throughfall, and (3) to analyze the distribution of measured throughfall isotopic composition associated with varying sampling regimes. We measured throughfall over two, three-month periods in western Oregon, USA under a Douglas-fir canopy. The mean spatial range of δ18O for each event was 1.6‰ and 1.2‰ through Fall 2009 (11 events) and Spring 2010 (7 events), respectively. However, the spatial pattern of isotopic composition was not temporally stable causing season-total throughfall to be less variable than event throughfall (1.0‰; range of cumulative δ18O for Fall 2009). Isotopic composition was not spatially autocorrelated and not explained by location relative to tree stems. Sampling error analysis for both field measurements and Monte-Carlo simulated datasets representing different sampling schemes revealed the standard deviation of differences from the true mean as high as 0.45‰ (δ18O) and 1.29‰ (d-excess). The magnitude of this isotopic variation suggests that small sample sizes are a source of substantial experimental error.

Monitoring BTEX degradation by CSIA - chances and challenges

NASA Astrophysics Data System (ADS)

Vogt, Carsten; Dorer, Conrad; Kümmel, Steffen; Bombach, Petra; Fischer, Anko; Richnow, Hans Hermann

2014-05-01

Monitoring is crucial for evaluating the success of any geobiotechnological applications. Compound- specific stable isotope analysis (CSIA) has emerged as a key method for monitoring biogeochemical transformation processes. Isotope compositions of residual reactants may change during the first rate-limiting step in (bio)chemical reactions; measurement of these changes are the basis for CSIA. Caused by differences in the activation energy, light isotopologues often react slightly faster than heavy isotopologues, resulting in enrichment of heavy isotopes at the reactive site in the substrate or of light isotopes in the product. This is termed isotope fractionation. Upon multi-dimensional CSIA (2D-CSIA, 3D-CSIA), the isotope fractionation of two or more different elements within a molecule is determined, allowing highly resolved analyses of degradation processes as masking effects typically occurring in one-dimensional CSIA are cancelled. In the last years, 2D-CSIA making use of the ratio of stable carbon to hydrogen isotopes (13C/12C, 2H/1H), turned out to be an important tool for elucidating the environmental biodegradation pattern of BTEX compounds which are global notorious contaminants. This presentation aims to summarize the current knowledge on 2D-CSIA of BTEX, to point out the prospects and to indicate future perspectives upon monitoring in the field. Degradation experiments for determining carbon and hydrogen isotope fractionation factors were carried out using several pure and mixed cultures performing different BTEX-activating reactions. Various anaerobic key reactions showed pronounced hydrogen isotope fractionation: (i) fumarate addition to the methyl moiety of toluene, xylene isomers and probably ethylbenzene catalyzed by benzylsuccinate synthases, (ii) anaerobic hydroxylation of the ethyl side chain of ethylbenzene catalyzed by ethylbenzene dehydrogenase, and (iii) anaerobic activation of benzene by yet unknown biochemical mechanisms. Due to the high hydrogen isotope fractionation, the ratios of hydrogen vs. carbon isotope fractionation in two-dimensional plots (lambda values, Λ) were generally higher than 10 (in extreme cases > 100). Upon aerobic activation reactions at the aromatic ring catalyzed by mono- or dioxygenases, usually Λ values smaller than 10 were observed due to small, absent or inverse hydrogen isotope fractionation. An exception is the aerobic monooxygenation of methyl or methylene moieties which is linked to large hydrogen and carbon isotope fractionation. Since Λ values are highly indicative for specific transformation reactions, 2D-CSIA has a great potential for evaluating biodegradation processes of BTEX in the environment. Moreover, reactions catalyzed by benzylsuccinate synthases showed partially variable Λ values, indicating slightly different reaction mechanisms of isoenzymes, probably permitting the detection of specific isoenzymes by 2D-CSIA in field applications. In contrast, ethylbenzene dehydrogenase of three tested organisms showed similar, very characteristic isotope fractionation pattern even under different redox conditions. The major goal of future investigations is to use 2D-CSIA at contaminated field sites for elucidating specific degradation pathways. Single data for benzene are promising, demonstrating e.g., anaerobic benzene degradation by 2D-CSIA at a highly contaminated site. Nevertheless, 2D-CSIA field data for BTEX are yet lacking and need to be surveyed for a proper evaluation of the 2D-CSIA concept for BTEX.

Isotope and chemical compositions of meteoric and thermal waters and snow from the greater Yellowstone National Park region

USGS Publications Warehouse

Kharaka, Yousif K.; Thordsen, James J.; White, Lloyd D.

2002-01-01

An intensive hydrogeologic investigation, mandated by U.S. Congress and centered on the Norris-Mammoth corridor was conducted by USGS and other scientists during 1988-90 to determine the effects of using thermal water from a private well located in the Corwin Springs Known Geothermal Resources Area, Montana, on the thermal springs of Yellowstone National Park (YNP), especially Mammoth Hot Springs. As part of this investigation, we carried out a detailed study of the isotopic and chemical compositions of meteoric water from cold springs and wells, of thermal water, especially from the Norris-Mammoth corridor and of snow. Additional sampling of meteoric and thermal waters from YNP and surrounding region in northwest Wyoming, southwest Montana and southeast Idaho was carried out in 1991-92 to characterize the distribution of water isotopes in this mountainous region and to determine the origin and possible recharge locations of thermal waters in and adjacent to the Park. The D and 18O values for 40 snow samples range from ?88 to ?178? and ?12.5 to ?23.9?, respectively, and define a well constrained line given by D = 8.2 18O + 14.7 (r2 = 0.99) that is nearly identical to the Global Meteoric Water Line. The D and 18O values of 173 cold water samples range from ?115 to ?153? and ?15.2 to ?20.2?, respectively, and exhibit a similar relationship although with more scatter and with some shift to heavier isotopes, most likely due to evaporation effects. The spatial distribution of cold-water isotopes shows a roughly circular pattern with isotopically lightest waters centered on the mountains and high plateau in the northwest corner of Yellowstone National Park and becoming heavier in all directions. The temperature effect due to altitude is the dominant control on stable water isotopes throughout the region; however, this effect is obscured in narrow 'canyons' and areas of high topographic relief. The effects due to distance (i.e. 'continental') and latitude on water isotopes probably are relatively minor and difficult to resolve from the major controls. The data indicate that the groundwater are derived predominantly from cold, isotopically light winter precipitation, and that the isotope values of groundwater from elevations above about 2.5-3.0 km in the Gallatin and northern Absaroka Ranges are light enough (The D ?149?) to be the presumed recharge water for the hydrothermal system in the Park. However, estimation of the present-day volume of this recharged, isotopically light water indicates that it is not adequate to supply the high (3-4 m3/s) thermal water discharges from YNP, and cooler temperatures at the time of recharge would be required. The volume of meteoric water with D values lighter than ?145? may be adequate for recharging the hydrothermal system, and this may be a more plausible value than the ?149? originally calculated from data that are subject to moderate uncertainties.

The use of stable isotope to evaluate water mixing and water use by flood plain trees along the Garonne valley

USGS Publications Warehouse

Lambs, L.; Loubiat, M.; Richardson, W.

2003-01-01

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (18O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. 18O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (??18O: -9.1??? to -9.0???, conductivity: 217-410??S/cm) was distinctly different from groundwater (??18O: -7.1??? to -6.6???, conductivity: 600-900??S/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (1m). Trees at both locations maintained sap with ionic charges much greater (2.3-3.7x) than that of source water. The combined use of 18O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.

Isotopic fingerprint of the middle Olt River basin, Romania.

PubMed

Popescu, Raluca; Costinel, Diana; Ionete, Roxana Elena; Axente, Damian

2014-01-01

One of the most important tributaries of the Danube River in Romania, the Olt River, was characterized in its middle catchment in terms of the isotopic composition using continuous flow-isotope ratio mass spectrometry (CF-IRMS). Throughout a period of 10 months, from November 2010 to August 2011, water samples from the Olt River and its more important tributaries were collected in order to investigate the seasonal and spatial isotope patterns of the basin waters. The results revealed a significant difference between the Olt River and its tributaries, by the fact that the Olt River waters show smaller seasonal variations in the stable isotopic composition and are more depleted in (18)O and (2)H. The waters present an overall enrichment in heavy isotopes during the warm seasons.

The Evolution of the Protoplanetary Disk Recorded by Nucleosynthetic Isotope Variations of Variable Stellar Origin in Refractory Inclusions

NASA Astrophysics Data System (ADS)

Schönbächler, M.; Lai, Y.-J.; Henshall, T.; Fehr, M. A.; Cook, D. L.; Bullock, E. S.

2017-07-01

New CAI data confirm the homogeneous distribution of the short-lived p-process isotope 92Nb in the early solar system with the exception of CAIs with group II REE pattern that show increased 92Nb abundances.

Patterns in stable isotope ratios of particulate material from the eastern US continental shelf

EPA Science Inventory

Stable isotope measurements of nitrogen and carbon (δ15N, δ13C) in estuarine, nearshore, and open ocean ecosystems are often utilized in order to characterize human influences, elucidate food web dynamics, or better understand nitrogen cycling. Reliable information a...

CARBOHYDRATE USE AND ASSIMILATION BY LITTER AND SOIL FUNGI ASSESSED BY CARBON ISOTOPES AND BIOLOG ASSAYS

EPA Science Inventory

Soil fungi are integral to decomposition in forests, yet identification of probable functional roles of different taxa is problematic. Here, we compared carbohydrate assimilation patterns derived from stable isotope analyses on cultures with those produced from cultures on Biolo...

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

NASA Astrophysics Data System (ADS)

Demény, Attila; Kern, Zoltán; Czuppon, György; Németh, Alexandra; Leél-Őssy, Szabolcs; Siklósy, Zoltán; Lin, Ke; Hu, Hsun-Ming; Shen, Chuan-Chou; Vennemann, Torsten W.; Haszpra, László

2017-04-01

Studies on the last interglacial (LIG) can provide information on how our environment behaved in a period of slightly higher global temperatures at about 125 ± 4 ka, even if it is not the best analogue for the Holocene. The available LIG climate proxy records are usually better preserved and can be studied at a higher resolution than those of the preceding interglacials, allowing detailed comparisons. This paper presents complex stable hydrogen, carbon and oxygen isotope records obtained for carbonate (δ13C and δ18Ocarb) and fluid inclusion hosted water (δD and δ18Ow) of a stalagmite from the Baradla Cave system in Central Europe that covers most of the LIG, as proven by U-Th dates. Comparing its C and O isotope data with records reported for other speleothem (cave-hosted carbonate) deposits from Europe revealed the complex behavior of these climate proxies, with a concerted relative increase in 18O of carbonates from 128 to 120 ka and synchronized shifts in the opposite direction after 119 ka. The hydrogen isotope analyses of inclusion-hosted water extracted from the BAR-II stalagmite also correspond to the regional climate proxy records, with meaningful deviations from global temperature trends. Beside following the general paleotemperature pattern from the climate optimum (high δD values up to -64‰ around 120 ka) to the subsequent cooling starting at about 119 ka (low δD values down to -90‰ at about 109 ka), a period between 126.5 and 123 ka with low δD values (down to -81‰) is detected in the BAR-II stalagmite. Although the isotope shifts are muted in the C-O isotope data of carbonate due to competitive fractionation processes, the δ13C data show a positive relationship with the δD pattern, indicating humidity - and possibly temperature - variations. The periods with low δD values fit well to temperature and humidity changes inferred from proxy records from western Europe to the eastern Mediterranean. Spatial distributions of these variables show, that at about 125 ± 2 ka the Mediterranean region was characterized by warm, humid conditions and enhanced seasonality with elevated winter precipitation. The combined interpretation of stable isotope data revealed that the Alpine and Mediterranean regions behaved differently during Greenland Stadial 26 (GS26, ∼119 to 116.2 ka). While the Alpine records fluctuated in close agreement with the Central Greenland ice core δ18O data, the BAR-II stalagmite show a positive δ18Ocarb anomaly. The Baradla data indicate enhanced aridity and seasonality for a part of GS26, with the relative dominance of summer precipitation and Mediterranean moisture contribution. Following the GS26 event, the effect of long-term global cooling becomes dominant in the Baradla isotope records and leads to glacial inception at about 109 ka.

Characterization of phenols biodegradation by compound specific stable isotope analysis

NASA Astrophysics Data System (ADS)

Wei, Xi; Gilevska, Tetyana; Wenzig, Felix; Hans, Richnow; Vogt, Carsten

2015-04-01

Biodegradation of phenol and alkylphenols has been described under both oxic and anoxic conditions. In the absence of molecular oxygen, the degradation of phenolic compounds is initiated by microorganisms through carboxylation, fumarate addition to the methyl moiety or anoxic hydroxylation of the methyl moiety. Comparatively, under aerobic condition, the initiation mechanisms are revealed to be monoxygenation or dihydroxylation for phenol and ring hydroxylation or methyl group oxidation for cresols. While several studies biochemically characterized the enzymes and reaction mechanisms in the relevant degradation pathways, isotope fractionation patterns were rarely reported possibly due to constraints in current analytical methods. In this study, the carbon isotope fractionation patterns upon the degradation of phenol and cresols by several strains were analyzed by using isotope ratio mass spectrometry connected with liquid chromatography (LC-IRMS). The corresponding enrichment factors for carbon (ƐC) have been obtained. Cresols degradation by various strains showed generally moderate carbon isotope fractionation patterns with notable differences. For p-cresol degradation, five strains were examined. The aerobic strain Acinetobacter calcoaceticus NCIMB8250 exploits ring hydroxylation by molecular oxygen as initial reaction, and a ƐC value of -1.4±0.2‰ was obtained. Pseudomonas pseudoalcaligenes NCIMB 9867, an aerobic strain initiating cresols degradation via oxygen-dependent side chain hydroxylation, yielded a ƐC value of -2.3±0.2‰. Under nitrate-reducing conditions, Geobacter metallireducens DSM 7210 and Azoarcus buckelii DSM 14744 attacks p-cresol at the side chain by monohydroxylation using water as oxygen source; the two strains produced ƐC values of -3.6±0.4‰ and -2±0.1‰, accordingly. The sulfate-reducing Desulfosarcina cetonica DSM 7267 activating cresols by fumarate addition to the methyl moiety yielded ƐC values of -1.9±0.2‰ for p-cresol degradation and 2.2±0.3‰ for m-cresol degradation, respectively. The carbon isotope fractionation patterns of phenol degradation differed more profoundly. Oxygen-dependent monooxygenation of phenol by A.calcoaceticus as the initial reaction yielded ƐC values of -1.5±0.02‰. In contrast, the anaerobic degradation initiated by ATP-dependent carboxylation performed by Thauera aromatia DSM 6984, produced no detectable fractionation (ƐC 0±0.1‰). D. cetonica showed a slight inverse carbon isotope fractionation (ƐC 0.4±0.1‰). In conclusion, a validated method for compound specific stable isotope analysis was developed for phenolic compounds, and the first data set of carbon enrichment factors upon the biodegradation of phenol and cresols with different activation mechanisms has been obtained in the present study. Carbon isotope fractionation analysis is a potentially powerful tool to monitor phenolic compounds degradation in the environment.

Terrestrial cycling of 13CO2 by photosynthesis, respiration, and biomass burning in SiBCASA

NASA Astrophysics Data System (ADS)

van der Velde, I. R.; Miller, J. B.; Schaefer, K.; van der Werf, G. R.; Krol, M. C.; Peters, W.

2014-12-01

We present an enhanced version of the SiBCASA terrestrial biosphere model that is extended with (a) biomass burning emissions from the SiBCASA carbon pools using remotely sensed burned area from the Global Fire Emissions Database (GFED), (b) an isotopic discrimination scheme that calculates 13C signatures of photosynthesis and autotrophic respiration, and (c) a separate set of 13C pools to carry isotope ratios into heterotrophic respiration. We quantify in this study the terrestrial exchange of CO2 and 13CO2 as a function of environmental changes in humidity and biomass burning. The implementation of biomass burning yields similar fluxes as CASA-GFED both in magnitude and spatial patterns. The implementation of isotope exchange gives a global mean discrimination value of 15.2‰, ranges between 4 and 20‰ depending on the photosynthetic pathway in the plant, and compares favorably (annually and seasonally) with other published values. Similarly, the isotopic disequilibrium is similar to other studies that include a small effect of biomass burning as it shortens the turnover of carbon. In comparison to measurements, a newly modified starch/sugar storage pool propagates the isotopic discrimination anomalies to respiration much better. In addition, the amplitude of the drought response by SiBCASA is lower than suggested by the measured isotope ratios. We show that a slight increase in the stomatal closure for large vapor pressure deficit would amplify the respired isotope ratio variability. Our study highlights the importance of isotope ratio observations of 13C to assess and improve biochemical models like SiBCASA, especially with regard to the allocation and turnover of carbon and the responses to drought.

Spatiotemporal patterns of plant water isotope values from a continental-scale sample network in Europe as a tool to improve hydroclimate proxies

NASA Astrophysics Data System (ADS)

Nelson, D. B.; Kahmen, A.

2016-12-01

The hydrogen and oxygen isotopic composition of water available for biosynthetic processes in vascular plants plays an important role in shaping the isotopic composition of organic compounds that these organisms produce, including leaf waxes and cellulose in leaves and tree rings. Characterizing changes in large scale spatial patterns of precipitation, soil water, stem water, and leaf water isotope values over time is therefore useful for evaluating how plants reflect changes in the isotopic composition of these source waters in different environments. This information can, in turn, provide improved calibration targets for understanding the environmental signals that plants preserve. The pathway of water through this continuum can include several isotopic fractionations, but the extent to which the isotopic composition of each of these water pools varies under normal field conditions and over space and time has not been systematically and concurrently evaluated at large spatial scales. Two season-long sampling campaigns were conducted at nineteen sites throughout Europe over the 2014 and 2015 growing seasons to track changes in the isotopic composition of plant-relevant waters. Samples of precipitation, soil water, stem water, and leaf water were collected over more than 200 field days and include more than 500 samples from each water pool. Measurements were used to validate continent-wide gridded estimates of leaf water isotope values derived from a combination of mechanistic and statistical modeling conducted with temperature, precipitation, and relative humidity data. Data-model comparison shows good agreement for summer leaf waters, and substantiates the incorporation of modeled leaf waters in evaluating how plants respond to hydroclimate changes at large spatial scales. These results also suggest that modeled leaf water isotope values might be used in future studies in similar ecosystems to improve the coverage density of spatial or temporal data.

Stable Isotope Mapping of Alaskan Grasses and Marijuana

NASA Astrophysics Data System (ADS)

Booth, A. L.; Wooller, M. J.

2008-12-01

The spatial variation of isotope signatures in organic material is a useful forensic tool, particularly when applied to the task of tracking the production and distribution of plant-derived illicit drugs. In order to identify the likely grow-locations of drugs such as marijuana from unknown locations (i.e., confiscated during trafficking), base isotope maps are needed that include measurements of plants from known grow-locations. This task is logistically challenging in remote, large regions such as Alaska. We are therefore investigating the potential of supplementing our base (marijuana) isotope maps with data derived from other plants from known locations and with greater spatial coverage in Alaska. These currently include >150 samples of modern C3 grasses (Poaceae) as well as marijuana samples (n = 18) from known grow-locations across the state. We conducted oxygen, carbon and nitrogen stable isotope analyses of marijuana and grasses (Poaceae). Poaceae samples were obtained from the University of Alaska Fairbanks (UAF) Museum of the North herbarium collection, originally collected by field botanists from around Alaska. Results indicate that the oxygen isotopic composition of these grasses range from 10‰ to 30‰, and broadly mirror the spatial pattern of water isotopes in Alaska. Our marijuana samples were confiscated around the state of Alaska and supplied to us by the UAF Police Department. δ13C, δ15N and δ18O values exhibit geographic patterns similar to the modern grasses, but carbon and nitrogen isotopes of some marijuana plants appear to be influenced by additional factors related to indoor growing conditions (supplementary CO2 sources and the application of organic fertilizer). As well as providing a potential forensic resource, our Poaceae isotope maps could serve additional value by providing resources for studying ecosystem nutrient cycling, for tracing natural ecological processes (i.e., animal migration and food web dynamics) and providing modern data for comparison with isotope analyses conducted on fossil leaf material in paleoecological studies.

Application of non-lethal stable isotope analysis to assess feeding patterns of juvenile pallid sturgeon Scaphirhynchus albus: a comparison of tissue types and sample preservation methods

USGS Publications Warehouse

Andvik, R.T.; VanDeHey, J.A.; Fincel, M.J.; French, William E.; Bertrand, K.N.; Chipps, Steven R.; Klumb, Robert A.; Graeb, B.D.S.

2010-01-01

Traditional techniques for stable isotope analysis (SIA) generally require sacrificing animals to collect tissue samples; this can be problematic when studying diets of endangered species such as the pallid sturgeon Scaphirhynchus albus. Our objectives were to (i) determine if pectoral fin tissue (non-lethal) could be a substitute for muscle tissue (lethal) in SIA of juvenile pallid sturgeon, and (ii) evaluate the influence of preservation techniques on stable isotope values. In the laboratory, individual juvenile pallid sturgeon were held for up to 186 day and fed chironomids, fish, or a commercially available pellet diet. Significant, positive relationships (r² ≥ 0.8) were observed between fin and muscle tissues for both δ15N and δ13C; in all samples isotopes were enriched in fins compared to muscle tissue. Chironomid and fish based diets of juvenile pallid sturgeon were distinguishable for fast growing fish (0.3 mm day−1) using stable δ15N and δ13C isotopes. Frozen and preserved fin tissue δ15N isotopes were strongly related (r2 = 0.89) but δ13C isotopes were weakly related (r2 = 0.16). Therefore, freezing is recommended for preservation of fin clips to avoid the confounding effect of enrichment by ethanol. This study demonstrates the utility of a non-lethal technique to assess time integrated food habits of juvenile pallid sturgeon and should be applicable to other threatened or endangered species.

Carbon Isotopes of Alkanes in Hydrothermal Abiotic Organic Synthesis Processes at High Temperatures and Pressures: An Experimental Study

NASA Technical Reports Server (NTRS)

Fu, Qi; Socki, Richard A.; Niles, Paul B.

2010-01-01

Observation of methane in the Martian atmosphere has been reported by different detection techniques [1-4]. With more evidence showing extensive water-rock interaction in Martian history [5-7], abiotic formation by Fischer-Tropsch Type (FTT) synthesis during serpentization reactions may be one possible process responsible for methane generation on Mars [8, 9]. While the experimental studies performed to date leave little doubt that chemical reactions exist for the abiotic synthesis of organic compounds by mineral surface-catalyzed reactions [10-12], little is known about the reaction pathways by which CO2 and/or CO are reduced under hydrothermal conditions. Carbon and hydrogen isotope measurements of alkanes have been used as an effective tool to constrain the origin and reaction pathways of hydrocarbon formation. Alkanes generated by thermal breakdown of high molecular weight organic compounds have carbon and hydrogen isotopic signatures completely distinct from those formed abiotically [13-15]. Recent experimental studies, however, showed that different abiogenic hydrocarbon formation processes (e.g., polymerization vs. depolymerization) may have different carbon and hydrogen isotopic patterns [16]. Results from previous experiments studying decomposition of higher molecular weight organic compounds (lignite) also suggested that pressure could be a crucial factor affecting fractionation of carbon isotopes [17]. Under high pressure conditions, no experimental data are available describing fractionation of carbon isotope during mineral catalyzed FTT synthesis. Thus, hydrothermal experiments present an excellent opportunity to provide the requisite carbon isotope data. Such data can also be used to identify reaction pathways of abiotic organic synthesis under experimental conditions.

Physiological responses to fertilization recorded in tree rings: isotopic lessons from a long-term fertilization trial - 2008

EPA Science Inventory

Nitrogen fertilizer applications are common land-use management tools, but details on physiological responses to these applications are often lacking, particularly for long-term responses over decades of forest management. We used tree-ring growth patterns and stable isotopes to...

Physiological responses to fertilization recorded in tree rings: Isotopic lessons from a long-term fertilization trial

EPA Science Inventory

Nitrogen fertilizer applications are common land use management tools, but details on physiological responses to these applications are often lacking, particularly for long-term responses over decades of forest management. We used tree ring growth patterns and stable isotopes to ...

Stable Isotope Values of Nitrogen and Carbon in Particulate Matter: Data

EPA Science Inventory

Data set from “Patterns in stable isotope values of nitrogen and carbon in particulate matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras” by Oczkowski et al. These are the data upon which all results and conclusion are made...

Transport-Induced Spatial Patterns of Sulfur Isotopes (δ34S) as Biosignatures

NASA Astrophysics Data System (ADS)

Mansor, Muammar; Harouaka, Khadouja; Gonzales, Matthew S.; Macalady, Jennifer L.; Fantle, Matthew S.

2018-01-01

Cave minerals deposited in the presence of microbes may host geochemical biosignatures that can be utilized to detect subsurface life on Earth, Mars, or other habitable worlds. The sulfur isotopic composition of gypsum (CaSO4·2H2O) formed in the presence of sulfur-oxidizing microbes in the Frasassi cave system, Italy, was evaluated as a biosignature. Sulfur isotopic compositions (δ34SV-CDT) of gypsum sampled from cave rooms with sulfidic air varied from -11 to -24‰, with minor deposits of elemental sulfur having δ34S values between -17 and -19‰. Over centimeter-length scales, the δ34S values of gypsum varied by up to 8.5‰. Complementary laboratory experiments showed negligible fractionation during the oxidation of elemental sulfur to sulfate by Acidithiobacillus thiooxidans isolated from the caves. Additionally, gypsum precipitated in the presence and absence of microbes at acidic pH characteristic of the sulfidic cave walls has δ34S values that are on average 1‰ higher than sulfate. We therefore interpret the 8.5‰ variation in cave gypsum δ34S (toward more negative values) to reflect the isotopic effect of microbial sulfide oxidation directly to sulfate or via elemental sulfur intermediate. This range is similar to that expected by abiotic sulfide oxidation with oxygen, thus complicating the use of sulfur isotopes as a biosignature at centimeter-length scales. However, at the cave room (meter-length) scale, reactive transport modeling suggests that the overall ˜13‰ variability in gypsum δ34S reflects isotopic distillation of circulating H2S gas due to microbial sulfide oxidation occurring along the cave wall-atmosphere interface. Systematic variations of gypsum δ34S along gas flow paths can thus be interpreted as biogenic given that slow, abiotic oxidation cannot produce the same spatial patterns over similar length scales. The expression and preservation potential of this biosignature is dependent on gas flow parameters and diagenetic processes that modify gypsum δ34S values over geological timescales.

A single-substrate model to interpret high-resolution intra-annual stable isotope signals in tree ring cellulose

NASA Astrophysics Data System (ADS)

Ogée, J.; Barbour, M. M.; Dewar, R. C.; Wingate, L.; Bert, D.; Bosc, A.; Lambrot, C.; Stievenard, M.; Bariac, T.; Berbigier, P.; Loustau, D.

2007-12-01

High-resolution measurements of the carbon and oxygen stable isotope composition of cellulose in annual tree rings (δ13Ccellulose and δ18Ocellulose, respectively) reveal well-defined seasonal patterns that could contain valuable records of past climate and tree function. Interpreting these signals is nonetheless complex because they not only record the signature of current assimilates, but also depend on carbon allocation dynamics within the trees. Here, we will present a single-substrate model for wood growth in order to interpret qualitatively and quantitatively these seasonal isotopic signals. We will also show how this model can relate to more complex models of phloem transport and cambial activity. The model will then be tested against an isotopic intra-annual chronology collected on a Pinus pinaster tree equipped with point dendrometers and growing on a Carboeurope site where climate, soil and flux variables are also monitored. The empirical δ13Ccellulose and δ18Ocellulose signals exhibit dynamic seasonal patterns with clear differences between years, which makes it suitable for model testing. We will show how our simple model of carbohydrate reserves, forced by sap flow and eddy covariance measurements, enables us to interpret these seasonal and inter-annual patterns. Finally, we will present a sensitivity analysis of the model, showing how gas-exchange parameters, carbon and water pool sizes or wood maturation times affect these isotopic signals. Acknowledgements: this study benefited from the CarboEurope-IP Bray site facilities and was funded by the French INSU programme Eclipse, with an additional support from the INRA department EFPA.

Investigating differences in light stable isotopes between Thai jasmine rice and Sungyod rice

NASA Astrophysics Data System (ADS)

Kukusamude, C.; Kongsri, S.

2017-10-01

We report the differences in light stable isotopes between two kinds of Thai rice (Thai jasmine and Sungyod rice). Thai jasmine rice and Sungyod rice were cultivated in the northeast and the south of Thailand. Light isotopes including 13C, 15N and 18O of Thai jasmine rice and Sungyod rice samples were carried out using isotope ratio mass spectrometry (IRMS). Thai jasmine rice (Khao Dawk Mali 105) was cultivated from Thung Kula Rong Hai area, whereas Sungyod rice was cultivated from Phathalung province. Hypothesis testing of difference of each isotope between Thai jasmine rice and Sungyod rice was also studied. The study was the feasibility test whether the light stable isotopes can be the variables to identify Thai jasmine rice and Sungyod rice. The result shows that there was difference in the isotope patterns of Thai jasmine rice and Sungyod rice. Our results may provide the useful information in term of stable isotope profiles of Thai rice.

Fast methodology for the reliable determination of nonylphenol in water samples by minimal labeling isotope dilution mass spectrometry.

PubMed

Fabregat-Cabello, Neus; Castillo, Ángel; Sancho, Juan V; González, Florenci V; Roig-Navarro, Antoni Francesc

2013-08-02

In this work we have developed and validated an accurate and fast methodology for the determination of 4-nonylphenol (technical mixture) in complex matrix water samples by UHPLC-ESI-MS/MS. The procedure is based on isotope dilution mass spectrometry (IDMS) in combination with isotope pattern deconvolution (IPD), which provides the concentration of the analyte directly from the spiked sample without requiring any methodological calibration graph. To avoid any possible isotopic effect during the analytical procedure the in-house synthesized (13)C1-4-(3,6-dimethyl-3-heptyl)phenol was used as labeled compound. This proposed surrogate was able to compensate the matrix effect even from wastewater samples. A SPE pre-concentration step together with exhaustive efforts to avoid contamination were included to reach the signal-to-noise ratio necessary to detect the endogenous concentrations present in environmental samples. Calculations were performed acquiring only three transitions, achieving limits of detection lower than 100ng/g for all water matrix assayed. Recoveries within 83-108% and coefficients of variation ranging from 1.5% to 9% were obtained. On the contrary a considerable overestimation was obtained with the most usual classical calibration procedure using 4-n-nonylphenol as internal standard, demonstrating the suitability of the minimal labeling approach. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

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.

Cenozoic climate evolution in Asian region and its influence on isotopic composition of precipitation

NASA Astrophysics Data System (ADS)

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

2015-04-01

The evolution of Asian climate during the Cenozoic as well as the onset of monsoon systems in this area is highly debated. Factors that control climate include the geographical position of continents, the land-sea distribution and altitude of orogens. In tern, several climatic parameters such as air temperature, precipitation amount and isotopic fractionation through mass-dependent processes impact precipitation δ18O lapse rate. Stable oxygen paleoaltimetry is considered to be a very efficient and widely applied technique, but the link between stable oxygen composition of precipitation and climate is not well established. To quantify the influence of paleogeography changes on climate and precipitation δ18O over Asia, the atmospheric general circulation model LMDZ-iso, with embedded stable oxygen isotopes, was used. For more realistic experiments, sea surface temperatures were calculated with the fully coupled model FOAM. Various scenarios of TP growth have been applied together with Paleocene, Eocene, Oligocene and Miocene boundary conditions. The results of our numerical modelling show a significant influence of paleogeography changes on the Asian climate. The retreat of the Paratethys ocean, the changes in latitudinal position of India, and the height of the Tibetan Plateau most likely control precipitation patterns over Asia and cause spatial and temporal isotopic variations linked with the amount effect. Indian Ocean currents restructuring during the Eocene induces a substantial warming over Asian continent. The adiabatic and non-adiabatic temperature effects explain some of δ18O signal variations. We highlight the importance of these multiple factor on paleoelevations estimates derived using oxygen stable isotopes.

Variable Isotopic Compositions of Host Plant Populations Preclude Assessment of Aphid Overwintering Sites

PubMed Central

Voegtlin, David J.; Hamilton, Krista L.; Hogg, David B.

2017-01-01

Soybean aphid (Aphis glycines Matsumura) is a pest of soybean in the northern Midwest whose migratory patterns have been difficult to quantify. Improved knowledge of soybean aphid overwintering sites could facilitate the development of control efforts with exponential impacts on aphid densities on a regional scale. In this preliminary study, we explored the utility of variation in stable isotopes of carbon and nitrogen to distinguish soybean aphid overwintering origins. We compared variation in bulk 13C and 15N content in buckthorn (Rhamnus cathartica L.) and soybean aphids in Wisconsin, among known overwintering locations in the northern Midwest. Specifically, we looked for associations between buckthorn and environmental variables that could aid in identifying overwintering habitats. We detected significant evidence of correlation between the bulk 13C and 15N signals of soybean aphids and buckthorn, despite high variability in stable isotope composition within and among buckthorn plants. Further, the 15N signal in buckthorn varied predictably with soil composition. However, lack of sufficient differentiation of geographic areas along axes of isotopic and environmental variation appears to preclude the use of carbon and nitrogen isotopic signals as effective predictors of likely aphid overwintering sites. These preliminary data suggest the need for future work that can further account for variability in 13C and 15N within/among buckthorn plants, and that explores the utility of other stable isotopes in assessing likely aphid overwintering sites. PMID:29206134

The evolution of Phanerozoic seawater - Isotope paleothermometry finds consensus on Early Paleozoic warmth and constant seawater δ18O

NASA Astrophysics Data System (ADS)

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

2015-12-01

Evolution of metazoan life is closely linked to the Phanerozoic evolution of ocean temperatures and chemistry. Oxygen isotopic evidence for early Phanerozoic paleotemperatures has been equivocal, with decreasing δ18O values with age being interpreted as warmer early oceans, decreasing seawater δ18O with age, or increasing diagenetic alteration in older samples. Here we compare an updated compilation of oxygen isotope data for carbonate and phosphate fossils and microfossils (Grossman, 2012, Geol. Time Scale, Elsevier, 195-220) with a compilation of new and existing clumped isotope data. Importantly, these data are curated based on sample preservation with special consideration given to screening techniques, and tectonic and burial history. Burial history is critical in the preservation of carbonate clumped isotope temperatures in particular, which can undergo reordering in the solid state. We use a model derived for reordering kinetics (Henkes et al., 2014, Geochim. Cosmochim. Acta 139:362-382) to screen clumped isotope data for the effects of solid-state burial alteration. With minor but significant exceptions (Late Cretaceous, Early Triassic), average δ18O values (4 m.y. window, 2 m.y. steps) for post-Devonian brachiopods, belemnites, and foraminifera, representing tropical-subtropical surface ocean conditions, yield average isotopic temperatures below 30°C (assuming a seawater δ18O value [ -1‰ VSMOW] of an "ice-free" world). In contrast, Ordovician to Devonian data show sustained temperatures of 35-40°C. Likewise, isotopic paleotemperatures from conodont apatite, known to be resistant to isotopic exchange, follow the same pattern. Clumped isotope data derived from Paleozoic brachiopod shells that experienced minimal burial (< 100 °C) and <1% reordering according to the taxon-specific clumped isotope reordering model yield typical temperatures of 25-30°C for the Carboniferous, and 35-40°C for the Ordovician-Silurian. Inserting clumped temperatures and δ18O values into the oxygen isotopic paleotemperature equation yields a mean seawater δ18O of -0.7 ± 1.4‰ for the Phanerozoic. Collectively, these findings argue for extremely warm early Paleozoic oceans, and constant seawater δ18O throughout the last ~450 million years.

Investigating inner-sphere reorganization via secondary kinetic isotope effects in the C-H cleavage reaction catalyzed by soybean lipoxygenase: tunneling in the substrate backbone as well as the transferred hydrogen.

PubMed

Meyer, Matthew P; Klinman, Judith P

2011-01-26

This work describes the application of NMR to the measurement of secondary deuterium (2° (2)H) and carbon-13 ((13)C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11-h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° (2)H and (13)C KIEs on k(cat)/K(m) directly for 11,11-d2-LA, whereas the values for the 2° (2)H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° (2)H and (13)C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° (2)H KIEs.

Isotopic characterization as a screening tool in authentication of organic produce commercially available in western North America.

PubMed

Verenitch, Sergei; Mazumder, Asit

2015-01-01

The use of nitrogen stable isotopes to discriminate between conventionally and organically grown crops has been further developed in this study. Soil and irrigation water from different regions, as well as nitrogen fertilizers used, have been examined in detail to determine their effects on nitrogen isotope composition of spinach, lettuce, broccoli and tomatoes. Over 1000 samples of various types of organically and conventionally grown produce of known origin, along with the samples of nitrogen fertilizers used for their growth, have been analysed in order to assemble the datasets of crop/fertilizer correlations. The results demonstrate that the developed approach can be used as a valuable component in the verification of agricultural practices for more than 25 different types of commercially grown green produce, either organic or conventional. Over a period of two years, various organic and non-organic greens, from different stores in Seattle (WA, USA) and Victoria (BC, Canada), were collected and analysed using this methodology with the objective of determining any pattern of misrepresentation.

Isotopic mapping of age provinces in Precambrian high-grade terrains: Sri Lanka

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

Milisenda, C.C.; Liew, T.C.; Hofmann, A.W.

1988-09-01

Nd model ages of amphibolite- and granulite-grade rocks in Sri Lanka form a simple region pattern that broadly correlates with mappable geological units, and is in effect an isotopic map of the island's basement. The granulite-grade units of the Highland Group and Southwest Group have model ages of 2.2-3.0 Ga indicating derivation mainly from late Archean sources. They are bounded to the east and west by late Proterozoic gneisses of the Vijayan Complex with model ages of 1.1-2.0 Ga. The isotopic data identify three distinct crustal provinces and are not consistent with earlier suggestions that the Vijayan gneisses are retrogrademore » equivalents of the Highland granulites. Sri Lanka is not a direct continuation of the Archean Dharwar Craton of southern India. Identification of Vijayan-type juvenile crustal terrains in other Gondwana fragments may play a key role in determining the precise attachment of southern India-Sri Lanka in eastern Gondwana.« less

High congruence of isotope sewage signals in multiple marine taxa.

PubMed

Connolly, Rod M; Gorman, Daniel; Hindell, Jeremy S; Kildea, Timothy N; Schlacher, Thomas A

2013-06-15

Assessments of sewage pollution routinely employ stable nitrogen isotope analysis (δ(15)N) in biota, but multiple taxa are rarely used. This single species focus leads to underreporting of whether derived spatial N patterns are consistent. Here we test the question of 'reproducibility', incorporating 'taxonomic replication' in the measurement of δ(15)N gradients in algae, seagrasses, crabs and fish with distance from a sewage outfall on the Adelaide coast (southern Australia). Isotopic sewage signals were equally strong in all taxa and declined at the same rate. This congruence amongst taxa has not been reported previously. It implies that sewage-N propagates to fish via a tight spatial coupling between production and consumption processes, resulting from limited animal movement that closely preserves the spatial pollution imprint. In situations such as this where consumers mirror pollution signals of primary producers, analyses of higher trophic levels will capture a broader ambit of ecological effects. Copyright © 2013 Elsevier Ltd. All rights reserved.

Automated isotope identification algorithm using artificial neural networks

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

Kamuda, Mark; Stinnett, Jacob; Sullivan, Clair

There is a need to develop an algorithm that can determine the relative activities of radio-isotopes in a large dataset of low-resolution gamma-ray spectra that contains a mixture of many radio-isotopes. Low-resolution gamma-ray spectra that contain mixtures of radio-isotopes often exhibit feature over-lap, requiring algorithms that can analyze these features when overlap occurs. While machine learning and pattern recognition algorithms have shown promise for the problem of radio-isotope identification, their ability to identify and quantify mixtures of radio-isotopes has not been studied. Because machine learning algorithms use abstract features of the spectrum, such as the shape of overlapping peaks andmore » Compton continuum, they are a natural choice for analyzing radio-isotope mixtures. An artificial neural network (ANN) has be trained to calculate the relative activities of 32 radio-isotopes in a spectrum. Furthermore, the ANN is trained with simulated gamma-ray spectra, allowing easy expansion of the library of target radio-isotopes. In this paper we present our initial algorithms based on an ANN and evaluate them against a series measured and simulated spectra.« less

Automated isotope identification algorithm using artificial neural networks

DOE PAGES

Kamuda, Mark; Stinnett, Jacob; Sullivan, Clair

2017-04-12

There is a need to develop an algorithm that can determine the relative activities of radio-isotopes in a large dataset of low-resolution gamma-ray spectra that contains a mixture of many radio-isotopes. Low-resolution gamma-ray spectra that contain mixtures of radio-isotopes often exhibit feature over-lap, requiring algorithms that can analyze these features when overlap occurs. While machine learning and pattern recognition algorithms have shown promise for the problem of radio-isotope identification, their ability to identify and quantify mixtures of radio-isotopes has not been studied. Because machine learning algorithms use abstract features of the spectrum, such as the shape of overlapping peaks andmore » Compton continuum, they are a natural choice for analyzing radio-isotope mixtures. An artificial neural network (ANN) has be trained to calculate the relative activities of 32 radio-isotopes in a spectrum. Furthermore, the ANN is trained with simulated gamma-ray spectra, allowing easy expansion of the library of target radio-isotopes. In this paper we present our initial algorithms based on an ANN and evaluate them against a series measured and simulated spectra.« less

Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

NASA Astrophysics Data System (ADS)

Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.

2016-03-01

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

Laser ablation-combustion-GC-IRMS--a new method for online analysis of intra-annual variation of delta13C in tree rings.

PubMed

Schulze, Brigit; Wirth, Christian; Linke, Petra; Brand, Willi A; Kuhlmann, Iris; Horna, Viviana; Schulze, Ernst-Detlef

2004-11-01

We present a new, rapid method for high-resolution online determination of delta13C in tree rings, combining laser ablation (LA), combustion (C), gas chromatography (GC) and isotope ratio mass spectrometry (IRMS) (LA-C-GC-IRMS). Sample material was extracted every 6 min with a UV-laser from a tree core, leaving 40-microm-wide holes. Ablated wood dust was combusted to CO2 at 700 degrees C, separated from other gases on a GC column and injected into an isotope ratio mass spectrometer after removal of water vapor. The measurements were calibrated against an internal and an external standard. The tree core remained intact and could be used for subsequent dendrochronological and dendrochemical analyses. Cores from two Scots pine trees (Pinus sylvestris spp. sibirica Lebed.) from central Siberia were sampled. Inter- and intra-annual patterns of delta13C in whole-wood and lignin-extracted cores were indistinguishable apart from a constant offset, suggesting that lignin extraction is unnecessary for our method. Comparison with the conventional method (microtome slicing, elemental analysis and IRMS) indicated high accuracy of the LA-C-GC-IRMS measurements. Patterns of delta13C along three parallel ablation lines on the same core showed high congruence. A conservative estimate of the precision was +/- 0.24 per thousand. Isotopic patterns of the two Scots pine trees were broadly similar, indicating a signal related to the forest stand's climate history. The maximum variation in delta13C over 22 years was about 5 per thousand, ranging from -27 to -22.3 per thousand. The most obvious pattern was a sharp decline in delta13C during latewood formation and a rapid increase with spring early growth. We conclude that the LA-C-GC-IRMS method will be useful in elucidating short-term climate effects on the delta13C signal in tree rings.

Evaluation of stereo-array isotope labeling (SAIL) patterns for automated structural analysis of proteins with CYANA.

PubMed

Ikeya, Teppei; Terauchi, Tsutomu; Güntert, Peter; Kainosho, Masatsune

2006-07-01

Recently we have developed the stereo-array isotope labeling (SAIL) technique to overcome the conventional molecular size limitation in NMR protein structure determination by employing complete stereo- and regiospecific patterns of stable isotopes. SAIL sharpens signals and simplifies spectra without the loss of requisite structural information, thus making large classes of proteins newly accessible to detailed solution structure determination. The automated structure calculation program CYANA can efficiently analyze SAIL-NOESY spectra and calculate structures without manual analysis. Nevertheless, the original SAIL method might not be capable of determining the structures of proteins larger than 50 kDa or membrane proteins, for which the spectra are characterized by many broadened and overlapped peaks. Here we have carried out simulations of new SAIL patterns optimized for minimal relaxation and overlap, to evaluate the combined use of SAIL and CYANA for solving the structures of larger proteins and membrane proteins. The modified approach reduces the number of peaks to nearly half of that observed with uniform labeling, while still yielding well-defined structures and is expected to enable NMR structure determinations of these challenging systems.

Springtime carbon emission episodes at the Gosan background site revealed by total carbon, stable carbon isotopic composition, and thermal characteristics of carbonaceous particles

NASA Astrophysics Data System (ADS)

Jung, J.; Kawamura, K.

2011-11-01

In order to investigate the emission of carbonaceous aerosols at the Gosan background super-site (33.17° N, 126.10° E) in East Asia, total suspended particles (TSP) were collected during spring of 2007 and 2008 and analyzed for particulate organic carbon, elemental carbon, total carbon (TC), total nitrogen (TN), and stable carbon isotopic composition (δ13C) of TC. The stable carbon isotopic composition of TC (δ13CTC) was found to be lowest during pollen emission episodes (range: -26.2‰ to -23.5‰, avg. -25.2 ± 0.9‰), approaching those of the airborne pollen (-28.0‰) collected at the Gosan site. Based on a carbon isotope mass balance equation, we found that ~42% of TC in the TSP samples during the pollen episodes was attributed to airborne pollen from Japanese cedar trees planted around tangerine farms in Jeju Island. A negative correlation between the citric acid-carbon/TC ratios and δ13CTC was obtained during the pollen episodes. These results suggest that citric acid emitted from tangerine fruit may be adsorbed on the airborne pollen and then transported to the Gosan site. Thermal evolution patterns of organic carbon during the pollen episodes were characterized by high OC evolution in the OC2 temperature step (450 °C). Since thermal evolution patterns of organic aerosols are highly influenced by their molecular weight, they can be used as additional information on the formation of secondary organic aerosols and the effect of aging of organic aerosols during the long-range atmospheric transport and sources of organic aerosols.

Range-wide patterns of migratory connectivity in the western sandpiper Calidris mauri

USGS Publications Warehouse

Franks, Samantha E.; Norris, D. Ryan; Kyser, T. Kurt; Fernández, Guillermo; Schwarz, Birgit; Carmona, Roberto; Colwell, Mark A.; Sandoval, Jorge Correa; Dondua, Alexey; Gates, H. River; Haase, Ben; Hodkinson, David J.; Jiménez, Ariam; Lanctot, Richard B.; Ortego, Brent; Sandercock, Brett K.; Sanders, Felicia J.; Takekawa, John Y.; Warnock, Nils; Ydenberg, Ron C.; Lank, David B.

2012-01-01

Understanding the population dynamics of migratory animals and predicting the consequences of environmental change requires knowing how populations are spatially connected between different periods of the annual cycle. We used stable isotopes to examine patterns of migratory connectivity across the range of the western sandpiper Calidris mauri. First, we developed a winter isotope basemap from stable-hydrogen (δD), -carbon (δ13C), and -nitrogen (δ15N) isotopes of feathers grown in wintering areas. δD and δ15N values from wintering individuals varied with the latitude and longitude of capture location, while δ13C varied with longitude only. We then tested the ability of the basemap to assign known-origin individuals. Sixty percent of wintering individuals were correctly assigned to their region of origin out of seven possible regions. Finally, we estimated the winter origins of breeding and migrant individuals and compared the resulting empirical distribution against the distribution that would be expected based on patterns of winter relative abundance. For breeding birds, the distribution of winter origins differed from expected only among males in the Yukon-Kuskokwim (Y-K) Delta and Nome, Alaska. Males in the Y-K Delta originated overwhelmingly from western Mexico, while in Nome, there were fewer males from western North America and more from the Baja Peninsula than expected. An unexpectedly high proportion of migrants captured at a stopover site in the interior United States originated from eastern and southern wintering areas, while none originated from western North America. In general, we document substantial mixing between the breeding and wintering populations of both sexes, which will buffer the global population of western sandpipers from the effects of local habitat loss on both breeding and wintering grounds.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

PubMed

Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-21

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

NASA Astrophysics Data System (ADS)

Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

2017-07-01

Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

Seasonality of stable isotope composition of atmospheric water input at the southern slopes of Mt. Kilimanjaro, Tanzania

USGS Publications Warehouse

Otte, Insa; Detsch, Florian; Gutlein, Adrian; Scholl, Martha A.; Kiese, Ralf; Appelhans, Tim; Nauss, Thomas

2017-01-01

To understand the moisture regime at the southern slopes of Mt. Kilimanjaro, we analysed the isotopic variability of oxygen (δ18O) and hydrogen (δD) of rainfall, throughfall, and fog from a total of 2,140 samples collected weekly over 2 years at 9 study sites along an elevation transect ranging from 950 to 3,880 m above sea level. Precipitation in the Kilimanjaro tropical rainforests consists of a combination of rainfall, throughfall, and fog. We defined local meteoric water lines for all 3 precipitation types individually and the overall precipitation, δDprec = 7.45 (±0.05) × δ18Oprec + 13.61 (±0.20), n = 2,140, R2 = .91, p < .001. We investigated the precipitation-type-specific stable isotope composition and analysed the effects of amount, altitude, and temperature. Aggregated annual mean values revealed isotope composition of rainfall as most depleted and fog water as most enriched in heavy isotopes at the highest elevation research site. We found an altitude effect of δ18Orain = −0.11‰ × 100 m−1, which varied according to precipitation type and season. The relatively weak isotope or altitude gradient may reveal 2 different moisture sources in the research area: (a) local moisture recycling and (b) regional moisture sources. Generally, the seasonality of δ18Orain values follows the bimodal rainfall distribution under the influences of south- and north-easterly trade winds. These seasonal patterns of isotopic composition were linked to different regional moisture sources by analysing Hybrid Single Particle Lagrangian Integrated Trajectory backward trajectories. Seasonality of dexcess values revealed evidence of enhanced moisture recycling after the onset of the rainy seasons. This comprehensive dataset is essential for further research using stable isotopes as a hydrological tracer of sources of precipitation that contribute to water resources of the Kilimanjaro region.

Patterns of local and nonlocal water resource use across the western U.S. determined via stable isotope intercomparisons

USDA-ARS?s Scientific Manuscript database

In this paper we develop an isotope-based statistical framework to evaluate the dynamics of the relationship between water supplies used for human consumption and several hydrological factors, including the spatiotemporal distribution of precipitation and snowmelt as well as the timing and rates of ...

PATTERNS OF NITROGEN AND CARBON STABLE ISOTOPE RATIOS IN MACROFUNGI, PLANTS AND SOILS IN TWO OLD-GROWTH CONIFER FORESTS

EPA Science Inventory

Natural abundance stable isotope ratios represent a potentially valuable tool for studying fungal ecology. We measured 15N and 13C in ectomycorrhizal and saprotrophic macrofungi from two old-growth conifer forests, and in plants, woody debris, and soils. Fungi, plants, and so...

Influence of forest disturbance on stable nitrogen isotope ratios in soil and vegetation profiles

Treesearch

Jennifer D. Knoepp; Scott R. Taylor; Lindsay R. Boring; Chelcy F. Miniat

2015-01-01

Soil and plant stable nitrogen isotope ratios (15 N) are influenced by atmospheric nitrogen (N) inputs and processes that regulate organic matter (OM) transformation and N cycling. The resulting 15N patterns may be useful for discerning ecosystem differences in N cycling. We studied two ecosystems; longleaf pine wiregrass (...

Revealing the structural nature of the Cd isotopes

NASA Astrophysics Data System (ADS)

Garrett, P. E.; Diaz Varela, A.; Green, K. L.; Jamieson, D. S.; Jigmeddorj, B.; Wood, J. L.; Yates, S. W.

2015-10-01

The even-even Cd isotopes have provided fertile ground for the investigation of collectivity in nuclei. Soon after the development of the Bohr model, the stable Cd isotopes were identified as nearly harmonic vibrators based on their excitation energy patterns. The measurements of enhanced B (E 2) values appeared to support this interpretation. Shape co-existing rotational-like intruder bands were discovered, and mixing between the configurations was invoked to explain the deviation of the decay pattern of multiphonon vibrational states. Very recently, a detailed analysis of the low-lying levels of 110Cd combining results of the (n ,n' γ) reaction and high-statistics β decay, provided strong evidence that the mixing between configurations is weak, except for the ground-state band and ``Kπ =0+ '' intruder band. The analysis of the levels in 110Cd has now been extended to 3 MeV, and combined with data for 112Cd and previous Coulomb excitation data for 114Cd, enables a detailed map of the E 2 collectivity in these nuclei, demanding a complete re-interpretation of the structure of the stable Cd isotopes.

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

NASA Astrophysics Data System (ADS)

Jacquet, Emmanuel; Marrocchi, Yves

2017-12-01

We report combined oxygen isotope and mineral-scale trace element analyses of amoeboid olivine aggregates (AOA) and chondrules in ungrouped carbonaceous chondrite, Northwest Africa 5958. The trace element geochemistry of olivine in AOA, for the first time measured by LA-ICP-MS, is consistent with a condensation origin, although the shallow slope of its rare earth element (REE) pattern is yet to be physically explained. Ferromagnesian silicates in type I chondrules resemble those in other carbonaceous chondrites both geochemically and isotopically, and we find a correlation between 16O enrichment and many incompatible elements in olivine. The variation in incompatible element concentrations may relate to varying amounts of olivine crystallization during a subisothermal stage of chondrule-forming events, the duration of which may be anticorrelated with the local solid/gas ratio if this was the determinant of oxygen isotopic ratios as proposed recently. While aqueous alteration has depleted many chondrule mesostases in REE, some chondrules show recognizable subdued group II-like patterns supporting the idea that the immediate precursors of chondrules were nebular condensates.

Sedimentary evidence for enhanced hydrological cycling in response to rapid carbon release during the early Toarcian oceanic anoxic event

NASA Astrophysics Data System (ADS)

Izumi, Kentaro; Kemp, David B.; Itamiya, Shoma; Inui, Mutsuko

2018-01-01

A pronounced excursion in the carbon-isotope composition of biospheric carbon and coeval seawater warming during the early Toarcian (∼183 Ma) has been linked to the large-scale transfer of 12C-enriched carbon to the oceans and atmosphere. A European bias in the distribution of available data means that the precise pattern, tempo and global expression of this carbon cycle perturbation, and the associated environmental responses, remain uncertain. Here, we present a new cm-scale terrestrial-dominated carbon-isotope record through an expanded lower Toarcian section from Japan that displays a negative excursion pattern similar to marine and terrestrial carbon-isotope records documented from Europe. These new data suggest that 12C-enriched carbon was added to the biosphere in at least one rapid, millennial-scale pulse. Sedimentological analysis indicates a close association between the carbon-isotope excursion and high-energy sediment transport and enhanced fluvial discharge. Together, these data support the hypothesis that a sudden strengthening of the global hydrological cycle occurred in direct and immediate response to rapid carbon release and atmospheric warming.

Sulfur cycling in plays an important role in the development of Ocean Anoxic Events

NASA Astrophysics Data System (ADS)

Gomes, M. L.; Raven, M. R.; Fike, D. A.; Gill, B. C.; Johnston, D. T.

2017-12-01

Ocean Anoxic Events (OAEs) are major carbon cycle perturbations marked by enhanced organic carbon deposition in the marine realm and carbon isotope excursions in organic and inorganic carbon. Although not as severe as the "big five" mass extinctions, OAEs had dire consequences for marine ecosystems and thus influenced Mesozoic evolutionary patterns. Sulfur cycle reconstructions provide insight into the biogeochemical processes that played a role in the development of OAEs because the sulfur cycle is linked with the carbon and oxygen cycles. We present sulfur and oxygen isotope records from carbonate-associated sulfate from the Toarcian OAE that documents a positive sulfate-oxygen isotope excursion of +6‰, which is similar to the magnitude of the positive sulfur isotope excursion documented at the same site and other globally distributed sites. This high-resolution record allows us to explore temporal variability in the onset of the isotopic excursions: the onset of the positive sulfate-oxygen isotope excursion occurs at the same stratigraphic interval as the onset of the positive carbon isotope excursion and both precede the onset of the positive sulfate-sulfur isotope excursion. Because oxygen is rapidly recycled during oxidative sulfur cycling, changes in oxidative sulfur cycling affect oxygen isotope values of sulfate without impacting sulfur isotope values. Thus, the early onset of the sulfate-oxygen isotope excursion implies a change in oxidative sulfur cycling, which is likely due to a shoaling of the zone of sulfate reduction. We explore the consequences of sulfate reduction zone shoaling for organic carbon preservation. Specifically, the sulfurization of organic matter, which makes organic matter less susceptible to degradation, occurs more rapidly when the top of the zone of sulfate reduction is near or above the sediment water interface. Therefore, we suggest that the shoaling of the sulfate reduction zone locally changed pathways of oxidative sulfur cycling and enhanced organic carbon preservation. Given synchronous changes in similar, globally-distributed depositional environments, this impacted the global biogeochemical cycles of oxygen, carbon, and nutrients in ways that sustained decreased oxygen availability and influenced extinction patterns of marine organisms.

Disentangling effects of growth and nutritional status on seabird stable isotope ratios

USGS Publications Warehouse

Sears, J.; Hatch, Shyla A.; O'Brien, D. M.

2009-01-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather ??15N and ??13C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing ??15N and ??13C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in ??15N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC ??15N, with chicks exhibiting lower ??15N when they were growing the fastest. As growth slowed, ??15N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted ??15N in chick RBCs by 0.92???. We propose that increased nitrogen-use efficiency is responsible for 15N depletion in both growing and food-restricted chicks. ??15N values in RBCs of free-ranging auklets fell within a range of only 1.03???, while feather ??15N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue. ?? 2008 Springer-Verlag.

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.

The Multi-Isotope Process (MIP) Monitor Project: FY13 Final Report

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

Meier, David E.; Coble, Jamie B.; Jordan, David V.

The Multi-Isotope Process (MIP) Monitor provides an efficient approach to monitoring the process conditions in reprocessing facilities in support of the goal of “… (minimization of) the risks of nuclear proliferation and terrorism.” The MIP Monitor measures the distribution of the radioactive isotopes in product and waste streams of a nuclear reprocessing facility. These isotopes are monitored online by gamma spectrometry and compared, in near-real-time, to spectral patterns representing “normal” process conditions using multivariate analysis and pattern recognition algorithms. The combination of multivariate analysis and gamma spectroscopy allows us to detect small changes in the gamma spectrum, which may indicatemore » changes in process conditions. By targeting multiple gamma-emitting indicator isotopes, the MIP Monitor approach is compatible with the use of small, portable, relatively high-resolution gamma detectors that may be easily deployed throughout an existing facility. The automated multivariate analysis can provide a level of data obscurity, giving a built-in information barrier to protect sensitive or proprietary operational data. Proof-of-concept simulations and experiments have been performed in previous years to demonstrate the validity of this tool in a laboratory setting for systems representing aqueous reprocessing facilities. However, pyroprocessing is emerging as an alternative to aqueous reprocessing techniques.« less

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

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.

Radioactive and magnetic investigations

NASA Technical Reports Server (NTRS)

Heye, D.; Beiersdorf, H.

1979-01-01

Age and growth pattern determination of manganese nodules were explored. Two methods are discussed: (1) measurement of the presence of radioactive iodine isotopes; which is effective only up to 3.105 years, and (2) measurements of magnetism. The growth rates of three nodules were determined. The surface of the nodule was recent, and the overall age of the nodule could be determined with accuracy of better than 30%. Measurement of paleomagnetic effect was attempted to determine wider age ranges, however, the measured sign changes could not be interpreted as paleomagnetic reversals.

Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis.

PubMed

Guttman, Miklos; Wales, Thomas E; Whittington, Dale; Engen, John R; Brown, Jeffery M; Lee, Kelly K

2016-04-01

Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra. Graphical Abstract ᅟ.

Movement patterns and dispersal potential of Pecos bluntnose shiner (Notropis simus pecosensis) revealed using otolith microchemistry

USGS Publications Warehouse

Chase, Nathan M.; Caldwell, Colleen A.; Carleton, Scott A.; Gould, William R.; Hobbs, James A.

2015-01-01

Natal origin and dispersal potential of the federally threatened Pecos bluntnose shiner (Notropis simus pecosensis) were successfully characterized using otolith microchemistry and swimming performance trials. Strontium isotope ratios (87Sr:86Sr) of otoliths within the resident plains killifish (Fundulus zebrinus) were successfully used as a surrogate for strontium isotope ratios in water and revealed three isotopically distinct reaches throughout 297 km of the Pecos River, New Mexico, USA. Two different life history movement patterns were revealed in Pecos bluntnose shiner. Eggs and fry were either retained in upper river reaches or passively dispersed downriver followed by upriver movement during the first year of life, with some fish achieving a minimum movement of 56 km. Swimming ability of Pecos bluntnose shiner confirmed upper critical swimming speeds (Ucrit) as high as 43.8 cm·s−1 and 20.6 body lengths·s−1 in 30 days posthatch fish. Strong swimming ability early in life supports our observations of upriver movement using otolith microchemistry and confirms movement patterns that were previously unknown for the species. Understanding patterns of dispersal of this and other small-bodied fishes using otolith microchemistry may help redirect conservation and management efforts for Great Plains fishes.

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.

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

On the progressive enrichment of the oxygen isotopic composition of water along a leaf.

PubMed

Farquhar, G. D.; Gan, K. S.

2003-06-01

A model has been derived for the enrichment of heavy isotopes of water in leaves, including progressive enrichment along the leaf. In the model, lighter water is preferentially transpired leaving heavier water to diffuse back into the xylem and be carried further along the leaf. For this pattern to be pronounced, the ratio of advection to diffusion (Péclet number) has to be large in the longitudinal direction, and small in the radial direction. The progressive enrichment along the xylem is less than that occurring at the sites of evaporation in the mesophyll, depending on the isolation afforded by the radial Péclet number. There is an upper bound on enrichment, and effects of ground tissue associated with major veins are included. When transpiration rate is spatially nonuniform, averaging of enrichment occurs more naturally with transpiration weighting than with area-based weighting. This gives zero average enrichment of transpired water, the modified Craig-Gordon equation for average enrichment at the sites of evaporation and the Farquhar and Lloyd (In Stable Isotopes and Plant Carbon-Water Relations, pp. 47-70. Academic Press, New York, USA, 1993) prediction for mesophyll water. Earlier results on the isotopic composition of evolved oxygen and of retro-diffused carbon dioxide are preserved if these processes vary in parallel with transpiration rate. Parallel variation should be indicated approximately by uniform carbon isotope discrimination across the leaf.

Food-web inferences of stable isotope spatial patterns in copepods and yellowfin tuna in the pelagic eastern Pacific Ocean

NASA Astrophysics Data System (ADS)

Olson, Robert J.; Popp, Brian N.; Graham, Brittany S.; López-Ibarra, Gladis A.; Galván-Magaña, Felipe; Lennert-Cody, Cleridy E.; Bocanegra-Castillo, Noemi; Wallsgrove, Natalie J.; Gier, Elizabeth; Alatorre-Ramírez, Vanessa; Ballance, Lisa T.; Fry, Brian

2010-07-01

Evaluating the impacts of climate and fishing on oceanic ecosystems requires an improved understanding of the trophodynamics of pelagic food webs. Our approach was to examine broad-scale spatial relationships among the stable N isotope values of copepods and yellowfin tuna ( Thunnus albacares), and to quantify yellowfin tuna trophic status in the food web based on stable-isotope and stomach-contents analyses. Using a generalized additive model fitted to abundance-weighted-average δ 15N values of several omnivorous copepod species, we examined isotopic spatial relationships among yellowfin tuna and copepods. We found a broad-scale, uniform gradient in δ 15N values of copepods increasing from south to north in a region encompassing the eastern Pacific warm pool and parts of several current systems. Over the same region, a similar trend was observed for the δ 15N values in the white muscle of yellowfin tuna caught by the purse-seine fishery, implying limited movement behavior. Assuming the omnivorous copepods represent a proxy for the δ 15N values at the base of the food web, the isotopic difference between these two taxa, “ ΔYFT-COP,” was interpreted as a trophic-position offset. Yellowfin tuna trophic-position estimates based on their bulk δ 15N values were not significantly different than independent estimates based on stomach contents, but are sensitive to errors in the trophic enrichment factor and the trophic position of copepods. An apparent inshore-offshore, east to west gradient in yellowfin tuna trophic position was corroborated using compound-specific isotope analysis of amino acids conducted on a subset of samples. The gradient was not explained by the distribution of yellowfin tuna of different sizes, by seasonal variability at the base of the food web, or by known ambit distances (i.e. movements). Yellowfin tuna stomach contents did not show a regular inshore-offshore gradient in trophic position during 2003-2005, but the trophic-position estimates based on both methods had similar scales of variability. We conclude that trophic status of yellowfin tuna increased significantly from east to west over the study area based on the spatial pattern of ΔYFT-COP values and the difference between the δ 15N values of glutamic acid and glycine, “trophic” and “source” amino acids, respectively. These results provide improved depictions of trophic links and biomass flows for food-web models, effective tools to evaluate climate and fishing effects on exploited ecosystems.

Geochemistry and mineralogy of kimberlites from the Arkhangelsk Region, NW Russia: evidence for transitional kimberlite magma types

NASA Astrophysics Data System (ADS)

Beard, A. D.; Downes, H.; Hegner, E.; Sablukov, S. M.

2000-03-01

The Arkhangelsk kimberlite province (AKP) is situated in the north of the Baltic Shield within the buried southeastern portion of the Kola-Kuloi craton. It forms part of the extensive Devonian magmatic event of the northern Baltic Shield and Kola Peninsula. Two main groups of kimberlites can be distinguished within the province: (1) kimberlites from the diamondiferous Zolotitsa field that have geochemical and isotopic affinities with Group 2 kimberlites and lamproites; (2) diamond-poor Ti-Fe-rich kimberlites from other Arkhangelsk fields that have geochemical and isotopic affinities with Group 1 kimberlites. However, the Zolotitsa and Ti-Fe-rich kimberlites have mineralogical characteristics that are not typical for their respective assigned kimberlite group classifications. Both groups of Arkhangelsk kimberlites are apparently transitional to Group 1 kimberlites, Group 2 kimberlites and lamproites as they are defined elsewhere in the world. An associated kimberlite from the Mela Sill Complex has strong affinities with carbonatites. The low Al 2O 3, high Ni and Cr contents, and high Mg# in both groups of kimberlites indicate strongly depleted lherzolitic-harzburgitic mantle sources. Trace element patterns show a variable enrichment of incompatible elements and strong LREE enrichment. However, kimberlites from the Zolotitsa field have overall lower trace element abundances and less steep REE patterns, suggesting a higher degree of partial melt and/or a less enriched source compared to that of the Ti-Fe-rich kimberlites. A calciocarbonatite of the Mela Sill Complex has trace element and REE patterns typical of other carbonatites closely associated with kimberlites. 87Sr/ 86Sri and 143Nd/ 144Ndi isotope compositions of the Arkhangelsk kimberlites and carbonatite reveal that at least two mantle sources are required to explain the isotopic variation: (1) most of the Zolotitsa and Mela kimberlites and the Mela carbonatite are derived from an ancient enriched lithospheric source (EMI); (2) the Ti-Fe-rich kimberlites are derived from a plume-related asthenospheric mantle source with an isotopic composition close to Bulk Earth. Present-day Pb isotope compositions reveal that the Zolotitsa kimberlites have values close to Group 1 kimberlites. However, the Ti-Fe-rich kimberlites generally have slightly more radiogenic Pb isotope values.

Stable isotope systematics in mesozoic granites of Central and Northern California and Southwestern Oregon

USGS Publications Warehouse

Masi, U.; O'Neil, J.R.; Kistler, R.W.

1981-01-01

18O, D, and H2O+ contents were measured for whole-rock specimens of granitoid rocks from 131 localitics in California and southwestern Oregon. With 41 new determinations in the Klamath Mountains and Sierra Nevada, initial strontium isotope ratios are known for 104 of these samples. Large variations in ??18O (5.5 to 12.4), ??D (-130 to -31), water contents (0.14 to 2.23 weight percent) and initial strontium isotope ratios (0.7028 to 0.7095) suggest a variety of source materials and identify rocks modified by secondary processes. Regular patterns of variation in each isotopic ratio exist over large geographical regions, but correlations between the ratios are generally absent except in restricted areas. For example, the regular decrease in ??D values from west to east in the Sierra Nevada batholith is not correlative with a quite complex pattern of ??18O values, implying that different processes were responsible for the isotopic variations in these two elements. In marked contrast to a good correlation between (87Sr/86Sr)o and ??18O observed in the Peninsular Ranges batholith to the south, such correlations are lacking except in a few areas. ??D values, on the other hand, correlate well with rock types, chemistry, and (87Sr/86Sr)o except in the Coast Ranges where few of the isotopic signatures are primary. The uniformly low ??D values of samples from the Mojave Desert indicate that meteoric water contributed much of the hydrogen to the rocks in that area. Even so, the ??18O values and 18O fractionations between quartz and feldspar are normal in these same rocks. This reconnaissance study has identified regularities in geochemical parameters over enormous geographical regions. These patterns are not well understood but merit more detailed examination because they contain information critical to our understanding of the development of granitoid batholiths. ?? 1981 Springer-Verlag.

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.

Deep and bottom water export from the Southern Ocean to the Pacific over the past 38 million years

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

The application of radiogenic isotopes to the study of Cenozoic circulation patterns in the South Pacific Ocean has been hampered by the fact that records from only equatorial Pacific deep water have been available. We present new Pb and Nd isotope time series for two ferromanganese crusts that grew from equatorial Pacific bottom water (D137-01, "Nova," 7219 m water depth) and southwest Pacific deep water (63KD, "Tasman," 1700 m water depth). The crusts were dated using 10Be/9Be ratios combined with constant Co-flux dating and yield time series for the past 38 and 23 Myr, respectively. The surface Nd and Pb isotope distributions are consistent with the present-day circulation pattern, and therefore the new records are considered suitable to reconstruct Eocene through Miocene paleoceanography for the South Pacific. The isotope time series of crusts Nova and Tasman suggest that equatorial Pacific deep water and waters from the Southern Ocean supplied the dissolved trace metals to both sites over the past 38 Myr. Changes in the isotopic composition of crust Nova are interpreted to reflect development of the Antarctic Circumpolar Current and changes in Pacific deep water circulation caused by the build up of the East Antarctic Ice Sheet. The Nd isotopic composition of the shallower water site in the southwest Pacific appears to have been more sensitive to circulation changes resulting from closure of the Indonesian seaway. Copyright 2004 by the American Geophysical Union.

Carnivore stable carbon isotope niches reflect predator-prey size relationships in African savannas.

PubMed

Codron, Jacqueline; Avenant, Nico L; Wigley-Coetsee, Corli; Codron, Daryl

2018-03-01

Predator-prey size relationships are among the most important patterns underlying the structure and function of ecological communities. Indeed, these relationships have already been shown to be important for understanding patterns of macroevolution and differential extinction in the terrestrial vertebrate fossil record. Stable isotope analysis (SIA) is a powerful remote approach to examining animal diets and paleodiets. The approach is based on the principle that isotope compositions of consumer tissues reflect those of their prey. In systems where resource isotope compositions are distributed along a body size gradient, SIA could be used to reconstruct predator-prey size relationships. We analyzed stable carbon isotope distributions amongst mammalian herbivores in extant and Plio-Pleistocene African savanna assemblages, and show that the range of δ 13 C values among mammalian prey species (herbivores and rodents) increases with body mass (BM), because C 4 plant feeding (essentially grazing) is more common among larger taxa. Consequently, δ 13 C values of mammalian carnivores in these systems are related to species' BM, reflecting a higher average C 4 prey component in the diets of larger-bodied carnivores. This pattern likely emerges because only the largest carnivores in these systems have regular access to the C 4 prey base, whereas smaller carnivores do not. The δ 13 C-BM relationship observed in mammalian carnivores is a potentially powerful approach for reconstructing and parameterizing predator-prey size relationships in contemporary and fossil savanna assemblages, and for interpreting how various behavioral, ecological and environmental factors influence prey size selection. © 2017 International Society of Zoological Sciences, Institute of Zoology/Chinese Academy of Sciences and John Wiley & Sons Australia, Ltd.

Angiosperm n-alkane distribution patterns and the geologic record of C4 grassland evolution

NASA Astrophysics Data System (ADS)

Henderson, A.; Graham, H. V.; Patzkowsky, M.; Fox, D. L.; Freeman, K. H.

2012-12-01

n-Alkane average chain-length (ACL) patterns vary regionally with community composition and climate. To clarify the influence of phylogenetic and community patterns, we compiled and analyzed a global database of published n-alkane abundance for n-C27 to C35 homologs in modern plant specimens (n=205). ACL for waxes in C4 non-woody plants are longer than for woody plants, suggesting ACL can serve as an indicator of the three-dimensional structure of local vegetation. Further, these findings suggest compound-specific isotopic data for longer alkane homologs (C31, C33, C35) will proportionately represent non-woody vegetation and isotope measurements of C29 are more representative of woody vegetation. Thus, the combination of ACL and carbon isotope compositions should allow us to disentangle C3 woody, C3 non-woody, and C4 non-woody signals in terrestrial paleorecords. Application of this approach to the geologic record of Miocene C4 grassland expansion in the US Great Plains and the Siwaliks in Pakistan illustrate two very different transition scenarios. Alkane-specific isotopic data indicate C4 grasslands appeared 2.5 Ma in the Great Plains and 6.5 Ma in the Siwaliks, and ACL analysis indicates that this transition involved the replacement of woody vegetation in the US and the replacement of C3 grasses in Pakistan. Our analysis illustrates that, consistent with differences in the timing of C4 grassland, the drivers of change were likely not the same in these regions. Oxygen isotope records suggest that the more recent transition in the Great Plains was associated with climate cooling and possibly changes in disturbance regimes and that the transition in the Siwaliks was likely associated with warming and drying.

Evaluation of the age related systematic patterns of stable oxygen and carbon isotope values of Swiss stone pine (Pinus cembra L.) Eastern Carpathians, Romania

NASA Astrophysics Data System (ADS)

Nagavciuc, Viorica; Popa, Ionel; Persoiu, Aurel; Kern, Zoltán

2016-04-01

Tree-ring derived stable isotope time series are becoming increasingly important parameters in investigation of past environmental changes. However, potential age related trend-bias on these parameters, and the proper handling of it, is still not well understood. We here present measurements on a new multicentennial data set of annually resolved stable oxygen (δ18O) and carbon (δ13C) isotope compositions from 3 living and 4 subfossil Stone pine (Pinus cembra) samples collected at a timberline habitat in the Eastern Carpathians (Romania) to evaluate any potential systematic ontogenetic pattern on their δ18O and δ13C data. Oldest analyzed ring represented 129th, 135th and 142th cambial year in the living and 115th, 130th, 165th and 250th cambial year in the subfossil samples. The fact that Stone pine samples are backbone of the longest dendrochronological series both in the Alps and the Carpathians arouses special interest concerning their potential in stable isotope dendroclimatological research. Whole-ring samples were prepared to alpha-cellulose by the modified Jayme-Wise method. Cellulose samples were analyzed by a high-temperature pyrolysis system (Thermo Quest TC-EA) coupled to an isotope ratio mass spectrometer (Thermo Finningan Delta V). A ring by ring (i.e., non-pooled) approach was followed since age-related trends are by definition intrinsic to individual tree-ring series so pooling of rings may distort the detection of the trends. Raw measured δ13C values have been corrected for changes in the atmospheric CO2 regarding both its stable isotope signature and mixing ratio. Neither isotopic parameter showed any age related variance bias suggesting a homoscedastic character. Alignment of the δ13C data by cambial age revealed a relatively short period (~40 years) of systematic behaviour manifested in a ~1‰ enrichment in 13C over a <40 year-long period after germination. While a moderate but persistent positive trend (~0.33‰ per 100years, p<10-10) can be observed for carbon discrimination afterwards. In contrast, hardly any systematic juvenile pattern or any long-term trend could be detected for δ18O data. Based on the 80 year-long common ontogenetic period (from the 35th to the 115th ontogenetic year) we found a very narrow range of offset ~1 ‰ both for δ18O (from 28.32‰ to 29.31‰) and for δ13C (from -23.07‰ to -22.14‰) between individual trees over the past 500 years. Despite the very coherent level found for the studied stone pine individuals scaling of the overlapping records is a highly recommended pre-processing step in future isotope chronology construction. The short juvenile-effect of δ13C record can be eliminated if <40 yr periods are omitted from the records. As an alternative approach, preliminary tests suggest that subtraction of a best-fit logarithmic trend might help to retain the juvenile rings into the final δ13C chronology to improve the replication over time. However, our preliminary results suggest that δ18O from Stone pine cellulose can be used without detrending to build isotope chronologies therefore the potential to preserve the low-frequency variability in the parameter is excellent. Thanks to LP2012-27/2012 and CLIMFOR 18SEE.

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.

Temporal migration patterns between natal locations of ruby-throated hummingbirds (Archilochus colubris) and their Gulf Coast stopover site.

PubMed

Zenzal, Theodore J; Contina, Andrea J; Kelly, Jeffrey F; Moore, Frank R

2018-01-01

Autumn latitudinal migrations generally exhibit one of two different temporal migration patterns: type 1 where southern populations migrate south before northern populations, or type 2 where northern populations overtake southern populations en route . The ruby-throated hummingbird ( Archilochus colubris ) is a species with an expansive breeding range, which allows opportunities to examine variation in the timing of migration. Our objective was to determine a relationship between natal origin of ruby-throated hummingbirds and arrival at a Gulf coast stopover site; and if so, what factors, such as differences in body size across the range as well as the cost of migration, might drive such a pattern. To carry out our objectives, we captured hummingbirds at a coastal stopover site during autumn migration, at which time we collected feathers from juveniles for analysis of hydrogen stable isotopes. Using the hydrogen stable isotope gradient of precipitation across North America and published hydrogen isotope values of feathers from populations of breeding ruby-throated hummingbirds, we assigned migrants to probable natal latitudes. Our results confirm that individuals from across the range (30-50° N) stopover along the Gulf of Mexico and there is a positive relationship between arrival day and latitude, suggesting a type 1 migration pattern. We also found no relationship between fuel load (proxy for migration cost) or fat-free body mass (proxy for body size) and natal latitude. Our results, coupled with previous work on the spatial migration patterns of hummingbirds, show a type 1 chain migration pattern. While the mechanisms we tested do not seem to influence the evolution of migratory patterns, other factors such as resource availability may play a prominent role in the evolution of this migration system.

Microbes: Agents of Isotopic Change

NASA Astrophysics Data System (ADS)

Fogel, M. L.

2012-12-01

Microbes drive many of the important oxidation and reduction reactions on Earth; digest almost all forms of organic matter; and can serve as both primary and secondary producers. Because of their versatile biochemistry and physiology, they impart unique isotopic signatures to organic and inorganic materials, which have proven to be key measurements for understanding elemental cycling now and throughout Earth's history. Understanding microbial isotope fractionations in laboratory experiments has been important for interpreting isotopic patterns measured in natural settings. In fact, the pairing of simple experiment with natural observation has been the pathway for interpreting the fingerprint of microbial processes in ancient sediments and rocks. Examples of how key experiments have explained stable isotope fractionations by microbes and advanced the field of microbial ecology will be presented. Learning the isotopic signatures of Earth's microbes is a valuable exercise for predicting what isotopic signatures could be displayed by possible extant or extinct extraterrestrial life. Given the potential for discovery on Mars, Enceladus, and other solar system bodies, new methods and techniques for pinpointing what is unique about microbial isotope signatures is particularly relevant.

Seeking the Signs of Life: Assessing the Presence of Biosignatures in the Returned Sample Suite

NASA Astrophysics Data System (ADS)

iMOST Team; Des Marais, D. J.; Grady, M. M.; Shaheen, R.; Steele, A.; Westall, F.; Altieri, F.; Amelin, Y.; Ammannito, E.; Anand, M.; Beaty, D. W.; Benning, L. G.; Bishop, J. L.; Borg, L. E.; Boucher, D.; Brucato, J. R.; Busemann, H.; Campbell, K. A.; Carrier, B. L.; Czaja, A. D.; Debaille, V.; Dixon, M.; Ehlmann, B. L.; Farmer, J. D.; Fernandez-Remolar, D. C.; Fogarty, J.; Glavin, D. P.; Goreva, Y. S.; Hallis, L. J.; Harrington, A. D.; Hausrath, E. M.; Herd, C. D. K.; Horgan, B.; Humayun, M.; Kleine, T.; Kleinhenz, J.; Mangold, N.; Mackelprang, R.; Mayhew, L. E.; McCubbin, F. M.; McCoy, J. T.; McLennan, S. M.; McSween, H. Y.; Moser, D. E.; Moynier, F.; Mustard, J. F.; Niles, P. B.; Ori, G. G.; Raulin, F.; Rettberg, P.; Rucker, M. A.; Schmitz, N.; Sefton-Nash, E.; Sephton, M. A.; Shuster, D. L.; Siljestrom, S.; Smith, C. L.; Spry, J. A.; Swindle, T. D.; ten Kate, I. L.; Tosca, N. J.; Usui, T.; Van Kranendonk, M. J.; Wadhwa, M.; Weiss, B. P.; Werner, S. C.; Wheeler, R. M.; Zipfel, J.; Zorzano, M. P.

2018-04-01

Biosignatures are objects, substances, and/or patterns whose origins require life. They occur as organic compounds, stable isotope patterns, minerals, and morphologies. Each type requires particular modes of preservation and analytical measurements.

Continuous and simultaneous measurements of precipitation and vapor isotopes over two monsoon seasons during 2016-2017 in Singapore

NASA Astrophysics Data System (ADS)

Jackisch, D.; He, S.; Ong, M. R.; Goodkin, N.

2017-12-01

Water isotopes are important tracers of climate dynamics and their measurement can provide valuable insights into the relationship between isotopes and atmospheric parameters and overall convective activities. While most studies provide data on daily or even monthly time scales, high-temporal in-situ stable isotope measurements are scarce, especially in the tropics. In this study, we presented δ18O and δ2H values in precipitation and vapor continuously and simultaneously measured using laser spectroscopy in Singapore during the 2016/2017 Northeast (NE) Asian monsoon and 2017 Southwest (SW) Asian monsoon. We found that δ-values of precipitation and vapor exhibit quite different patterns during individual events, although there is a significant correlation between the δ-values of precipitation and of vapor. δ-values in precipitation during individual precipitation events show a distinct V-shape pattern, with the lowest isotope values observed in the middle of the event. However, isotopes in water vapor mostly show an L-shape and are characterized by a gradual decrease with the onset of rainfall. The difference in δ-values of precipitation and vapor is generally constant during the early stage of the events but gradually increases near the end. It is likely that vapor and precipitation are closer to equilibrium at the early stage of a rain event, but diverge at the later stages. This divergence can be largely attributed to the evaporation of raindrops. We notice a frequent drop in d-excess of precipitation, whereas d-excess in vapor increases. In addition, a significant correlation exists between outgoing longwave radiation (OLR) and isotopes in both precipitation and vapor, suggesting an influence of regional convective activity.

Should Variations of d2H, d18O and d17O in Precipitation be Considered 'Settled Science' or a 'New Frontier' For Understanding Cloud Dynamics and Microphysics?

NASA Astrophysics Data System (ADS)

Aggarwal, P. K.; araguas Araguas, L.; Belachew, D.; Terzer, S.; Wassenaar, L. I.; Longstaffe, F. J.; Schumacher, C.; Funk, A. B.; Steinacker, R.; Kaltenboeck, R.

2017-12-01

After more than 60 years of isotope measurements in precipitation, there are relatively well established patterns of variation, but their origin and controlling parameters remain a matter of debate, preventing a fuller integration of isotope-based information in meteorology. The prevailing hypothesis based on temperature and Rayleigh distillation has been successful in explaining many of the patterns, particularly at a seasonal or annual scale, and attempts to explain variances by 'tweaking' the prevailing hypothesis suggest that the underlying science may be considered to be 'settled'. A rigorous evaluation at the storm event scale, where precipitation acquires its isotope composition, however, does not provide a satisfactory explanation in most cases. We have conducted an year-long study with high-frequency sampling (5-15 min) of mid-latitude precipitation at Vienna and more than 1000 samples have been analyzed for d2H, d18O and d17O. We have also collected profiles of reflectivity and doppler velocity using a vertically pointed micro-rain radar, particle size distribution in precipitation using a disdrometer, and conducted aerological analysis of air and moisture circulation using sounding data. A combined evaluation of isotope and meteorological data provides a detailed understanding of isotope variability. We will discuss these results and the light they shed on boundary layer and tropospheric moisture circulation in frontal or convective precipitation, the relative roles of vapor deposition and riming growth of precipitation, and the origin of d-excess. The agreement between meteorological observations and isotopic variability is extremely promising and may help open a new frontier in the use of isotopes for weather and climate studies.

Stable isotope patterns in micronekton from the Mozambique Channel

NASA Astrophysics Data System (ADS)

Ménard, Frédéric; Benivary, Hermann Doris; Bodin, Nathalie; Coffineau, Nathalie; Le Loc'h, François; Mison, Thomas; Richard, Pierre; Potier, Michel

2014-02-01

We measured the stable carbon (δ13C) and nitrogen (δ15N) isotopic composition of tissues of micronektonic organisms (fishes, squids, crustaceans and gelatinous organisms) collected in the Mozambique Channel during two scientific cruises in 2008 and 2009. The oceanic circulation in the Mozambique Channel is dominated by mesoscale cyclonic and anticyclonic eddies which play a key role in biological processes of less-productive deep-sea ecosystems. We investigated the potential impact of mesoscale features on the δ13C and δ15N values of 32 taxa of micronekton. Fishes, squids, crustaceans and gelatinous organisms encompassed a wide range of isotopic niches, with large overlaps among species. Our results showed that mesoscale features did not really influence the isotopic signatures of the sampled organisms, although cyclonic eddies can occasionally impact the nitrogen signatures of micronekton. We show that δ13C values were intermediate between standard offshore and nearshore signatures, suggesting that pelagic production in the Mozambique Channel could be partly supported by the transport and export of inorganic and organic particles from the Mozambican coast toward the offshore area. Trophic levels calculated from δ15N values ranged from 2.6 to 4.2, showing that micronekton taxa can be tertiary consumers in the Mozambique Channel. Our findings evidenced clusters of micronektonic organisms according to their δ15N or δ13C isotopic signatures, but variations in stable isotope values reflect a complex set of embedded processes linked to physical mesoscale dynamics (rotational dynamics of eddies) and basic biology and ecology of micronektonic organisms (vertical habitat, migration pattern, dietary habits, body length) that are discussed with regard to the stable isotope method based on time-integrated assimilated food.

Shifts in Ross Sea food web structure as indicated by δ15N and δ13C values of fossil Antarctic seals

NASA Astrophysics Data System (ADS)

Leopold, A.; Brault, E.; McMahon, K.

2013-12-01

As climate change continues to mount, there is a growing need for understanding its effects on biological-physical interactions of marine ecosystems. Assessing the effects of anthropogenic activities on the coastal marine ecosystem involves understanding the underlying mechanisms driving these changes as well as establishing baselines of the natural system. Preliminary findings have indicated shifts in bulk carbon (C) and nitrogen (N) isotopic values of southern elephant seal (Mirounga leonina) samples, collected in the Dry Valleys of Antarctica in the Ross Sea region, over approximately the last 7,000 years. These shifts could result from 1) seals changing their foraging location and/or diet over this time, 2) climate change-induced shifts in the biogeochemistry at the base of the food web, or 3) some combination of both processes. We explored the patterns of long-term change in Ross Sea food web structure by examining the stable isotope values of three top predators in this system, Weddell seals (Leptonychotes weddellii), leopard seals (Hydrurga leptonyx), and crabeater seals (Lobodon carcinophagus). Fossil seal samples were collected in the Dry Valleys during the austral summer of 2012/13 and then analyzed for bulk C and N isotopes via an elemental analyzer/isotope-ratio mass spectrometer (EA/IRMS). Our initial findings indicate that C isotopic values of fossil seal samples from Weddell, leopard, and crabeater seals were more enriched than isotopic values of modern seals of the same species (e.g., δ13C = -22.79 × 0.92 ‰ and -26.71 × 0.50 ‰ for fossil and modern crabeater seals, respectively). Given the relatively consistent diet of crabeater seals, these findings suggest a shift in baseline food web structure occurred over the last 10,000 years, either through changes in foraging location or local shifts in biogeochemistry. For all species, N isotopic values are widely variable (e.g., 7.28 to 16.0 δ15N ‰ for the Weddell seal), which may be a result of greatly changing diets in the last ~10,000 years, or a changing baseline N value for the Ross Sea. Seal bones will be radiocarbon-dated to isolate the key shifts in C and N isotopic values. Once those major shifts are temporally constrained, compound-specific isotopic analysis of the bone samples will be used to tease apart the diet vs. baseline effects on the bulk isotopic signatures of the seals. Our results suggests that during the last ~10,000 years, there was a fundamental shift in Ross Sea food web structure likely related to long term climatic variability.

Vapour-Phase Processes Control Liquid-Phase Isotope Profiles in Unsaturated Sphagnum Moss

NASA Astrophysics Data System (ADS)

Edwards, T. W.; Yi, Y.; Price, J. S.; Whittington, P. N.

2009-05-01

Seminal work in the early 1980s clearly established the basis for predicting patterns of heavy-isotope enrichment of pore waters in soils undergoing evaporation. A key feature of the process under steady-state conditions is the development of stable, convex-upward profiles whose shape is controlled by the balance between downward-diffusing heavy isotopologues concentrated by evaporative enrichment at the surface and the upward capillary flow of bulk water that maintains the evaporative flux. We conducted an analogous experiment to probe evaporation processes within 20-cm columns of unsaturated, living and dead (but undecomposed) Sphagnum moss evaporating under controlled conditions, while maintaining a constant water table. The experiment provided striking evidence of the importance of vapour-liquid mass and isotope exchange in the air-filled pores of the Sphagnum columns, as evidenced by the rapid development of hydrologic and isotopic steady-state within hours, rather than days, i.e., an order of magnitude faster than possible by liquid-phase processes alone. This is consistent with the notion that vapour-phase processes effectively "short-circuit" mass and isotope fluxes within the Sphagnum columns, as proposed also in recent characterizations of water dynamics in transpiring leaves. Additionally, advection-diffusion modelling of our results supports independent estimates of the effective liquid-phase diffusivities of the respective heavy water isotopologues, 2.380 x 10-5 cm2 s-1 for 1H1H18O and 2.415 x 10-5 cm2 s-1 for 1H2H16O, which are in notably good agreement with the "default" values that are typically assumed in soil and plant water studies.

Earth's Coming of Age: Isotopically Tracking the Global Transformation from the Hadean to the Geologically Modern Earth

NASA Astrophysics Data System (ADS)

Bennett, V. C.; Nutman, A. P.

2017-12-01

Some of the strongest direct evidence that documents fundamental changes in the chemistry and organisation of Earth's interior derives from radiogenic isotopic compositions that include both long-lived (particularly 176Lu-176Hf and 147Sm-143Nd) and short-lived, i.e., now extinct parent isotope, systems (182Hf-182W, 146Sm-142Nd). Changes in patterns of isotopic evolution are linked to changes in mantle dynamics such that tracking these signatures in geologically well-characterised rocks can be used to discover the the nature and evolution of tectonic processes. Over the past decade, intensive geochemical investigations by various groups focussing on the oldest (> 4.0 Ga to 3.6 Ga) rock record, as preserved in several localities, have revealed isotopic distinctions in the early Earth compared with those in Proterozoic and younger rocks. For example, whilst the major and trace element compositions of Eoarchean gneisses have analogs in younger rocks in accord with a continuum of crust formation processes, radiogenic isotopic signatures from both long and short half-life decay schemes record an image of the Earth in transition from early differentiation processes, likely associated with planetary accretion and formation, to more modern style characterised by plate tectonics. The emerging image is that many Eoarchean rocks possess extinct nuclide anomalies in the form of 142Nd and 182Hf isotopic signatures that are absent in modern terrestrial samples; these signatures are evidence of chemical fractionation processes occuring within the first ca. 10-300 million years of Solar System history. In addition, viewing the global database, patterns of long-half life isotope signatures i.e., 143Nd and 176Hf differ from those seen in younger (<3.6 Ga) rocks, again providing a tracer of mantle dynamics and reflecting the influence of early processes. It is becoming increasingly apparent that the well demonstrated "coupled" 176Hf-143Nd isotopic evolution generated by plate tectonic processes and characterizing Phanerozoic and Proterozoic mantle derived rocks is absent in the Eoarchean record. Here, we track this isotopic transition in key regions and demonstrate how this places limits on the timing and style of transition from early to modern Earth.

Neodymium Isotope associated with planktonic foraminifera as a proxy of deglacial changes in Pacific ocean circulation

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

Neodymium isotopes of ferromanganese oxide coatings precipitated on planktonic foraminifera have been intensively used as a proxy for water mass reconstruction in the deep Atlantic and Indian Ocean, but their suitability is not well constrained in the Pacific and may be affected by enhanced inputs and scavenging relative to advection. In this study, Nd isotopes and Rare Earth Element (REE) concentrations of planktonic foraminifera from ~60 sites widely distributed throughout the Pacific are presented. We found that the REE pattern associated with planktonic foraminifera in our study and Fe-Mn oxides/coatings in the global ocean have a common heavy REE depleted pattern when normalized to their ambient seawater due to preferential removal of light REEs onto particles relative to heavy REEs during scavenging. The core-top ɛNd results agree with the proximal seawater compositions, indicating that planktonic foraminiferal coatings can give a reliable record of past changes in bottom water Nd isotopes in the Pacific. A good correlation between foraminifera Nd isotopes and seawater phosphate suggests that Nd with a predominantly radiogenic isotopic composition was probably added gradually along continental boundaries so that the Nd isotopic composition change paralleled the accumulation of nutrients in the deep Pacific. By confirming Nd isotopes as a reliable water mass tracer in the Pacific Ocean, this proxy is then applied to reconstruct how the water mass circulation changes during the Last Glacial Maximum (LGM). Most of the cores in deep North Pacific show essentially invariant Nd isotopic compositions during the LGM compared with core-top values, suggesting that Nd isotope of Pacific end-member did not change during glacial times. However, the LGM Southwest Pacific cores have more radiogenic ɛNd than core-tops corroborating the previous findings of reduced inflow of North Atlantic Deep Water. The Eastern Equatorial Pacific cores above ~2 km showed consistently lower LGM ɛNd values, which might suggest a reduced influence of more radiogenic North Pacific Deep Water return flow. Taken together, our results indicate a slower Pacific overturning circulation during the glacial times, and the inflow and return flow of the Pacific meridional overturning were closely linked in the glacial-interglacial cycles.

Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

NASA Technical Reports Server (NTRS)

Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

2016-01-01

Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay of (sup 26) Al. Delta (sup 25) Mg (mass-dependent fractionation) in hibonite is approximately -5 per mille per atomic mass unit relative to Madagascar hibonite, but is not well constrained for perovskite due to very large uncertainties owing to extremely low Mg contents. Similar to Mg isotopes, SHAL hibonite and perovskite show essentially the same Ti isotopic compositions, with anomalies in (sup 50) Ti of approximately 14 per mille, but the former shows greater Ti isotope fractionation than the latter (2.5 per mille per atomic mass unit versus 0 per mille). Discussion and Conclusions: The Al-Mg and Ti isotopic compositions of SHAL hibonite are consistent with those of HAL, suggesting that SHAL hibonite is a FUN inclusion and likely formed prior to homogenization of (sup 26) Al and Ti isotope variations in the solar nebula. However, the formation mechanisms for SHAL and HAL differ, given the differences in the REE patterns and degrees of oxygen mass-dependent fractionation. The Group-II to Group-III like REE patterns, the Yb depletions, and negative delta (sup 25) Mg observed in SHAL hibonite are all consistent with condensation of the hibonite precursor in a reducing environment.. The lack of large Ce depletions in SHAL hibonite implies that distillation processes that fractionated hibonite's oxygen isotopes must have taken place under a reducing condition, but the extent to which SHAL hibonite was distilled appears to be less than HAL because of the smaller degree of oxygen mass-dependent fractionation. The perovskite shares essentially the same Ti and Mg isotopic compositions as hibonite and probably formed in the same reservoir.. The ultrarefractory REE pattern seen in perovskite likely resulted from gas-solid fractionation which depleted HREEs in this reservoir. This process also explains why SHAL hibonite is generally depleted in HREEs relative to LREEs.

β decay studies of n-rich Cs isotopes with the ISOLDE Decay Station

NASA Astrophysics Data System (ADS)

Lică, R.; Benzoni, G.; Morales, A. I.; Borge, M. J. G.; Fraile, L. M.; Mach, H.; Madurga, M.; Sotty, C.; Vedia, V.; De Witte, H.; Benito, J.; Berry, T.; Blasi, N.; Bracco, A.; Camera, F.; Ceruti, S.; Charviakova, V.; Cieplicka-Oryńczak, N.; Costache, C.; Crespi, F. C. L.; Creswell, J.; Fernández-Martínez, G.; Fynbo, H.; Greenlees, P.; Homm, I.; Huyse, M.; Jolie, J.; Karayonchev, V.; Köster, U.; Konki, J.; Kröll, T.; Kurcewicz, J.; Kurtukian-Nieto, T.; Lazarus, I.; Leoni, S.; Lund, M.; Marginean, N.; Marginean, R.; Mihai, C.; Mihai, R.; Negret, A.; Orduz, A.; Patyk, Z.; Pascu, S.; Pucknell, V.; Rahkila, P.; Regis, J. M.; Rotaru, F.; Saed-Sami, N.; Sánchez-Tembleque, V.; Stanoiu, M.; Tengblad, O.; Thuerauf, M.; Turturica, A.; Van Duppen, P.; Warr, N.

2017-05-01

Neutron-rich Ba isotopes are expected to exhibit octupolar correlations, reaching their maximum in isotopes around mass A = 146. The odd-A neutron-rich members of this isotopic chain show typical patterns related to non-axially symmetric shapes, which are however less marked compared to even-A ones, pointing to a major contribution from vibrations. In the present paper we present results from a recent study focused on 148-150Cs β-decay performed at the ISOLDE Decay Station equipped with fast-timing detectors. A detailed analysis of the measured decay half-lives and decay scheme of 149Ba is presented, giving a first insight in the structure of this neutron-rich nucleus.

Geologically Controlled Isotope-Time Patterns Reveal Early Differentiation and Crust Formation Processes

NASA Astrophysics Data System (ADS)

Bennett, V. C.; Nutman, A. P.

2014-12-01

The mechanisms of continental crust production and evolution in the early Earth remain controversial, as are questions of the relative roles of early differentiation versus subsequent tectonic procssing in creating Earth's chemical signatures. Here we present geologic observations integrated with whole rock major, trace element and Sm-Nd isotopic signatures and combined with U-Pb and Lu-Hf isotopic compositions of zircon populations from the same rocks, from the most extensive early rock record comprising the 3.9 Ga to 3.6 Ga terranes of southwest Greenland. These data reveal repeated patterns of formation of juvenile TTG crust and associated mafic and ultramafic rocks in convergent margin settings followed by formation of more evolved granites [1]. Our new zircon Lu-Hf data from rare 3.6-3.7 Ga tonalites within the Itsaq Gneiss Complex, obtained from single component, non-migmatitic gneisses with simple zircon populations, limited within sample Hf isotopic variability and accurate U-Pb ages, now document extraction of juvenile tonalites from a near chondritic mantle source between 3.9 Ga and 3.6 Ga. The more evolved, granitic rocks in each area show slightly negative initial ɛHf in accord with crustal reworking of the older (3.8-3.9 Ga) gniesses. There is no evidence for Hadean material in the sources of the granitoids. The Hf isotope-time patterns are consistent with juvenile crust production from a mantle source that experienced only modest amounts of prior crustal extraction. They are distinct from those predicted by reprocessing of an enriched Hadean mafic crust, as has been proposed for this region [2] and for the source of the Hadean Jack Hills zircons [3]. The well-documented, time decreasing, positive 142Nd anomalies [e.g., 4] from these rocks are further evidence of crustal derivation from a convecting mantle source, rather than reworking of an enriched mafic lithosphere. The 143Nd isotopic -time patterns are more complex, reflecting the interplay between early Sm/Nd fractionation processes as required by the 142Nd data, juvenile crustal growth and in some cases geologic disturbance of the whole rock Sm-Nd system. [1] Nutman, et al, (2013) Amer. Jour. Sci. 313, 877-911. [2] Naeraa et al.. (2012) Nature 485, 627-631. [3] Kemp et al., (2010) EPSL 296, 45-56. [4] Bennett et al., (20070 Science 318, 1907.

Stable Isotope Values of Nitrogen and Carbon in Particulate ...

EPA Pesticide Factsheets

Data set from “Patterns in stable isotope values of nitrogen and carbon in particulate matter from the Northwest Atlantic Continental Shelf, from the Gulf of Maine to Cape Hatteras” by Oczkowski et al. These are the data upon which all results and conclusion are made. Publishing the data allow for use by wider audience. Stable isotope dynamics on the shelf can inform both nearshore and open ocean research efforts, providing an important link along the marine continuum. To our knowledge, this data set is unique in its spatial coverage and variables measured.

Combining Solvent Isotope Effects with Substrate Isotope Effects in Mechanistic Studies of Alcohol and Amine Oxidation by Enzymes*

PubMed Central

Fitzpatrick, Paul F.

2014-01-01

Oxidation of alcohols and amines is catalyzed by multiple families of flavin-and pyridine nucleotide-dependent enzymes. Measurement of solvent isotope effects provides a unique mechanistic probe of the timing of the cleavage of the OH and NH bonds, necessary information for a complete description of the catalytic mechanism. The inherent ambiguities in interpretation of solvent isotope effects can be significantly decreased if isotope effects arising from isotopically labeled substrates are measured in combination with solvent isotope effects. The application of combined solvent and substrate (mainly deuterium) isotope effects to multiple enzymes is described here to illustrate the range of mechanistic insights that such an approach can provide. PMID:25448013

Baseline study of Oxygen 18 and deuterium in the Roswell, New Mexico, groundwater basin

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

Hoy, R.N.; Gross, G.W.

The isotopic ratios of deuterium and oxygen 18 were measured in precipitation, surface, and ground water samples from the Roswell Artesian ground water basin in south-central New Mexico. The narrow range of D and 180 indicates mixing effects which are ascribed to one or more of the following factors: long ground water flow paths; large temperature fluctuations affecting which overwhelm the influence of elevation on precipitation; two sources of atmospheric moisture; interaquifer leakage; and recharge from intermittent streams with the flow-length expanding and contracting over large distances. It is concluded that a more precise definition of circulation patterns on themore » basis of stable isotope differences will require a much greater sampling frequency in both space and time.« less

Recent and Late Holocene Alaskan Lake Changes Identified from Water Isotopes

NASA Astrophysics Data System (ADS)

Anderson, L.; Birks, S. J.; Rover, J.; Guldager, N.

2014-12-01

To identify the existence and cause of recent lake area changes in the Yukon Flats, a region of discontinuous permafrost in north central Alaska, we evaluate lake water isotope compositions with remotely sensed imagery and hydroclimatic parameters. Estimates of the ratio of water lost by evaporation to that gained by inflow (E/I) were derived from an isotope-based water balance model. The isotope labels are also used to identify the dominant sources for lakes such as rainfall and snowfall, groundwater, rivers, or thawed permafrost. These parameters are then used in conjunction with climatic data and remotely sensed imagery to identify the patterns and causes of recent lake area changes and for evaluation with lake sediment oxygen isotope records of late Holocene lake water isotope variations. Lake water isotope samples from 83 lakes were acquired in July, August or September between 2007 and 2010 by fixed wing aircraft. An additional set of smaller lakes (n = 33) was sampled by helicopter in September 2009. In July 2011 59 lakes were sampled on foot within five distinct 11.2-km2 areas. River water data used here are previously collected during the months of June through October between 2006 and 2008. Isotope compositions indicate that mixtures of precipitation, river water, and groundwater source ~95% of the studied lakes. The remaining minority are more dominantly sourced by snowmelt and/or permafrost thaw. Isotope-based water balance estimates indicate 58% of lakes lose more than half of inflow by evaporation. For 26% of the lakes studied, evaporative losses exceeded supply. Surface area trend analysis indicates that most lakes were near their maximum extent in the early 1980s during a relatively cool and wet period. Subsequent reductions can be explained by moisture deficits and greater evaporation. Comparison with late Holocene isotope values and trends indicates recent changes are within the range of late Holocene variability. The records indicate a drier and warmer than present climate prior to 4000 years ago, whereas it was wetter and cooler between 4000 and 2000 years ago. These findings indicate that attempts to project future high-latitude lake change will benefit from considering the effects of decade to multi-decadal scale hydroclimatic variations.

Spatial distribution and controlling factors of stable isotopes in meteoric waters on the Tibetan Plateau: Implications for paleoelevation reconstruction

NASA Astrophysics Data System (ADS)

Li, Lin; Garzione, Carmala N.

2017-02-01

Debates persist about the interpretations of stable isotope based proxies for the surface uplift of the central-northern Tibetan Plateau. These disputes arise from the uncertain relationship between elevation and the δ18 O values of meteoric waters, based on modern patterns of isotopes in precipitation and surface waters. We present a large river water data set (1,340 samples) covering most parts of the Tibetan Plateau to characterize the spatial variability and controlling factors of their isotopic compositions. Compared with the amount-weighted mean annual oxygen isotopic values of precipitation, we conclude that river water is a good substitute for isotopic studies of precipitation in the high flat (e.g., elevation >3,300 m) interior of the Tibetan Plateau in the mean annual timescale. We construct, for the first time based on field data, contour maps of isotopic variations of meteoric waters (δ18 O, δD and d-excess) on the Tibetan Plateau. In the marginal mountainous regions of the Plateau, especially the southern through eastern margins, the δ18 O and δD values of river waters decrease with increasing mean catchment elevation, which can be modeled as a Rayleigh distillation process. However, in the interior of the Plateau, northward increasing trends in δ18 O and δD values are pronounced and present robust linear relations; d-excess values are lower than the marginal regions and exhibit distinct contrasts between the eastern (8 ‰- 12 ‰) and western (<8‰) Plateau. We suggest that these isotopic features of river waters in the interior of the Tibetan Plateau result from the combined effects of: 1) mixing of different moisture sources transported by the South Asian monsoon and Westerly winds; 2) contribution of moisture from recycled surface water; and 3) sub-cloud evaporation. We further provide a sub-cloud evaporation modified Rayleigh distillation and mixing model to simulate the isotopic variations in the western Plateau. Results of this work suggest that stable isotope-based paleoaltimetry studies are reliable in the southern through eastern Plateau margins; towards the central-northern Plateau, this method cannot be applied without additional constraints and/or large uncertainties.

The Isotopologue Record of Repeat Vital Effect Offenders: Tracking (Dis)equilibrium Effects in Sea Urchins and Nannofossil Using Clumped Isotopes

NASA Astrophysics Data System (ADS)

John, C. M.; Davies, A.; Drury, A. J.

2016-12-01

Vital effects vary between species and affect various isotopic systems in unequal proportion. The magnitude of the response of different isotopic systems might thus be key in understanding biologically-mediated disequilibrium, especially in groups that show a tendency to be "repeat offenders" with regards to vital effects. Here we present carbon, oxygen, and clumped isotope data from echinoderm calcite and nannofossil ooze, both of which exhibit strong vital effects in bulk isotopes. Our study is the first to investigate the clumped isotope (dis)equilibrium of echinoids. Results from two echinoids, three marine gastropods and a bivalve mollusk from modern beach deposits of Bali, Indonesia, highlight a significant offset in clumped isotopes of a regular echinoid test from expected values, interpreted as evidence of a similar "vital effect" as observed in surface corals. This is in contrast to the test of an irregular "sand dollar" echinoid, with clumped isotope values within error of expected sea surface temperature. Furthermore, data on the inter-skeletal variability in the clumped isotopic composition of two regular echinoid species shows that the spines of the echinoids are in equilibrium with seawater with respect to clumped isotopes, but the test is not. For the nannofossil material, no clumped isotope vital effects are observed, consistent with previously published studies but at odds with strong vital effects in carbon and oxygen isotopes, often correlated with cell-size. In addition, we reveal that the <63 micron fraction of deep-sea ooze could constitute useful material for clumped isotope studies. An intriguing result of our study is that vital effects are mostly absent in clumped isotopes, even in phylums known for important isotopic effects. It remains to be explained why some parts of the echinoids show clear vital effects, notably enrichment in clumped isotopes of urchin tests. Mechanisms that could explain this include pH effects during calcification. Rapid precipitation of calcite is however not considered as a likely mechanism as skeletal components with the largest growth rates show no clear clumped isotope vital effects.

Combinatorial effects on clumped isotopes and their significance in biogeochemistry

NASA Astrophysics Data System (ADS)

Yeung, Laurence Y.

2016-01-01

The arrangement of isotopes within a collection of molecules records their physical and chemical histories. Clumped-isotope analysis interrogates these arrangements, i.e., how often rare isotopes are bound together, which in many cases can be explained by equilibrium and/or kinetic isotope fractionation. However, purely combinatorial effects, rooted in the statistics of pairing atoms in a closed system, are also relevant, and not well understood. Here, I show that combinatorial isotope effects are most important when two identical atoms are neighbors on the same molecule (e.g., O2, N2, and D-D clumping in CH4). When the two halves of an atom pair are either assembled with different isotopic preferences or drawn from different reservoirs, combinatorial effects cause depletions in clumped-isotope abundance that are most likely between zero and -1‰, although they could potentially be -10‰ or larger for D-D pairs. These depletions are of similar magnitude, but of opposite sign, to low-temperature equilibrium clumped-isotope effects for many small molecules. Enzymatic isotope-pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect, although it is not limited to biological reactions. Chemical-kinetic isotope effects, which are related to a bond-forming transition state, arise independently and express second-order combinatorial effects related to the abundance of the rare isotope. Heteronuclear moeties (e.g., Csbnd O and Csbnd H), are insensitive to direct combinatorial influences, but secondary combinatorial influences are evident. In general, both combinatorial and chemical-kinetic factors are important for calculating and interpreting clumped-isotope signatures of kinetically controlled reactions. I apply this analytical framework to isotope-pairing reactions relevant to geochemical oxygen, carbon, and nitrogen cycling that may be influenced by combinatorial clumped-isotope effects. These isotopic signatures, manifest as either directly bound isotope ;clumps; or as features of a molecule's isotopic anatomy, are linked to molecular mechanisms and may eventually provide additional information about biogeochemical cycling on environmentally relevant spatial scales.

Amino acid specific stable nitrogen isotope values in avian tissues: Insights from captive American kestrels and wild herring gulls

USGS Publications Warehouse

Hebert, Craig E.; Popp, B.N.; Fernie, K.J.; Ka'apu-Lyons, C.; Rattner, Barnett A.; Wallsgrove, N.

2016-01-01

Through laboratory and field studies, the utility of amino acid compound-specific nitrogen isotope analysis (AA-CSIA) in avian studies is investigated. Captive American kestrels (Falco sparverius) were fed an isotopically characterized diet and patterns in δ15N values of amino acids (AAs) were compared to those in their tissues (muscle and red blood cells) and food. Based upon nitrogen isotope discrimination between diet and kestrel tissues, AAs could mostly be categorized as source AAs (retaining baseline δ15N values) and trophic AAs (showing 15N enrichment). Trophic discrimination factors based upon the source (phenylalanine, Phe) and trophic (glutamic acid, Glu) AAs were 4.1 (muscle) and 5.4 (red blood cells), lower than those reported for metazoan invertebrates. In a field study involving omnivorous herring gulls (Larus argentatus smithsonianus), egg AA isotopic patterns largely retained those observed in the laying female’s tissues (muscle, red blood cells, and liver). Realistic estimates of gull trophic position were obtained using bird Glu and Phe δ15N values combined with β values (difference in Glu and Phe δ15N in primary producers) for aquatic and terrestrial food webs. Egg fatty acids were used to weight β values for proportions of aquatic and terrestrial food in gull diets. This novel approach can be applied to generalist species that feed across ecosystem boundaries.

Late Pleistocene C4 plant dominance and summer rainfall in the southwestern United States from isotopic study of herbivore teeth

USGS Publications Warehouse

Connin, S.L.; Betancourt, J.; Quade, Jay

1998-01-01

Patterns of climate and C4 plant abundance in the southwestern United States during the last glaciation were evaluated from isotopic study of herbivore tooth enamel. Enamel ??13C values revealed a substantial eastward increase in C4 plant consumption for Mammuthus spp., Bison spp., Equus spp., and Camelops spp. The ??13C values were greatest in Bison spp. (-6.9 to + 1.7???) and Mammuthus spp. (-9.0 to +0.3???), and in some locales indicated C4-dominated grazing. The ??13C values of Antilocaprids were lowest among taxa (-12.5 to -7.9???) and indicated C3 feeding at all sites. On the basis of modern correlations between climate and C4 grass abundance, the enamel data imply significant summer rain in parts of southern Arizona and New Mexico throughout the last glaciation. Enamel ??18O values range from +19.0 to +31.0??? and generally increase to the east. This pattern could point to a tropical or subtropical source of summer rainfall. At a synoptic scale, the isotope data indicate that interactions of seasonal moisture, temperature, and lowered atmospheric pCO2 determined glacial-age C4 abundance patterns.

ICPD-a new peak detection algorithm for LC/MS.

PubMed

Zhang, Jianqiu; Haskins, William

2010-12-01

The identification and quantification of proteins using label-free Liquid Chromatography/Mass Spectrometry (LC/MS) play crucial roles in biological and biomedical research. Increasing evidence has shown that biomarkers are often low abundance proteins. However, LC/MS systems are subject to considerable noise and sample variability, whose statistical characteristics are still elusive, making computational identification of low abundance proteins extremely challenging. As a result, the inability of identifying low abundance proteins in a proteomic study is the main bottleneck in protein biomarker discovery. In this paper, we propose a new peak detection method called Information Combining Peak Detection (ICPD ) for high resolution LC/MS. In LC/MS, peptides elute during a certain time period and as a result, peptide isotope patterns are registered in multiple MS scans. The key feature of the new algorithm is that the observed isotope patterns registered in multiple scans are combined together for estimating the likelihood of the peptide existence. An isotope pattern matching score based on the likelihood probability is provided and utilized for peak detection. The performance of the new algorithm is evaluated based on protein standards with 48 known proteins. The evaluation shows better peak detection accuracy for low abundance proteins than other LC/MS peak detection methods.

[A study on feeding ecology and migration patterns of Dosidicus gigas off Peru using stable isotope analysis].

PubMed

Gong, Yi; Chen, Xin-jun; Li, Yun-kai; Han, Meng-jie

2015-09-01

As a pelagic cephalopod and one of the main target species of Chinese distant water fishery, jumbo squids (Dosidicus gigas) play a major role in the marine ecosystems of the eastern Pacific. Understanding the feeding ecology and migration patterns of jumbo squids is of importance for better utilizing the resources. The isotopic signatures of gladius, have been proved to be a powerful tool to reveal high resolution and ontogenic variations in individual foraging strategies of squids; which is an archival tissue with no elemental turnover after formation. In this study, the growth equation of gladius proostracum was established based on the age information determined by statolith. Gladius was cut successionally by the growth curve of gladius proostracum, the stable isotopic values of the gladius profiles were determined, and the feeding ecology and migration patterns of jumbo squids during its growth process were investigated. Results showed that the jumbo squids began to migrate after 180 days of postnatal, and their trophic levels tended to decrease throughout the life span. These results demonstrated the feasibility of using continuous sampling hard tissue to study the feeding ecology and habitat transfer of jumbo squids.

Cadmium cycling in the water column of the Kuroshio-Oyashio Extension region: Insights from dissolved and particulate isotopic composition

NASA Astrophysics Data System (ADS)

Yang, Shun-Chung; Zhang, Jing; Sohrin, Yoshiki; Ho, Tung-Yuan

2018-07-01

We measured dissolved and particulate Cd isotopic composition in the water column of a meridional transect across the Kuroshio-Oyashio Extension region in a Japanese GEOTRACES cruise to investigate the relative influence of physical and biogeochemical processes on Cd cycling in the Northwestern Pacific Ocean. Located at 30-50°N along 165°E, the transect across the extension region possesses dramatic hydrographic contrast. Cold surface water and a relatively narrow and shallow thermocline characterizes the Oyashio Extension region in contrast to a relatively warm and highly stratified surface water and thermocline in the Kuroshio Extension region. The contrasting hydrographic distinction at the study site provides us with an ideal platform to investigate the spatial variations of Cd isotope fractionation systems in the ocean. Particulate samples demonstrated biologically preferential uptake of light Cd isotopes, and the fractionation effect varied dramatically in the surface water of the two regions, with relatively large fractionation factors in the Oyashio region. Based on the relationship of dissolved Cd concentrations and isotopic composition, we found that a closed system fractionation model can reasonably explain the relationship in the Kuroshio region. However, using dissolved Cd isotopic data, either a closed system or steady-state open system fractionation model may explain the relationship in the surface water of the Oyashio region. Particulate δ114/110Cd data further supports that the surface water of the Oyashio region matches a steady-state open system model more closely. Contrary to the surface water, the distribution of potential density exhibits comparable patterns with Cd elemental and isotopic composition in the thermocline and deep water in the two extension regions, showing that physical processes are the dominant forcing controlling Cd cycling in the deep waters. The results demonstrate that Cd isotope fractionation can match either a closed or open system Rayleigh fractionation model, depending on the relative contribution of physical and biogeochemical processes on its cycling.

Do birds of like feather flock together? The use of a novel 13C+D combustion isotope analyzer to track bird migration

NASA Astrophysics Data System (ADS)

Saad, N.

2011-12-01

Information on spring migration routes, geographic linkages among winter, spring, and breeding locations, and potential geographic effects on arrival body condition of a variety of avian species is so far little known. Stable isotope ratios are exquisitely sensitive to the biochemistry of living organisms and the nutrients available to them. Isotope ratios provide detailed knowledge useful in a variety of fields, including birds migration, through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of flight feathers and breast feathers of tissues representing different periods of dietary integration and body composition analyses. Associations among specific geographic areas, habitat use, and arrival condition can be elucidated through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample with an application to bird migration. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. This CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1 permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows ecologists to leverage the science and elucidate the avian migration patterns.

Isotopic constraints on the origin of meteoritic organic matter

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1991-01-01

Salient features of the isotopic distribution of H, C and N in the organic material found in carbonaceous meteorites are noted. Most organic fractions are strongly enriched in D with respect to the D/H ratio characteristic of H2 in the protosolar system; substantial variations in C-13/C-12 ratio are found among different molecular species, with oxidised species tending to be C-13 enriched relative to reduced species; some homologous series reveal systematic decrease in C-13/C-12 with increasing C number; considerable variation in N-15/N-14 ratio is observed within organic matter, though no systematic pattern to its distribution has yet emerged; no interelement correlations have been observed between isotope enrichments for the different biogenic elements. The isotopic complexity echoes the molecular diversity observed in meteoritic organic matter and suggests that the organic matter was formed by multiple processes and/or from multiple sources. However, existence of a few systematic patterns points towards survival of isotopic signatures characteristic of one or more specific processes. The widespread D enrichment implies either survival of many species of interstellar molecule or synthesis from a reservoir containing a significant interstellar component. Several of the questions raised above can be addressed by more detailed determination of the distribution of the H, C and N isotopes among different well-characterized molecular fractions. Thus, the present study is aimed at discovering whether the different amino acids have comparable D enrichments, which would imply local synthesis from a D-enriched reservoir, or very viable D enrichments, which would imply survival of some interstellar amino acids. The same approach is also being applied to polycyclic aromatic hydrocarbons. Because the analytical technique employed (secondary ion mass spectrometry) can acquire data for all three isotopic systems from each molecular fraction, any presently obscured interelement isotopic correlation should also be revealed, which will aid in identifying pertinent synthetic processes.

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.

Plutonium isotopes offer an alternative approach to establishing chronological profiles in coarse sediments

NASA Astrophysics Data System (ADS)

Pondell, C.; Kuehl, S. A.; Canuel, E. A.

2016-12-01

There are several methodologies used to determine chronologies for sediments deposited within the past 100 years, including 210Pb and 137Cs radioisotopes and organic and inorganic contaminants. These techniques are quite effective in fine sediments, which generally have a high affinity for metals and organic compounds. However, the application of these chronological tools becomes limited in systems where coarse sediments accumulate. Englebright Lake is an impoundment in northern California where sediment accumulation is characterized by a combination of fine and coarse sediments. This combination of sediment grain size complicated chronological analysis using the more traditional 137Cs chronological approach. This study established a chronology of these sediments using 239+240Pu isotopes. While most of the 249+240Pu activity was measured in the fine grain size fraction (<63 microns), up to 25% of the plutonium activity was detected in the coarse size fractions of sediments from Englebright Lake. Profiles of 239+240Pu were similar to available 137Cs profiles, verifying the application of plutonium isotopes for determining sediment chronologies and expanding the established geochronology for Englebright Lake sediments. This study of sediment accumulation in Englebright Lake demonstrates the application of plutonium isotopes in establishing chronologies in coarse sediments and highlights the potential for plutonium to offer new insights into patterns of coarse sediment accumulation.

Water use patterns of three species in subalpine forest, Southwest China: the deuterium isotope approach

Treesearch

Qing Xu; Harbin Li; Jiquan Chen; Jiquan Cheng; Xiaoli Cheng; Shirong Liu; Shuqing An

2011-01-01

Determination of water sources of plant species in a community is critical for understanding the hydrological processes and their importance in ecosystem functions. Such partitioning of plant xylem water into specific sources (i.e. precipitation, groundwater) can be achieved by analyzing deuterium isotopic composition (δD) values for source waters. A subalpine dark...

Isotopic evidence indicates saprotrophy in post-fire Morchella in Oregon and Alaska

Treesearch

Erik A. Hobbie; Samuel F. Rice; Nancy S. Weber; Jane E. Smith

2016-01-01

We assessed the nutritional strategy of true morels (genus Morchella) collected in 2003 and 2004 in Oregon and Alaska, 1 or 2 y after forest fires. We hypothesized that the patterns of stable isotopes (δ13C and δ15N) in the sporocarps would match those of saprotrophic fungi and that radiocarbon (Δ

Stable isotope fingerprinting: a novel method for identifying plant, fungal, or bacterial origins of amino acids

Treesearch

Thomas Larsen; D. Lee Taylor; Mary Beth Leigh; Diane M. O' Brien

2009-01-01

Amino acids play an important role in ecology as essential nutrients for animals and as currencies in symbiotic associations. Here we present a new approach to tracing the origins of amino acids by identifying unique patterns of carbon isotope signatures generated by amino acid synthesis in plants, fungi, and bacteria ("13C fingerprints...

ChelomEx: Isotope-assisted discovery of metal chelates in complex media using high-resolution LC-MS.

PubMed

Baars, Oliver; Morel, François M M; Perlman, David H

2014-11-18

Chelating agents can control the speciation and reactivity of trace metals in biological, environmental, and laboratory-derived media. A large number of trace metals (including Fe, Cu, Zn, Hg, and others) show characteristic isotopic fingerprints that can be exploited for the discovery of known and unknown organic metal complexes and related chelating ligands in very complex sample matrices using high-resolution liquid chromatography mass spectrometry (LC-MS). However, there is currently no free open-source software available for this purpose. We present a novel software tool, ChelomEx, which identifies isotope pattern-matched chromatographic features associated with metal complexes along with free ligands and other related adducts in high-resolution LC-MS data. High sensitivity and exclusion of false positives are achieved by evaluation of the chromatographic coherence of the isotope pattern within chromatographic features, which we demonstrate through the analysis of bacterial culture media. A built-in graphical user interface and compound library aid in identification and efficient evaluation of results. ChelomEx is implemented in MatLab. The source code, binaries for MS Windows and MAC OS X as well as test LC-MS data are available for download at SourceForge ( http://sourceforge.net/projects/chelomex ).

Effects of Natural and Experimental Drought on Growth and Water Use Efficiency in Amazon trees

NASA Astrophysics Data System (ADS)

Vadeboncoeur, M. A.; Brum, M., Jr.; Oliveira, R. S.; Moutinho, V. H. P.; Flores, C. F.; Llerena, C. A.; Palace, M. W.; Asbjornsen, H.

2016-12-01

Severe regional droughts in the Amazon basin, mostly associated with El Nino events, have attracted considerable attention over the past decade, especially with regard to their effects on tree mortality, vulnerability to fire, and changes in the terrestrial budgets of carbon, water, and energy. Understanding the complex responses of forest ecosystems to such droughts is key to predicting how these globally critical forest ecosystems will respond to a changing climate with higher temperatures and greater precipitation variability. Though tree rings are not formed by all tropical tree species, they offer a unique retrospective approach for investigating patterns of climatic responses in both carbon cycling (primary production inferred from diameter growth) and water cycling (water use efficiency calculated from stable C isotope ratios). We sampled increment cores from 40 tree species at the Tapajos National Forest in Brazil, as well as the Cocha Cashu Biological Station in Peru, for an isotopic dendrochronological investigation into the effects of past droughts on the growth and water-use efficiency of canopy and mid-story tree species. We found that many but not all trees responded to drought years with periods of reduced growth lasting 2-3 years. Forthcoming data on carbon isotope ratios will allow us to compare the sensitivity of species and sites in terms of water use under drought conditions.

Golan Heights Groundwater Systems: Separation By REE+Y And Stable Isotopes

NASA Astrophysics Data System (ADS)

Siebert, C.; Geyer, S.; Knoeller, K.; Roediger, T.; Weise, S.; Dulski, P.; Moeller, P.; Guttman, J.

2008-12-01

In a semi-arid to arid country like Israel, all freshwater resources are under (over-) utilization. Particularly, the Golan Heights rank as one of the most important extraction areas of groundwater of good quality and quantity. Additionally the mountain range feed to a high degree the most important freshwater reservoir of Israel, the Sea of Galilee. Hence, knowing the sources and characters of the Golan Heights groundwater systems is an instantaneous demand regarding sustainable management and protection. Within the "German-Israeli-Jordanian-Palestinian Joint Research Program for the Sustainable Utilisation of Aquifer Systems", hundreds of water samples were taken from all over the Jordan-Dead Sea rift-system to understand groundwater flow-systems and salinisation. For that purpose, each sample was analysed for major and minor ions, rare earth elements including yttrium (REY) and stable isotopes of water (d18O, d2H). The REY distribution in groundwater is established during infiltration by the first water-rock interaction and consequently reflects the leachable components of sediments and rocks of the recharge area. In well- developed flow-systems, REY are adsorbed onto pore surfaces are in equilibrium with the percolating groundwater, even if the lithology changes (e.g. inter-aquifer flow). Thus, groundwater sampled from wells and springs still show the REY distribution pattern established in the recharge area. Since high temperatures do not occur in Golan Heights, d2H and d18O are less controlled by water-rock interaction than by climatic and geomorphological factors at the time of replenishment. Applying the REY signature as a grouping criterion of groundwaters, d18O vs. d2H plots yield a new dimension in interpreting isotope data. The combined use of hydrochemical and isotopic methods enabled us to contain the areas of replenishment and the flow-paths of all investigated groundwater in the Golan Heights. Despite location, salinity or temperature of spring or well waters, stable isotopes showed, that the main area of recharge is the elevated Hermon-Massif, with high annually precipitation amounts. The major element composition of fresh water well Alonei HaBashan 3, situated in the basaltic Upper Golan Heights, is defined by a pre-Neogenic limy aquifer and the contact to basalts. However, REY pattern refer to a calcareous infiltration area. Stable isotope signatures are lighter than in the recharge of comparable elevated Upper Galilee. Further to the south, in the Yarmouk gorge hot Mezar springs occur, which show stable isotope signatures even lighter than in water of Alonei Habshan 3. Both, REY pattern and hydrochemistry show infiltration into and contact to the Sr-rich limestone aquifer of the Mt. Scopus group. That adds up to an infiltration area some 50 km to the north, the nearest elevated area where carbonates crop out. Nearby Mezar, hot Hammat Gader springs occur, which show comparable isotopic signatures and hydrochemical composition. However, the REY-patterns indicate infiltration in basalts. By means of those three examples we could show, that the use of a combined hydrochemical and isotopic approach reveals complex and large-scale groundwater infiltration- and flow-systems much better than a focused view on a specific band of elements.

Rb-Sr systematics and REE abundances in Shalka and several other diogenites

NASA Astrophysics Data System (ADS)

Takahashi, K.; Yabuki, S.; Kagi, H.; Masuda, A.

1994-07-01

The diogenites have been regarded as igneous products in the early solar system and they have been considered to have genetically close relationship with eucrites. Depsite their simple mineralogical compositions and narrow range for major-element compositions, diogenites have been known to show wide Rare Earth Elements (REE) variations in absolute concentration and in mutual abundance ratios. Furthermore, some diogenites have peculiar Rb-Sr isotope systematics (ages younger than 4.5 b.y.). The Shalka meteorite belongs to the diogenites, and a unique REE abundance pattern has been reported. We performed Rb-Sr isotopic analyses and measured REE abundances in the Shalka diogenite with several other diogenites to discuss their genesis. Roughly speaking, REE patterns in diogenites are characterized by the negative Eu anomaly and the depletion of light REE. For Shalka, some heterogeneity in REE abundance patterns have been observed. While one sample chip shows the REE pattern with a large negative Eu anomaly and depleted light REE, particularly characterized by the concave curvature for the La-Nd span, other samples show the pattern nearly flat or the pattern enriched in light REE. These variations could not be explained easily by the simple mixing process of LREE-depleted components and LREE-enriched melt, but they imply some metamorphism process. The Rb-Sr isotopic data for Shalka are shown with the data for other several diogenites. These observations indicate that Shalka would undergo a significant extent of metamorphism followed by redistribution of REE and the disturbance of the Rb-Sr systematics. We are going to do further studies on Shalka to discuss the metamorphic process and compare it with other diogenites.

Detecting climate-change responses of plants and soil organic matter using isotopomers

NASA Astrophysics Data System (ADS)

Schleucher, Jürgen; Ehlers, Ina; Segura, Javier; Haei, Mahsa; Augusti, Angela; Köhler, Iris; Zuidema, Pieter; Nilsson, Mats; Öquist, Mats

2015-04-01

Responses of vegetation and soils to environmental changes will strongly influence future climate, and responses on century time scales are most important for feedbacks on the carbon cycle, climate models, prediction of crop productivity, and for adaptation to climate change. That plants respond to increasing CO2 on century time scales has been proven by changes in stomatal index, but very little is known beyond this. In soil, the complexity of soil organic matter (SOM) has hampered a sufficient understanding of the temperature sensitivity of SOM turnover. Here we present new stable isotope methodology that allows detecting shifts in metabolism on long time scales, and elucidating SOM turnover on the molecular level. Compound-specific isotope analysis measures isotope ratios of defined metabolites, but as average of the entire molecule. Here we demonstrate how much more detailed information can be obtained from analyses of intramolecular distributions of stable isotopes, so-called isotopomer abundances. As key tool, we use nuclear magnetic resonance (NMR) spectroscopy, which allows detecting isotope abundance with intramolecular resolution and without risk for isotope fractionation during analysis. Enzyme isotope fractionations create non-random isotopomer patterns in biochemical metabolites. At natural isotope abundance, these patterns continuously store metabolic information. We present a strategy how these patterns can be used as to extract signals on plant physiology, climate variables, and their interactions. Applied in retrospective analyses to herbarium samples and tree-ring series, we detect century-time-scale metabolic changes in response to increasing atmospheric CO2, with no evidence for acclimatory reactions by the plants. In trees, the increase in photosynthesis expected from increasing CO2 ("CO2 fertilization) was diminished by increasing temperatures, which resolves the discrepancy between expected increases in photosynthesis and commonly observed lack of biomass increases. Isotopomer patterns are a rich source of metabolic information, which can be retrieved from archives of plant material covering centuries and millennia, the time scales relevant for climate change. Boreal soils contain a huge carbon pool that may be particularly vulnerable to climate change. Biological activity persists in soils under frozen conditions, but it is largely unknown what controls it, and whether it differs from unfrozen conditions. In an incubation experiment, we traced the metabolism of 13C-labeled cellulose by soil microorganisms. NMR analysis revealed that the 13C label was converted both to respired CO2 and to phospholipid fatty acids, indicating that the polymeric substrate cellulose entered both catabolic and anabolic pathways. Both applications demonstrate a fundamental advantage of isotopomer analysis, namely that their abundances directly reflect biochemical processes. This allows obtaining metabolic information on millennial time scales, thus bridging between plant-physiology and paleo sciences. It may also be key to characterizing SOM with sufficient resolution to understand current biogeochemical fluxes involving SOM and to identify molecular components and organisms that are key for SOM turnover.

Nitrogen isotope effects induced by anammox bacteria

PubMed Central

Brunner, Benjamin; Contreras, Sergio; Lehmann, Moritz F.; Matantseva, Olga; Rollog, Mark; Kalvelage, Tim; Klockgether, Gabriele; Lavik, Gaute; Jetten, Mike S. M.; Kartal, Boran; Kuypers, Marcel M. M.

2013-01-01

Nitrogen (N) isotope ratios (15N/14N) provide integrative constraints on the N inventory of the modern ocean. Anaerobic ammonium oxidation (anammox), which converts ammonium and nitrite to dinitrogen gas (N2) and nitrate, is an important fixed N sink in marine ecosystems. We studied the so far unknown N isotope effects of anammox in batch culture experiments. Anammox preferentially removes 14N from the ammonium pool with an isotope effect of +23.5‰ to +29.1‰, depending on factors controlling reversibility. The N isotope effects during the conversion of nitrite to N2 and nitrate are (i) inverse kinetic N isotope fractionation associated with the oxidation of nitrite to nitrate (−31.1 ± 3.9‰), (ii) normal kinetic N isotope fractionation during the reduction of nitrite to N2 (+16.0 ± 4.5‰), and (iii) an equilibrium N isotope effect between nitrate and nitrite (−60.5 ± 1.0‰), induced when anammox is exposed to environmental stress, leading to the superposition of N isotope exchange effects upon kinetic N isotope fractionation. Our findings indicate that anammox may be responsible for the unresolved large N isotope offsets between nitrate and nitrite in oceanic oxygen minimum zones. Irrespective of the extent of N isotope exchange between nitrate and nitrite, N removed from the combined nitrite and nitrate (NOx) pool is depleted in 15N relative to NOx. This net N isotope effect by anammox is superimposed on the N isotope fractionation by the co-occurring reduction of nitrate to nitrite in suboxic waters, possibly enhancing the overall N isotope effect for N loss from oxygen minimum zones. PMID:24191043

Vegetation effects on event water dynamics - Insights from in-situ stable isotope observations and dye patterns

NASA Astrophysics Data System (ADS)

Volkmann, Till; Haberer, Kristine; Gessler, Arthur; Weiler, Markus

2014-05-01

The predicted changes of climate and land-use could have drastic effects on the water balance of ecosystems, particularly under frequent drought and subsequent rewetting conditions. Yet, inference of these effects and related consequences for the structure and functioning of ecosystems, groundwater recharge, leaching of nutrients and pollutants, drinking water availability, and the water cycle is currently impeded by gaps in our understanding of the manifold interactions between vegetation and soil water dynamics. While plants require water and nutrients, they also exert, for instance, important below-ground controls on the distribution and movement of water and chemicals in the rooted soil horizons via uptake and redistribution of water, modification of soil hydraulic properties, and formation of conduits for rapid preferential water flow. This work aims to contribute to fill existing gaps by assessing the effects of different plant types and their rooting systems on the soil water dynamics. Therefore, we conducted artificial drought and subsequent rewetting experiments using isotopically and dye (Brilliant Blue FCF) labeled water on plots of various surface cover (bare soil, grass, beech, oak, vine) established on relatively homogeneous luvisol on loess in southwestern Germany. Detailed insight into the short-term dynamics of event water infiltration and root uptake during the field experiments was facilitated by the application of novel techniques for high-frequency in-situ monitoring of stable isotope signatures in pore and transpiration water using commercial laser-based spectrometers, augmenting conventional observations of soil physicochemical states (soil water content, matric potential, electrical conductivity). The temporal point information is complemented by dye staining profiles, providing a detailed picture of spatial infiltration patterns, and by root density observations. The results of the experiments allow for a comprehensive spatiotemporal characterization of the effects of differing vegetation cover and rooting systems on infiltration, preferential flow path characteristics, and water storage in the rooted soil horizons. This will contribute to an improved ability to estimate environmental change impacts on the fate of water, nutrients, and pollutants in this critical zone and associated feedbacks within the soil-vegetation-atmosphere system.

Urban water - a new frontier in isotope hydrology.

PubMed

Ehleringer, James R; Barnette, Janet E; Jameel, Yusuf; Tipple, Brett J; Bowen, Gabriel J

2016-01-01

Isotope hydrology has focused largely on landscapes away from densely inhabited regions. In coming decades, it will become increasingly more important to focus on water supplies and dynamics within urban systems. Stable isotope analyses provide important information to water managers within large cities, particularly in arid regions where evaporative histories of water sources, vulnerabilities, and reliabilities of the water supplies can be major issues. Here the spatial and vertical understanding of water supporting urban systems that comes from stable isotope analyses can serve as a useful management tool. We explore this research frontier using the coupled natural-human landscape of the Salt Lake Valley, USA, with its greater than one million inhabitants. We first provide data on the stable isotope ratios of the hydrologic system's primary components: precipitation, incoming surface waters, and terminus waters in this closed basin. We then explore the spatial and temporal patterns of drinking waters within the urban landscape and the new opportunities to better link isotope ratio data with short- and long-term management interests of water managers.

Isotopic anomalies from neutron reactions during explosive carbon burning

NASA Technical Reports Server (NTRS)

Lee, T.; Schramm, D. N.; Wefel, J. P.; Blake, J. B.

1978-01-01

The possibility that the newly discovered correlated isotopic anomalies for heavy elements in the Allende meteorite were synthesized in the secondary neutron capture episode during the explosive carbon burning, the possible source of the O-16 and Al-26 anomalies, is examined. Explosive carbon burning calculations under typical conditions were first performed to generate time profiles of temperature, density, and free particle concentrations. These quantities were inputted into a general neutron capture code which calculates the resulting isotopic pattern from exposing the preexisting heavy seed nuclei to these free particles during the explosive carbon burning conditions. The interpretation avoids the problem of the Sr isotopic data and may resolve the conflict between the time scales inferred from 1-129, Pu-244, and Al-26.

Recent terebratulide brachiopods: Do they faithfully record oceanographic conditions throughout ontogeny?

NASA Astrophysics Data System (ADS)

Kercher, P.; Carlson, S. J.

2012-12-01

Brachiopods have commonly been used to infer secular changes in ocean chemistry over the Phanerozoic Eon since Lowenstam (1961) concluded that Recent brachiopod calcite was precipitated in equilibrium with seawater. In order to infer paleoenvironmental conditions with confidence, however, the impact of potential kinetic and metabolic fractionation effects on the final isotopic signature, as it varies among individuals, must be determined. In this study, we analyzed the oxygen and carbon isotopic composition of closely spaced (~2/mm) samples of calcite along growth transects from individuals of the rhynchonelliform brachiopod, Laqueus californianus. By combining local oceanographic information with knowledge of brachiopod shell structure and growth patterns through ontogeny, in individuals of different ages from the same locality that died simultaneously, we can address the fidelity of brachiopod shell calcite as both an environmental proxy and a recorder of biological activity among conspecific individuals, in real time. This is an essential, but largely ignored, component in the paleoenvironmental interpretation of brachiopod shell calcite. In May 2011, more than 75 live L. californianus specimens were collected by Dr. J. Barry at Monterey Bay Aquarium Research Institute (MBARI) from Monterey Bay at 160 m water depth (36.7322N, 121.9739W) and generously given to us for use in this study. The specimens range in length from 5.75 to 46.16 mm, representing a range of ontogenetic ages. Water temperatures at 160 m range annually from 8C in the spring/summer upwelling season to 10C during the winter, while salinity fluctuates from 33.76 ppt in the winter to 34.11 ppt in the summer. Daily temperature and salinity data collected by MBARI over three decades allow us to calculate approximate equilibrium calcite values. We use these values to evaluate the claim that brachiopods mineralize in isotopic equilibrium with seawater throughout their lifespan with minimal intraspecific variation. We also use the MBARI data to correlate annual temperature fluctuations with δ18O trends within the calcite to estimate ontogenetic ages and growth rates. Full-grown adults were 10-11 years old when collected live, and grow an average of about 4 mm/year over their lifespan, growing faster before sexual maturity and slowing down after. The early results of the ontogenetic sampling tracts indicate calcite δ18O and δ13C values are strongly positively correlated. This relationship suggests kinetic fractionation effects are likely influencing the isotopic composition of the shells. Cyclic isotopic fluctuations are also recorded, in accordance with seasonal temperature oscillations in Monterey Bay, apparent even at 160 m depth. In most of the specimens, the amplitudes of the isotopic fluctuations exceed those of the predicted equilibrium values. Furthermore, our data support the claim made by other researchers that the outer primary layer of the shell is significantly depleted in both oxygen and carbon isotopes, below the range of equilibrium calcite. Isotopic oscillations across individuals align reasonably well both with each other and with ambient water temperature patterns. These results suggest that intraspecific variability is low in L. californianus and that these organisms are recording their environment similarly.

Re-constructing nutritional history of Serengeti wildebeest from stable isotopes in tail hair: seasonal starvation patterns in an obligate grazer.

PubMed

Rysava, K; McGill, R A R; Matthiopoulos, J; Hopcraft, J G C

2016-07-15

Nutritional bottlenecks often limit the abundance of animal populations and alter individual behaviours; however, establishing animal condition over extended periods of time using non-invasive techniques has been a major limitation in population ecology. We test if the sequential measurement of δ(15) N values in a continually growing tissue, such as hair, can be used as a natural bio-logger akin to tree rings or ice cores to provide insights into nutritional stress. Nitrogen stable isotope ratios were measured by continuous-flow isotope-ratio mass spectrometry (IRMS) from 20 sequential segments along the tail hairs of 15 migratory wildebeest. Generalized Linear Models were used to test for variation between concurrent segments of hair from the same individual, and to compare the δ(15) N values of starved and non-starved animals. Correlations between δ(15) N values in the hair and periods of above-average energy demand during the annual cycle were tested using Generalized Additive Mixed Models. The time series of nitrogen isotope ratios in the tail hair are comparable between strands from the same individual. The most likely explanation for the pattern of (15) N enrichment between individuals is determined by life phase, and especially the energetic demands associated with reproduction. The mean δ(15) N value of starved animals was greater than that of non-starved animals, suggesting that higher δ(15) N values correlate with periods of nutritional stress. High δ(15) N values in the tail hair of wildebeest are correlated with periods of negative energy balance, suggesting they may be used as a reliable indicator of the animal's nutritional history. This technique might be applicable to other obligate grazers. Most importantly, the sequential isotopic analysis of hair offers a continuous record of the chronic condition of wildebeest (effectively converting point data into time series) and allows researchers to establish the animal's nutritional diary. © 2016 The Authors. Rapid Communications in Mass Spectrometry Published by John Wiley & Sons Ltd.

Deuterium excess reveals diurnal sources of water vapor in forest air.

PubMed

Lai, Chun-Ta; Ehleringer, James R

2011-01-01

An understanding of atmospheric water vapor content and its isotopic composition is important if we are to be able to model future water vapor dynamics and their potential feedback on future climate change. Here we present diurnal and vertical patterns of water isotope ratios in forest air (δ(2)H(v) and δ(18)O(v)) not observed previously. Water vapor observed at three heights over 3 consecutive days in a coniferous forest in the Pacific Northwest of the United States, shows a stratified nocturnal structure of δ(2)H(v) and δ(18)O(v), with the most positive values consistently observed above the canopy (60 m). Differences between 0.5 m and 60 m range between 2-6‰ for δ(18)O and 20-40‰ for δ(2)H at night. Using a box model, we simulated H(2)O isotope fluxes and showed that the low to high δ(2)H(v) and δ(18)O(v) profiles can be explained by the vapor flux associated with evaporation from the forest floor and canopy transpiration. We used d-excess as a diagnostic tracer to identify processes that contribute to the diurnal variation in atmospheric moisture. Values of d-excess derived from water vapor measurements showed a repeated diel pattern, with the lowest values occurring in the early morning and the highest values occurring at midday. The isotopic composition of rain water, collected during a light rain event in the first morning of our experiment, suggested that considerable below-cloud secondary evaporation occurred during the descent of raindrops. We conclude that atmospheric entrainment appears to drive the isotopic variation of water vapor in the early morning when the convective boundary layer rapidly develops, while evapotranspiration becomes more important in the mid-afternoon as a primary moisture source of water vapor in this forest. Our results demonstrate the interplay between the effects of vegetation and boundary layer mixing under the influence of rain evaporation, which has implications for larger-scale predictions of precipitation across the terrestrial landscape.

Estimates of water source contributions in a dynamic urban water supply system inferred via a Bayesian stable isotope mixing model

NASA Astrophysics Data System (ADS)

Jameel, M. Y.; Brewer, S.; Fiorella, R.; Tipple, B. J.; Bowen, G. J.; Terry, S.

2017-12-01

Public water supply systems (PWSS) are complex distribution systems and critical infrastructure, making them vulnerable to physical disruption and contamination. Exploring the susceptibility of PWSS to such perturbations requires detailed knowledge of the supply system structure and operation. Although the physical structure of supply systems (i.e., pipeline connection) is usually well documented for developed cities, the actual flow patterns of water in these systems are typically unknown or estimated based on hydrodynamic models with limited observational validation. Here, we present a novel method for mapping the flow structure of water in a large, complex PWSS, building upon recent work highlighting the potential of stable isotopes of water (SIW) to document water management practices within complex PWSS. We sampled a major water distribution system of the Salt Lake Valley, Utah, measuring SIW of water sources, treatment facilities, and numerous sites within in the supply system. We then developed a hierarchical Bayesian (HB) isotope mixing model to quantify the proportion of water supplied by different sources at sites within the supply system. Known production volumes and spatial distance effects were used to define the prior probabilities for each source; however, we did not include other physical information about the supply system. Our results were in general agreement with those obtained by hydrodynamic models and provide quantitative estimates of contributions of different water sources to a given site along with robust estimates of uncertainty. Secondary properties of the supply system, such as regions of "static" and "dynamic" source (e.g., regions supplied dominantly by one source vs. those experiencing active mixing between multiple sources), can be inferred from the results. The isotope-based HB isotope mixing model offers a new investigative technique for analyzing PWSS and documenting aspects of supply system structure and operation that are otherwise challenging to observe. The method could allow water managers to document spatiotemporal variation in PWSS flow patterns, critical for interrogating the distribution system to inform operation decision making or disaster response, optimize water supply and, monitor and enforce water rights.

Estimating blue whale skin isotopic incorporation rates and baleen growth rates: Implications for assessing diet and movement patterns in mysticetes

PubMed Central

Busquets-Vass, Geraldine; Newsome, Seth D.; Calambokidis, John; Serra-Valente, Gabriela; Jacobsen, Jeff K.; Aguíñiga-García, Sergio; Gendron, Diane

2017-01-01

Stable isotope analysis in mysticete skin and baleen plates has been repeatedly used to assess diet and movement patterns. Accurate interpretation of isotope data depends on understanding isotopic incorporation rates for metabolically active tissues and growth rates for metabolically inert tissues. The aim of this research was to estimate isotopic incorporation rates in blue whale skin and baleen growth rates by using natural gradients in baseline isotope values between oceanic regions. Nitrogen (δ15N) and carbon (δ13C) isotope values of blue whale skin and potential prey were analyzed from three foraging zones (Gulf of California, California Current System, and Costa Rica Dome) in the northeast Pacific from 1996–2015. We also measured δ15N and δ13C values along the lengths of baleen plates collected from six blue whales stranded in the 1980s and 2000s. Skin was separated into three strata: basale, externum, and sloughed skin. A mean (±SD) skin isotopic incorporation rate of 163±91 days was estimated by fitting a generalized additive model of the seasonal trend in δ15N values of skin strata collected in the Gulf of California and the California Current System. A mean (±SD) baleen growth rate of 15.5±2.2 cm y-1 was estimated by using seasonal oscillations in δ15N values from three whales. These oscillations also showed that individual whales have a high fidelity to distinct foraging zones in the northeast Pacific across years. The absence of oscillations in δ15N values of baleen sub-samples from three male whales suggests these individuals remained within a specific zone for several years prior to death. δ13C values of both whale tissues (skin and baleen) and potential prey were not distinct among foraging zones. Our results highlight the importance of considering tissue isotopic incorporation and growth rates when studying migratory mysticetes and provide new insights into the individual movement strategies of blue whales. PMID:28562625

Visualizing Single Cell Biology: Nanosims Studies of Carbon and Nitrogen Metabolism in Diazotrophic Cyanobacteria

NASA Astrophysics Data System (ADS)

Pett-Ridge, J.; Finzi, J. A.; Capone, D. G.; Popa, R.; Nealson, K. H.; Ng, W.; Spormann, A. M.; Hutcheon, I. D.; Weber, P. K.

2007-12-01

Filamentous nitrogen fixing (diazotrophic) cyanobacteria are key players in global nutrient cycling, but the relationship between CO2- and N2-fixation and intercellular exchange of these elements remains poorly understood in many genera. These bacteria are faced with the challenge of isolating regions of N-fixation (O2 inhibited) and photosynthetic (O2 producing) activity. We used isotope labeling in conjunction with a high-resolution isotope and elemental mapping technique (NanoSIMS) to quantitatively describe 13C and 15N uptake and transport in two aquatic cyanobacteria grown on NaH13CO3 and 15N2. The technical challenges of tracing isotopes within individual bacteria can be overcome with high resolution Secondary Ion Mass Spectrometry (NanoSIMS). In NanoSIMS analysis, samples are sputtered with an energetic primary beam (Cs+, O-) liberating secondary ions that are separated by the mass spectrometer and detected in a suite of electron multipliers. Five isotopic species may be analyzed concurrently with spatial resolution as fine as 50nm. A high sensitivity isotope ratio 'map' can then be generated for the analyzed area. Using sequentially harvested cyanobacteria in conjunction with enriched H13CO3 and 15N2 incubations, we measured temporal enrichment patterns that evolve over the course of a day's growth and suggest tightly regulated changes in fixation kinetics. With a combination of TEM, SEM and NanoSIMS analyses, we also mapped the distribution of C, N and Mo (a critical nitrogenase co-factor) isotopes in intact cells. Our results suggest that NanoSIMS mapping of metal enzyme co-factors may be a powerful method of identifying physiological and morphological characteristics within individual bacterial cells, and could be used to provide a 3-dimensional context for more traditional analyses such as immunogold labeling. Finally, we resolved patterns of isotope enrichment at multiple spatial scales: sub-cellular variation, cell-cell differences along filaments, inter-species transfers (with Rhizobium epibionts), and within-cell depth profiles. Spatial enrichment patterns were correlated with morphological features evidenced in TEM images of microtomed filaments. These features indicate how 15N and 13C "hotspots" are dispersed throughout individual cells in different species, and may indicate isolated locations of increased N2 fixation, sites of amino acid/protein synthesis, or cyanophycin storage granules. This combination of Nano-Secondary Ion Mass Spectrometry (NanoSIMS) analysis and high resolution microscopy allows isotopic analysis to be linked to morphological features and holds great promise for fine-scale studies of bacteria metabolism.

CISOCUR - Hydrodynamic circulation in the Curonian Lagoon inferred through stable isotope measurements and numerical modelling

NASA Astrophysics Data System (ADS)

Umgiesser, Georg; Razinkovas-Baziukas, Arturas; Barisevičiūtė, Ruta; Baziukė, Dalia; Ertürk, Ali; Gasiūnaitė, Jovita; Gulbinskas, Saulius; Lubienė, Irma; Maračkinaite, Jurgita; Petkuvienė, Jolita; Pilkaitytė, Renata; Ruginis, Tomas; Zemlys, Petras; Žilius, Mindaugas

2013-04-01

The spatial pattern of the hydrodynamic circulation of the Curonian lagoon, the largest European coastal lagoon, is still little understood. In absence of automatic current registration data all the existing models relied mostly on such data as water levels leaving high level of uncertainty. Here we present CISOCUR, a new project financed by the European Social Fund under the Global Grant measure. The project applies a new methodology that uses the carbon stable isotope (SI) ratio of C12 and C13 that characterize different water sources entering the lagoon and may be altered by internal kinetic processes. Through the tracing of these isotope ratios different water masses can be identified. This gives the possibility to validate several hypotheses of water circulation and validate hydrodynamic models. In particular it will be possible to 1) trace water masses entering the lagoon through the Nemunas and the Klaipeda strait; 2) test the hypothesis of sediment transport mechanisms inside the lagoon; 3) evaluate the importance of physical forcing on the lagoon circulation. The use of a hydrodynamic finite element model, coupled with the SI method, will allow for a realistic description of the transport processes inside the Curonian lagoon. So the main research goal is to apply the stable isotope tracers and a finite element model to determine the circulation patterns in the Curonian lagoon. Overall, the project will develop according to 4 main phases: 1) A pilot study to measure the isotope composition of different carbon compounds (dissolved and suspended) in different water bodies that feed water into the central lagoon. Through this pilot study the optimal study sites for the seasonal campaign will be identified as well. 2) Seasonal field campaigns in the monitoring stations identified in phase 1 to measure the carbon isotope ratio. 3) Development of a model that describes the kinetics of carbon isotopes and its transformation. 4) Application of a hydrodynamic model that includes the kinetic model and uses the data in order to describe the overall circulation patterns in the Curonian lagoon. Project activities will be carried out as common co-ordinated effort of field an SI group and the modeling group that will have to calibrate the hydrodynamic model. In this way the expertise of different groups (physicists and oceanographers) will result in added value, providing the best available expertise along the eastern coast of the Baltic.

Rb-Sr Isotopic Systematics of Alkali-Rich Fragments in the Yamato-74442 LL-Chondritic Breccia

NASA Technical Reports Server (NTRS)

Yokoyama, T.; Misawa, K.; Okano, O.; Shih, C.-Y.; Nyquist, L. E.; Simo, J. I.; Tappa, M. J.; Yoneda, S.

2012-01-01

Alkali-rich igneous fragments were identified in the brecciated LL-chondrites, Kr henberg (LL5)], Bhola (LL3-6) and Yamato (Y)-74442 (LL4), and show characteristic fractionation patterns of alkaline elements. The K-Rb-Cs-rich fragments in Kr henberg, Bhola, and Y-74442 are very similar in mineralogy and petrography (olivine + pyroxene + glass), suggesting that they could have come from related precursor materials. We have undertaken Rb-Sr isotopic studies on alkali-rich fragments in Y-74442 to precisely determine their crystallization ages and the isotopic signatures of their precursor material(s).

Origin of the Sudbury Complex by meteoritic impact: Neodymium isotopic evidence

USGS Publications Warehouse

Faggart, B.E.; Basu, A.R.; Tatsumoto, M.

1985-01-01

Samarium-neodymium isotopic data on whole rocks and minerals of the Sudbury Complex in Canada gave an igneous crystallization age of 1840 ?? 21 ?? 106 years. The initial epsilon neodymium values for 15 whole rocks are similar to those for average upper continental crust, falling on the crustal trend of neodymium isotopic evolution as defined by shales. The rare earth element concentration patterns of Sudbury rocks are also similar to upper crustal averages. These data suggest that the Sudbury Complex formed from melts generated in the upper crust and are consistent with a meteoritic impact.

400 Years of summer hydroclimate from stable isotopes in Iberian trees

NASA Astrophysics Data System (ADS)

Andreu-Hayles, Laia; Ummenhofer, Caroline C.; Barriendos, Mariano; Schleser, Gerhard H.; Helle, Gerhard; Leuenberger, Markus; Gutiérrez, Emilia; Cook, Edward R.

2017-07-01

Tree rings are natural archives that annually record distinct types of past climate variability depending on the parameters measured. Here, we use ring-width and stable isotopes in cellulose of trees from the northwestern Iberian Peninsula (IP) to understand regional summer hydroclimate over the last 400 years and the associated atmospheric patterns. Correlations between tree rings and climate data demonstrate that isotope signatures in the targeted Iberian pine forests are very sensitive to water availability during the summer period, and are mainly controlled by stomatal conductance. Non-linear methods based on extreme events analysis allow for capturing distinct seasonal climatic variability recorded by tree-ring parameters and asymmetric signals of the associated atmospheric features. Moreover, years with extreme high (low) values in the tree-ring records were characterised by coherent large-scale atmospheric circulation patterns with reduced (enhanced) moisture transport onto the northwestern IP. These analyses of extremes revealed that high/low proxy values do not necessarily correspond to mirror images in the atmospheric anomaly patterns, suggesting different drivers of these patterns and the corresponding signature recorded in the proxies. Regional hydroclimate features across the broader IP and western Europe during extreme wet/dry summers detected by the northwestern IP trees compare favourably to independent multicentury sea level pressure and drought reconstructions for Europe. Historical records also validate our findings that attribute non-linear moisture signals recorded by extreme tree-ring values to distinct large-scale atmospheric patterns and allow for 400-year reconstructions of the frequency of occurrence of extreme conditions in late spring and summer hydroclimate.

400 years of summer hydroclimate from stable isotopes in Iberian trees

NASA Astrophysics Data System (ADS)

Andreu-Hayles, Laia; Ummenhofer, Caroline C.; Barriendos, Mariano; Schleser, Gerhard H.; Helle, Gerhard; Leuenberger, Markus; Gutierrez, Emilia; Cook, Edward R.

2017-04-01

Tree rings are natural archives that annually record distinct types of past climate variability depending on the parameters measured. Here, we use ring-width and stable isotopes in cellulose of trees from the northwestern Iberian Peninsula (IP) to understand regional summer hydroclimate over the last 400 years and the associated atmospheric patterns. Correlations between tree rings and climate data demonstrate that isotope signatures in the targeted Iberian pine forests are very sensitive to water availability during the summer period, and are mainly controlled by stomatal conductance. Non-linear methods based on extreme events analysis allow for capturing distinct seasonal climatic variability recorded by tree-ring parameters and asymmetric signals of the associated atmospheric features. Moreover, years with extreme high (low) values in the tree-ring records were characterised by coherent large-scale atmospheric circulation patterns with reduced (enhanced) moisture transport onto the northwestern IP. These analyses of extremes revealed that high/low proxy values do not necessarily correspond to mirror images in the atmospheric anomaly patterns, suggesting different drivers of these patterns and the corresponding signature recorded in the proxies. Regional hydroclimate features across the broader IP and western Europe during extreme wet/dry summers detected by the northwestern IP trees compare favourably to an independent multicentury sea level pressure and drought reconstruction for Europe. Historical records also validate our findings that attribute non-linear moisture signals recorded by extreme tree-ring values to distinct large-scale atmospheric patterns and allow for 400-yr reconstructions of the frequency of occurrence of extreme conditions in summer hydroclimate. We will discuss how the results for Lillo compare with other records.

Condensation and Evaporation of Solar System Materials

NASA Astrophysics Data System (ADS)

Davis, A. M.; Richter, F. M.

2003-12-01

It is widely believed that the materials making up the solar system were derived from a nebular gas and dust cloud that went through an early high-temperature stage during which virtually all of the material was in the gas phase. At one time, it was thought that the entire inner solar nebula was hot, but it is now believed that most material was processed through regions where high temperatures were achieved. Certainly some material, such as presolar grains (cf., Mendybaev et al., 2002a), has never been exposed to high temperatures. As the system cooled, solids and perhaps liquids began to condense, but at some point the partially condensed materials became isolated from the remaining gas. Various lines of evidence support this view. At the largest scale, there is the observation that the Earth, Moon, Mars, and all chondritic meteorites except for the CI chondrites are depleted to varying degrees in the abundances of moderately volatile elements relative to bulk solar system composition. The CI chondrites reflect the bulk composition of the solar system for all but hydrogen, carbon, nitrogen, oxygen, and the rare gases, the most volatile elements (see Chapter 1.03; Palme et al., 1988; McDonough and Sun, 1995; Humayun and Cassen, 2000). The depletions in moderately volatile elements are, to a significant degree, correlated with condensation temperature, suggesting progressive removal of gas as condensation proceeded ( Cassen, 1996). Additional observations that can be explained by partial condensation are that various particularly primitive components of meteorites (e.g., calcium-, aluminum-rich refractory inclusions, and certain metal grains) have mineralogy and/or details of their chemical composition that are remarkably similar to what is calculated for equilibrium condensates from a solar composition gas. For example, the calcium-, aluminum-rich inclusions (CAIs) in chondritic meteorites have compositions very similar to that calculated for the first 5% of total condensable matter (see Chapter 1.08; Grossman, 1973; Wänke et al., 1974; Grossman and Ganapathy, 1976; Grossman et al., 1977), where CI chondrites are taken to represent total condensable matter.Elemental abundance patterns ordered by volatility certainly could have been produced by partial condensation, but they could also have been caused by partial evaporation. The relative importance of these opposite processes is still subject to debate and uncertainty. It should be remembered that condensation calculations typically assume chemical equilibrium in a closed system, in which case the system has no memory of the path by which it arrived at a given state, and thus the chemical and isotopic composition of the condensed phase cannot be used to distinguish between partial condensation and partial evaporation. Humayun and Clayton (1995) have taken a somewhat different view by arguing that condensation and evaporation are distinguishable, in that evaporation, but not condensation, will produce isotopically fractionated residues. With this idea in mind, they carefully measured the potassium isotopic compositions of a broad range of solar system materials with different degrees of potassium depletion and found them to be indistinguishable. This they took as evidence that evaporation could not have been a significant process in determining the diverse elemental abundance patterns of the various solar system materials they measured, because had evaporation been important in fractionating potassium it would have also fractionated the potassium isotopes. We will qualify this line of reasoning by arguing that evaporation and condensation can under certain conditions produce isotopically fractionated condensed phases (i.e., that partial evaporation can produce isotopically heavy residues and that partial condensation can produce isotopically light condensates) but that under other conditions both can produce elemental fractionations without significant isotopic fractionation. The absence of isotopic fractionation in a volatile element-depleted condensed phase is more a measure of the degree to which the system maintained thermodynamic equilibrium than a diagnostic of whether the path involved condensation or evaporation.The pervasive volatile element depletion of inner solar system planets and the asteroidal parent bodies of most meteorites is a major, but by no means the only reason to consider evaporation and condensation processes in the early history of the solar system. Chondrules appear to have been rapidly heated and then cooled over a period of minutes to hours (see Chapter 1.07). If this occurred in a gas of solar composition under nonequilibrium conditions, chondrules should have partially evaporated and an isotopic fractionation record should remain. The absence of such effects can be used to chonstrain the conditions of chondrule formation (e.g., Alexander et al., 2000; Alexander and Wang, 2001). There is good petrologic, chemical, and isotopic evidence suggesting that certain solar system materials such as the coarse-grained CAIs are likely evaporation residues. For example, the type B CAIs are often found to have correlated enrichments in the heavy isotopes of silicon and magnesium ( Figure 1), and these isotopic fractionations are very much like those of evaporation residues produced in laboratory experiments. Condensation also appears to be a major control of elemental zoning patterns in metal grains in CH chondrites (Meibom et al., 1999, 2001; Campbell et al., 2001; Petaev et al., 2001; Campbell et al., 2002). A more contemporary example is the isotopic and chemical compositions of deep-sea spherules that have been significantly affected by evaporative loss during atmospheric entry ( Davis et al., 1991a; Davis and Brownlee, 1993; Herzog et al., 1994, 1999; Xue et al., 1995; Alexander et al., 2002). (7K)Figure 1. Isotopic mass fractionation effects in CAIs. Most coarse-grained CAIs have enrichments of a few ‰ amu-1 in magnesium and silicon, whereas "fractionation and unknown nuclear" (FUN) CAIs are isotopically heavier. The volatile element depletion patterns of planetary size objects and the chemical and isotopic composition of numerous smaller objects such as chondrules and CAIs provide the motivation to consider evaporation and condensation process in the early solar system. The key point is that the processes that led to chondrules and planets appear to have occurred under conditions very close to equilibrium, whereas the processes that led to CAIs involved significant departures from equilibrium.

Lead spatio-temporal pattern identification in urban microenvironments using moss bags and the Kohonen self-organizing maps

NASA Astrophysics Data System (ADS)

Deljanin, Isidora; Antanasijević, Davor; Vuković, Gordana; Urošević, Mira Aničić; Tomašević, Milica; Perić-Grujić, Aleksandra; Ristić, Mirjana

2015-09-01

The first investigation of the use of the Kohonen self-organizing map (SOM) which includes lead concentration and its isotopic composition in moss bags to assess the spatial and temporal patterns of lead in the urban microenvironments is presented in this paper. The moss bags experiment was carried out during 2011 in the city tunnel in Belgrade, as well as in street canyons at different heights (4, 8 and 16 m) and in public garages. The moss bags were exposed for 5 and 10 weeks. The results revealed that the 10 weeks period represents suitable exposure time in screening Pb isotopic composition in active biomonitoring analysis. The obtained results showed that the SOM analysis, by recognizing slight differences among moss samples regarding exposure time, horizontal and vertical spatial distribution, with both, contribution of stable lead isotopes and Pb concentration, could be recommended in biomonitoring analysis of lead distribution in urban microenvironments.

Distinct Dual C-Cl Isotope Fractionation Patterns during Anaerobic Biodegradation of 1,2-Dichloroethane: Potential To Characterize Microbial Degradation in the Field.

PubMed

Palau, J; Yu, R; Hatijah Mortan, S; Shouakar-Stash, O; Rosell, M; Freedman, D L; Sbarbati, C; Fiorenza, S; Aravena, R; Marco-Urrea, E; Elsner, M; Soler, A; Hunkeler, D

2017-03-07

This study investigates, for the first time, dual C-Cl isotope fractionation during anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) via dihaloelimination by Dehalococcoides and Dehalogenimonas-containing enrichment cultures. Isotopic fractionation of 1,2-DCA (ε bulk C and ε bulk Cl ) for Dehalococcoides (-33.0 ± 0.4‰ and -5.1 ± 0.1‰) and Dehalogenimonas-containing microcosms (-23 ± 2‰ and -12.0 ± 0.8‰) resulted in distinctly different dual element C-Cl isotope correlations (Λ = Δδ 13 C/Δδ 37 Cl ≈ ε bulk C /ε bulk Cl ), 6.8 ± 0.2 and 1.89 ± 0.02, respectively. Determined isotope effects and detected products suggest that the difference on the obtained Λ values for biodihaloelimination could be associated with a different mode of concerted bond cleavage rather than two different reaction pathways (i.e., stepwise vs concerted). Λ values of 1,2-DCA were, for the first time, determined in two field sites under reducing conditions (2.1 ± 0.1 and 2.2 ± 2.9). They were similar to the one obtained for the Dehalogenimonas-containing microcosms (1.89 ± 0.02) and very different from those reported for aerobic degradation pathways in a previous laboratory study (7.6 ± 0.1 and 0.78 ± 0.03). Thus, this study illustrates the potential of a dual isotope analysis to differentiate between aerobic and anaerobic biodegradation pathways of 1,2-DCA in the field and suggests that this approach might also be used to characterize dihaloelimination of 1,2-DCA by different bacteria, which needs to be confirmed in future studies.

Multi-isotope (carbon and chlorine) analysis for fingerprinting and site characterization at a fractured bedrock aquifer contaminated by chlorinated ethenes.

PubMed

Palau, Jordi; Marchesi, Massimo; Chambon, Julie C C; Aravena, Ramon; Canals, Àngels; Binning, Philip J; Bjerg, Poul L; Otero, Neus; Soler, Albert

2014-03-15

The use of compound specific multi-isotope approach (C and Cl) in the characterization of a chlorinated ethenes contaminated fractured aquifer allows the identification of several sources and contaminant plumes, as well as the occurrence of biodegradation and mixing processes. The study site is located in Spain with contamination resulting in groundwater concentrations of up to 50mg/L of trichloroethene (TCE), the most abundant chlorinated ethene, and 7 mg/L of tetrachloroethene (PCE). The potential sources of contamination including abandoned barrels, an underground tank, and a disposal lagoon, showed a wide range in δ(13)C values from -15.6 to -40.5‰ for TCE and from -18.5 to -32.4‰ for PCE, allowing the use of isotope fingerprinting for tracing of the origin and migration of these contaminants in the aquifer. In contrast, there is no difference between the δ(37)Cl values for TCE in the contaminant sources, ranging from +0.53 to +0.66‰. Variations of δ(37)Cl and δ(13)C in the different contaminant plumes were used to investigate the role of biodegradation in groundwater. Moreover, the isotopic data were incorporated into a reactive transport model for determination of whether the isotope pattern observed downstream from the tank's source could be explained by the simultaneous effect of mixing and biodegradation. The results demonstrate that a multi-isotope approach is a valuable tool for characterization of complex sites such as fractured bedrock aquifer contaminated by multiple sources, providing important information which can be used by consultants and site managers to prioritize and design more successful remediation strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

Magnesium stable isotope ecology using mammal tooth enamel

NASA Astrophysics Data System (ADS)

Martin, Jeremy E.; Vance, Derek; Balter, Vincent

2015-01-01

Geochemical inferences on ancient diet using bone and enamel apatite rely mainly on carbon isotope ratios (δ13C) and to a lesser extent on strontium/calcium (Sr/Ca) and barium/calcium (Ba/Ca) elemental ratios. Recent developments in nontraditional stable isotopes provide an unprecedented opportunity to use additional paleodietary proxies to disentangle complex diets such as omnivory. Of particular relevance for paleodietary reconstruction are metals present in large quantity in bone and enamel apatite, providing that biologically mediated fractionation processes are constrained. Calcium isotope ratios (δ44Ca) meet these criteria but exhibit complex ecological patterning. Stable magnesium isotope ratios (δ26Mg) also meet these criteria but a comprehensive understanding of its variability awaits new isotopic data. Here, 11 extant mammal species of known ecology from a single locality in equatorial Africa were sampled for tooth enamel and, together with vegetation and feces, analyzed for δ26Mg, δ13C, Sr/Ca, and Ba/Ca ratios. The results demonstrate that δ26Mg incorporated in tooth enamel becomes heavier from strict herbivores to omnivores/faunivores. Using data from experimentally raised sheep, we suggest that this 26Mg enrichment up the trophic chain is due to a 26Mg enrichment in muscle relative to bone. Notably, it is possible to distinguish omnivores from herbivores, using δ26Mg coupled to Ba/Ca ratios. The potential effects of metabolic and dietary changes on the enamel δ26Mg composition remain to be explored but, in the future, multiproxy approaches would permit a substantial refinement of dietary behaviors or enable accurate trophic reconstruction despite specimen-limited sampling, as is often the case for fossil assemblages.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Landscape cultivation alters δ30Si signature in terrestrial ecosystems

PubMed Central

Vandevenne, Floor I.; Delvaux, Claire; Hughes, Harold J.; André, Luc; Ronchi, Benedicta; Clymans, Wim; Barão, Lúcia; Govers, Gerard; Meire, Patrick; Struyf, Eric

2015-01-01

Despite increasing recognition of the relevance of biological cycling for Si cycling in ecosystems and for Si export from soils to fluvial systems, effects of human cultivation on the Si cycle are still relatively understudied. Here we examined stable Si isotope (δ30Si) signatures in soil water samples across a temperate land use gradient. We show that – independent of geological and climatological variation – there is a depletion in light isotopes in soil water of intensive croplands and managed grasslands relative to native forests. Furthermore, our data suggest a divergence in δ30Si signatures along the land use change gradient, highlighting the imprint of vegetation cover, human cultivation and intensity of disturbance on δ30Si patterns, on top of more conventionally acknowledged drivers (i.e. mineralogy and climate). PMID:25583031

Disentangling effects of growth and nutritional status on seabird stable isotope ratios.

PubMed

Sears, Justine; Hatch, Scott A; O'Brien, Diane M

2009-02-01

A growing number of studies suggest that an individual's physiology affects its carbon and nitrogen stable isotope signatures, obscuring a signal often assumed to be only a reflection of diet and foraging location. We examined effects of growth and moderate food restriction on red blood cell (RBC) and feather delta(15)N and delta(13)C in rhinoceros auklet chicks (Cerorhinca monocerata), a piscivorous seabird. Chicks were reared in captivity and fed either control (75 g/day; n = 7) or ~40% restricted (40 g/day; n = 6) amounts of high quality forage fish. We quantified effects of growth on isotopic fractionation by comparing delta(15)N and delta(13)C in control chicks to those of captive, non-growing subadult auklets (n = 11) fed the same diet. To estimate natural levels of isotopic variation, we also collected blood from a random sample of free-living rhinoceros auklet adults and chicks in the Gulf of Alaska (n = 15 for each), as well as adult feather samples (n = 13). In the captive experiment, moderate food restriction caused significant depletion in delta(15)N of both RBCs and feathers in treatment chicks compared to control chicks. Growth also induced depletion in RBC delta(15)N, with chicks exhibiting lower delta(15)N when they were growing the fastest. As growth slowed, delta(15)N increased, resulting in an overall pattern of enrichment over the course of the nestling period. Combined effects of growth and restriction depleted delta(15)N in chick RBCs by 0.92 per thousand. We propose that increased nitrogen-use efficiency is responsible for (15)N depletion in both growing and food-restricted chicks. delta(15)N values in RBCs of free-ranging auklets fell within a range of only 1.03 per thousand, while feather delta(15)N varied widely. Together, our captive and field results suggest that both growth and moderate food restriction can affect stable isotope ratios in an ecologically meaningful way in RBCs although not feathers due to greater natural variability in this tissue.

[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.

Isoscapes of the Sierra Nevada, California: Inferences from Landscape Patterns of Carbon, Nitrogen and Hydrogen in Lakes and Their Watersheds

NASA Astrophysics Data System (ADS)

Sickman, J. O.; Sadro, S.; Lucero, D. M.

2016-12-01

Montane aquatic ecosystems integrate conditions within their catchments and act as sentinels for environmental change. Variations in elevation, atmospheric deposition, and bedrock chemistry produce complex environmental gradients that influence the flow of materials and energy between lakes and their watersheds. We investigated the landscape-level variations in stable isotopes (Isoscapes) of C, N and H in foodwebs of 12 Sierra Nevada lakes and watersheds spanning an elevation range of 1500 to 3500 m a.s.l. Collections included terrestrial plants, soils and insects and the entire aquatic food chain from dissolved organic matter (DOM) through plankton, benthic invertebrates and fish. Our major objective was to understand how environmental gradients such as temperature and precipitation (distance-for-time proxies for climate change) effect foodweb structure and reciprocal subsidies of C and energy between lakes and their watersheds. Possibly related to its role as a limiting nutrient for aquatic and terrestrial ecosystems, we observed no consistent pattern for δ15N across any environmental gradient. In contrast, there was a strong pattern of enrichment in 13C with increasing elevation (slope = +3.4 permil per km). Similarly, δ2H of snowfall and foodweb components showed a depletion of 2H with elevation (slope = -17 permil per km for foodwebs and -20 permil per km for water) suggesting strong influence of snowmelt on aquatic ecosystem function. We will further explore these isotope patterns and draw inferences on how changes in montane climate, including trends toward earlier snowmelt and lower snowfall, will impact aquatic ecosystems of the Sierra Nevada.

Bioavailability and uptake of smelter emissions in freshwater zooplankton in northeastern Washington, USA lakes using Pb isotope analysis and trace metal concentrations.

PubMed

Child, A W; Moore, B C; Vervoort, J D; Beutel, M W

2018-07-01

The upper Columbia River and associated valley systems are highly contaminated with metal wastes from nearby smelting operations in Trail, British Columbia, Canada (Teck smelter), and to a lesser extent, Northport, Washington, USA (Le Roi smelter). Previous studies have investigated depositional patterns of airborne emissions from these smelters, and documented the Teck smelter as the primary metal contamination source. However, there is limited research directed at whether these contaminants are bioavailable to aquatic organisms. This study investigates whether smelter derived contaminants are bioavailable to freshwater zooplankton. Trace metal (Zn, Cd, As, Sb, Pb and Hg) concentrations and Pb isotope compositions of zooplankton and sediment were measured in lakes ranging from 17 to 144 km downwind of the Teck smelter. Pb isotopic compositions of historic ores used by both smelters are uniquely less radiogenic than local geologic formations, so when zooplankton assimilate substantial amounts of smelter derived metals their compositions deviate from local baseline compositions toward ore compositions. Sediment metal concentrations and Pb isotope compositions in sediment follow significant (p < 0.001) negative exponential and sigmoidal patterns, respectively, as distance from the Teck smelting operation increases. Zooplankton As, Cd, and Sb contents were related to distance from the Teck smelter (p < 0.05), and zooplankton Pb isotope compositions suggest As, Cd, Sb and Pb from historic and current smelter emissions are biologically available to zooplankton. Zooplankton from lakes within 86 km of the Teck facility display isotopic evidence that legacy ore pollution is biologically available for assimilation. However, without water column data our study is unable to determine if legacy contaminants are remobilized from lake sediments, or erosional pathways from the watershed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Detection of counterfeit antiviral drug Heptodin and classification of counterfeits using isotope amount ratio measurements by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) and isotope ratio mass spectrometry (IRMS).

PubMed

Santamaria-Fernandez, Rebeca; Hearn, Ruth; Wolff, Jean-Claude

2009-06-01

Isotope ratio mass spectrometry (IRMS) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) are highly important techniques that can provide forensic evidence that otherwise would not be available. MC-ICP-MS has proved to be a very powerful tool for measuring high precision and accuracy isotope amount ratios. In this work, the potential of combining isotope amount ratio measurements performed by MC-ICP-MS and IRMS for the detection of counterfeit pharmaceutical tablets has been investigated. An extensive study for the antiviral drug Heptodin has been performed for several isotopic ratios combining MC-ICP-MS and an elemental analyser EA-IRMS for stable isotope amount ratio measurements. The study has been carried out for 139 batches of the antiviral drug and analyses have been performed for C, S, N and Mg isotope ratios. Authenticity ranges have been obtained for each isotopic system and combined to generate a unique multi-isotopic pattern only present in the genuine tablets. Counterfeit tablets have then been identified as those tablets with an isotopic fingerprint outside the genuine isotopic range. The combination of those two techniques has therefore great potential for pharmaceutical counterfeit detection. A much greater power of discrimination is obtained when at least three isotopic systems are combined. The data from these studies could be presented as evidence in court and therefore methods need to be validated to support their credibility. It is also crucial to be able to produce uncertainty values associated to the isotope amount ratio measurements so that significant differences can be identified and the genuineness of a sample can be assessed.

Mid-late Holocene palaeoclimate of northern Jordan from speleothem geochemistry

NASA Astrophysics Data System (ADS)

Robinson, S. A.; Black, S.; Lovell, J.; Atkinson, T. C.

2009-04-01

The southern Levant region (encompassing the modern countries of Israel and Jordan) is a climatically sensitive area due to the proximity of the Negev and Arabian Deserts to the south and east. Although there is a general pattern of decreasing rainfall to the south and east of the region, local topographic features, most notably the Dead Sea Rift Valley, have a significant effect on detailed rainfall patterns. Our understanding of the Holocene climate of the southern Levant is principally known from records obtained to the west of the Dead Sea Rift, on the borders of the Negev Desert and from the lakes within the rift valley itself. Palaeoclimate records from the more interior regions, such as Jordan, are fewer in number and, generally at lower stratigraphic resolution. A recent archaeological survey has revealed the existence of limestone caves in northern Jordan, many of which were previously unknown to academics working in the region. These caves contain a variety of architectures, including stalagmites, stalactites, flowstones and soda straws. We present geochemical data (oxygen and carbon-isotopes, and uranium-series dates) from a small speleothem that provides the first detailed mid-late Holocene climate record for the area east. The new data are similar in value and contain similar magnitude shifts to previously published data from Israel (Soreq and Nahal Qanah Caves) and Lebanon (Jeita Cave). Through comparison with these other speleothem records we suggest that the oxygen-isotopic composition of the Jordanian speleothem is consistent with rainfall from Mediterranean-sourced weather systems that evolved to lighter isotopic compositions through rainout of 18O as they moved into the interior of the southern Levant. The Ras Muneef GNIP monitoring station provides a limited record of precipitation rates and isotopic compositions of rainwater. Combining this data with the speleothem data, suggests that Holocene temperatures in northern Jordan were broadly similar to present day mean annual temperatures and that the fluctuations in δ18O are likely the result of changes in the amount of precipitation.

Boron Isotopes in Modern and Cenozoic Scleractinian Fossil Corals

NASA Astrophysics Data System (ADS)

Gothmann, A.; Bender, M. L.; Adkins, J. F.

2016-12-01

Recent measurements of boron isotopes in modern coral support the hypothesis that coral biologically up-regulate the pH of the fluid from which they calcify to facilitate skeletal mineralization [1]. While this evidence of biological pH adjustment provides important insight into the mechanism by which coral make their skeletons, it also complicates the use of coral boron isotopes as a paleoseawater pH proxy. We measured boron isotopes in 11 modern and well preserved fossil corals using Secondary Ion Mass Spectrometry to characterize fine-scale ( 30 µm) patterns of δ11B variability. In addition to δ11B, we measured B/Ca, Mg/Ca, Sr/Ca, and Mn/Ca ratios in order to compare isotopes with element/Ca variability and monitor for diagenetic alteration. We find that in different species of modern and well preserved fossil coral, the measured range of δ11B varies from 5 to 15 ‰. Also, while corals of similar geologic age have similar average δ11B compositions, at the scale of our measurements they do not appear to share a consistent pattern of minimum δ11B, maximum δ11B, or range in δ11B. The δ11B of fossil corals increases by 7 ‰ between the Early Cenozoic and today. While the general pattern of coral δ11B change is similar to the pattern found in foraminifera-based δ11B records [e.g., 2], the magnitude of the coral change is approximately 2-3 times as large as changes inferred from foraminifera. Although it is not possible to separate the influence of changing seawater pH and changing δ11Bseawater on fossil coral boron isotope compositions, the record can be explained by a combination of lower seawater pH and lower seawater δ11B during the the Early Cenozoic. Our coral results suggest an Early Cenozoic δ11Bseawater composition that is much lower than inferred from other approaches, and similar to Early Cenozoic δ11Bseawater as inferred from brine inclusions in halite [3]. [1.] McCulloch, M.T., Trotter, J., Montagna, P., Falter, J., Dunbar, R., Freiwald, A., Forsterra, G., Lopez Correa, M., Maier, C., Ruggeberg, A., Taviani, M., 2012. Geochimica et Cosmochimica Acta 87, 21-34. [2.] Pearson, P.N., Palmer, M.R., 2000. Nature 406, 695-699. [3.] Paris, G., Gaillardet, J., Louvat, P. 2010. Geology 38, 1035-1038.

Marked spatial gradient in the topographic evolution of the Andes spanning the Chilean flat-slab transition: evidence from stable isotope paleoaltimetry and zircon double dating

NASA Astrophysics Data System (ADS)

Hoke, G. D.; McPhillips, D. F.; Giambiagi, L.; Garzione, C. N.; Mahoney, J. B.; Strecker, M. R.

2015-12-01

The major changes in the subduction angle of the Nazca plate are often hypothesized to have important consequences for the tectonic evolution of the Andes. Temporal and spatial patterns of topographic growth and exhumation are indicators that should help elucidate any linkages to subduction angle. Here, we combine observations from stable isotope paleoaltimetry with detrital zircon double dating between 30 and 35°S to demonstrate a consistent increase in surface and rock uplift in the Andes south of 32°S. The stable isotope data are from Miocene pedogenic carbonates collected from seven different basin sequences spanning different tectonic and topographic positions in the range. Paleoelevations between 1 km and 1.9 km are calculated using modern local isotope-elevation gradients along with carbonate-formation temperatures determined from clumped isotope studies in modern soils. Present day, low elevation foreland localities were at their present elevations during the Miocene, while three of the intermontane basins experienced up to 2 km of surface uplift between the end of deposition during the late Miocene and present. Detrital zircon (U-Th-Sm)/He and U-Pb double dating in three modern drainage basins (Tunuyán, Arroyo Grande and Río de los Patos) reveals clear Miocene exhumation signals south of the flat slab with no recent exhumation apparent at 32°S. The exhumation pattern is consistent with paleoaltimetry results. Interestingly, the maximum inferred surface uplift is greatest where the crust is thinnest, and the timing of the observed changes in elevation and exhumation has not been linked to any documented episodes of large-magnitude crustal shortening in the eastern half of the range. The spatial pattern of surface uplift and exhumation seems to mimic the Pampean flat slab's geometry, however, it could be equally well explained by eastward migration of a crustal root via ductile deformation in the lower crust and is not related to flat-slab subduction.

Platinum isotopes in iron meteorites: Galactic cosmic ray effects and nucleosynthetic homogeneity in the p-process isotope 190Pt and the other platinum isotopes

NASA Astrophysics Data System (ADS)

Hunt, Alison C.; Ek, Mattias; Schönbächler, Maria

2017-11-01

Platinum isotopes are sensitive to the effects of galactic cosmic rays (GCR), which can alter isotope ratios and mask nucleosynthetic isotope variations. Platinum also features one p-process isotope, 190Pt, which is very low abundance and therefore challenging to analyse. Platinum-190 is relevant for early solar-system chronology because of its decay to 186Os. Here, we present new Pt isotope data for five iron meteorite groups (IAB, IIAB, IID, IIIAB and IVA), including high-precision measurements of 190Pt for the IAB, IIAB and IIIAB irons, determined by multi-collector ICPMS. New data are in good agreement with previous studies and display correlations between different Pt isotopes. The slopes of these correlations are well-reproduced by the available GCR models. We report Pt isotope ratios for the IID meteorite Carbo that are consistently higher than the predicted effects from the GCR model. This suggests that the model predictions do not fully account for all the GCR effects on Pt isotopes, but also that the pre-atmospheric radii and exposure times calculated for Carbo may be incorrect. Despite this, the good agreement of relative effects in Pt isotopes with the predicted GCR trends confirms that Pt isotopes are a useful in-situ neutron dosimeter. Once GCR effects are accounted for, our new dataset reveals s- and r-process homogeneity between the iron meteorite groups studied here and the Earth. New 190Pt data for the IAB, IIAB and IIIAB iron meteorites indicate the absence of GCR effects and homogeneity in the p-process isotope between these groups and the Earth. This corresponds well with results from other heavy p-process isotopes and suggests their homogenous distribution in the inner solar system, although it does not exclude that potential p-process isotope variations are too diluted to be currently detectable.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Malic enzyme: Tritium isotope effects with alternative dinucleotide substrates and divalent metal ions

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

Karsten, W.E.; Harris, B.G.; Cook, P.F.

1992-01-01

The NAD-malic enzyme from Ascaris suum catalyzes the divalent metal ion dependent oxidative decarboxylation of L-malate to yield pyruvate, carbon dioxide and NADH. Multiple isotope effect studies suggest a stepwise chemical mechanism with hydride transfer from L-malate to NAD occurring first to form oxalacetate, followed by decarboxylation. Utilizing L-malate-2-T, tritium V/K isotope effects have been determined for the hydride transfer step using a variety of alternative dinucleotide substrates and divalent metal ions. Combination of these data with deuterium isotope effects data and previously determined [sup 13]C isotope effects has allowed the calculation of intrinsic isotope effects for the malic enzymemore » catalyzed reaction. The identity of both the dinucleotide substrate and divalent metal ion has an effect of the size of the intrinsic isotope effect for hydride transfer.« less

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

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

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ 15N and δ 13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ~10 000 years. In multiple regression analyses, δ 15N and δ 13C correlated strongly with depth, plot location, C/N, %N, and each other. Correlations with %N, %C, C/N, and the other isotope accounted for 80 % of variance for δ 15N and 38 % of variance for δ 13C, reflecting N and C losses.more » In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ 15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ 13CO 2 since the Industrial Revolution) lowered δ 13C in recent surficial samples. High δ 15N from –35 to –5 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to –35 cm depth. High δ 13C at ~4000 years BP (–65 to –105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ 13C and high δ 15N at –213 and –225 cm (~8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. As a result, the above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ 13C patterns.« less

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

NASA Astrophysics Data System (ADS)

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.; Iversen, Colleen M.; McFarlane, Karis J.; Thorp, Nathan R.; Hofmockel, Kirsten S.

2017-05-01

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ15N and δ13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ˜ 10 000 years. In multiple regression analyses, δ15N and δ13C correlated strongly with depth, plot location, C / N, %N, and each other. Correlations with %N, %C, C / N, and the other isotope accounted for 80 % of variance for δ15N and 38 % of variance for δ13C, reflecting N and C losses. In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ13CO2 since the Industrial Revolution) lowered δ13C in recent surficial samples. High δ15N from -35 to -55 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to -35 cm depth. High δ13C at ˜ 4000 years BP (-65 to -105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ13C and high δ15N at -213 and -225 cm ( ˜ 8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. The above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ13C patterns.

Long-term carbon and nitrogen dynamics at SPRUCE revealed through stable isotopes in peat profiles

DOE PAGES

Hobbie, Erik A.; Chen, Janet; Hanson, Paul J.; ...

2017-05-17

Peatlands encode information about past vegetation dynamics, climate, and microbial processes. Here, we used δ 15N and δ 13C patterns from 16 peat profiles to deduce how the biogeochemistry of the Marcell S1 forested bog in northern Minnesota responded to environmental and vegetation change over the past ~10 000 years. In multiple regression analyses, δ 15N and δ 13C correlated strongly with depth, plot location, C/N, %N, and each other. Correlations with %N, %C, C/N, and the other isotope accounted for 80 % of variance for δ 15N and 38 % of variance for δ 13C, reflecting N and C losses.more » In contrast, correlations with depth and topography (hummock or hollow) reflected peatland successional history and climate. Higher δ 15N in plots closer to uplands may reflect upland-derived DON inputs and accompanying shifts in N dynamics in the lagg drainage area surrounding the bog. The Suess effect (declining δ 13CO 2 since the Industrial Revolution) lowered δ 13C in recent surficial samples. High δ 15N from –35 to –5 cm probably indicated the depth of ectomycorrhizal activity after tree colonization of the peatland over the last 400 years, as confirmed by the occasional presence of wood down to –35 cm depth. High δ 13C at ~4000 years BP (–65 to –105 cm) could reflect a transition at that time to slower rates of peat accumulation, when 13C discrimination during peat decomposition may increase in importance. Low δ 13C and high δ 15N at –213 and –225 cm (~8500 years BP) corresponded to a warm period during a sedge-dominated rich fen stage. As a result, the above processes appear to be the primary drivers of the observed isotopic patterns, whereas there was no clear evidence for methane dynamics influencing δ 13C patterns.« less

Variation in carbon isotope discrimination in Cleistogenes squarrosa (Trin.) Keng: patterns and drivers at tiller, local, catchment, and regional scales

PubMed Central

Yang, Hao; Auerswald, Karl; Bai, Yongfei; Wittmer, Maximilian H. O. M.; Schnyder, Hans

2011-01-01

Understanding the patterns and drivers of carbon isotope discrimination in C4 species is critical for predicting the effects of global change on C3/C4 ratio of plant community and consequently on ecosystem functioning and services. Cleistogenes squarrosa (Trin.) Keng is a dominant C4 perennial bunchgrass of arid and semi-arid ecosystems across the Mongolian plateau of the Eurasian steppe. Its carbon isotope discrimination (13Δ) during photosynthesis is relatively large among C4 species and it is variable. Here the 13Δ of C. squarrosa and its potential drivers at a nested set of scales were examined. Within cohorts of tillers, 13Δ of leaves increased from 5.1‰ to 8.1‰ from old to young leaves. At the local scale, 13Δ of mature leaves varied from 5.8‰ to 8.4‰, increasing with decreasing grazing intensity. At the catchment scale, 13Δ of mature leaves varied from 6.2‰ to 8.5‰ and increased with topsoil silt content. At the regional scale, 13Δ of mature leaves varied from 5.5‰ to 8.9‰, increasing with growing-season precipitation. At all scales, 13Δ decreased with increasing leaf nitrogen content (Nleaf). Nleaf was positively correlated with grazing intensity and leaf position along tillers, but negatively correlated with precipitation. The presence of the correlations across a range of different environmental contexts strongly implicates Nleaf as a major driver of 13Δ in C. squarrosa and, possibly, other C4 species. PMID:21527626

Carbon and hydrogen isotopic composition of methane and C2+ alkanes in electrical spark discharge: implications for identifying sources of hydrocarbons in terrestrial and extraterrestrial settings.

PubMed

Telling, Jon; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2013-05-01

The low-molecular-weight alkanes--methane, ethane, propane, and butane--are found in a wide range of terrestrial and extraterrestrial settings. The development of robust criteria for distinguishing abiogenic from biogenic alkanes is essential for current investigations of Mars' atmosphere and for future exobiology missions to other planets and moons. Here, we show that alkanes synthesized during gas-phase radical recombination reactions in electrical discharge experiments have values of δ(2)H(methane)>δ(2)H(ethane)>δ(2)H(propane), similar to those of the carbon isotopes. The distribution of hydrogen isotopes in gas-phase radical reactions is likely due to kinetic fractionations either (i) from the preferential incorporation of (1)H into longer-chain alkanes due to the more rapid rate of collisions of the smaller (1)H-containing molecules or (ii) by secondary ion effects. Similar δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns may be expected in a range of extraterrestrial environments where gas-phase radical reactions dominate, including interstellar space, the atmosphere and liquid hydrocarbon lakes of Saturn's moon Titan, and the outer atmospheres of Jupiter, Saturn, Neptune, and Uranus. Radical recombination reactions at high temperatures and pressures may provide an explanation for the combined reversed δ(13)C(C1-C2+) and δ(2)H(C1-C2+) patterns of terrestrial alkanes documented at a number of high-temperature/pressure crustal sites.

Petrology and geochemistry of komatiites and tholeiites from Gorgona Island, Colombia

NASA Astrophysics Data System (ADS)

Aitken, Bruce G.; Echeverría, Lina M.

1984-04-01

Komatiitic rocks from Gorgona Island, Colombia, in contrast to their Archaean counterparts, occur as rather structureless flows. In addition, textural and mineralogical features indicate that the Gorgona komatiites may have crystallized from superheated liquids. Komatiitic rocks have MgO contents which range from 24 to 11 wt.% and plot on well-defined olivine (Fo90) control lines. Calculations show that potential evolved liquids (MgO<11 wt%) will be SiO2-poor. Komatiites, in this case, cannot be regarded as parental to the associated tholeiitic basalt sequence. On the basis of REE concentrations and Sr, Nd isotopic compositions, the associated basalts are found to be of two types. One type (K-tholeiite) is characterized by noticeably fractionated REE patterns and relatively primitive isotopic compositions similar to those of the komatiites. K-tholeiites, together with komatiites, are regarded as comprising a distinctive komatiitic suite. REE patterns within this suite show progressive depletion in the LREE from K-tholeiites to komatiites, and represent increasingly higher degrees of melting of the same mantle source region. The other type (T-tholeiite), representative of the bulk of the exposed basalt sequence, has flat REE patterns and relatively evolved isotopic compositions. This tholeiitic suite is clearly genetically unrelated to the komatiitic suite.

ICPD-A New Peak Detection Algorithm for LC/MS

PubMed Central

2010-01-01

Background The identification and quantification of proteins using label-free Liquid Chromatography/Mass Spectrometry (LC/MS) play crucial roles in biological and biomedical research. Increasing evidence has shown that biomarkers are often low abundance proteins. However, LC/MS systems are subject to considerable noise and sample variability, whose statistical characteristics are still elusive, making computational identification of low abundance proteins extremely challenging. As a result, the inability of identifying low abundance proteins in a proteomic study is the main bottleneck in protein biomarker discovery. Results In this paper, we propose a new peak detection method called Information Combining Peak Detection (ICPD ) for high resolution LC/MS. In LC/MS, peptides elute during a certain time period and as a result, peptide isotope patterns are registered in multiple MS scans. The key feature of the new algorithm is that the observed isotope patterns registered in multiple scans are combined together for estimating the likelihood of the peptide existence. An isotope pattern matching score based on the likelihood probability is provided and utilized for peak detection. Conclusions The performance of the new algorithm is evaluated based on protein standards with 48 known proteins. The evaluation shows better peak detection accuracy for low abundance proteins than other LC/MS peak detection methods. PMID:21143790

The Nature of Antarctic Temperature Change

NASA Astrophysics Data System (ADS)

Markle, B. R.; Steig, E. J.

2017-12-01

The Antarctic is an important component of global climate. While the Arctic has warmed significantly in the last century, the Antarctic as a whole has shown considerably less variability. There is, however, a pronounced spatial pattern to modern Antarctic temperature change. The high East Antarctic Ice Sheet shows little to no warming over recent decades while West Antarctica and the Peninsula shows some of the largest rates of warming on the globe. Examining past climate variability can help reveal the physical processes governing this spatial pattern of Antarctic temperature change. Modern Antarctic temperature variability is known from satellite and weather station observations. Understanding changes in the past, however, requires paleoclimate-proxies such as ice-core water-isotope records. Here we assess the spatial pattern of Antarctic temperature changes across a range of timescales, from modern decadal changes to millennial and orbital-scale variability. We reconstruct past changes in absolute temperatures from a suite of deep ice core records and an improved isotope-temperature reconstruction method. We use δ18O and deuterium excess records to reconstruct both evaporation source and condensation site temperatures. In contrast to previous studies we use a novel method that accounts for nonlinearities in the water-isotope distillation process. We quantify past temperature changes over the Southern Ocean and Antarctic Continent and the magnitude of polar amplification. We identify patterns of Antarctic temperature change that are common across a wide range of timescales and independent of the source of forcing. We examine the nature of these changes and their relationship to atmospheric thermodynamics.

Study of hydrogen bond polarized IR spectra of cinnamic acid crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Jabłońska, Magdalena

2004-11-01

This paper presents the results of investigation of the polarized IR spectra of cinnamic acid and of its deuterium derivative crystals. The spectra were measured by a transmission method, using polarized light, at the room temperature and at 77 K, for two different crystalline faces. Theoretical analysis of the results concerned linear dichroic effects, H/D isotopic and temperature effects, observed in the spectra of the hydrogen and of the deuterium bonds in cinnamic acid crystals, at the frequency ranges of the νO-H and the νO-D bands. The basic crystal spectral properties could be satisfactorily interpreted in a quantitative way for a centrosymmetric cyclic hydrogen bond dimer model. Such a model explains not only a two-branch structure of the νO-H and νO-D bands in crystalline spectra, but also some essential linear dichroic effects in the band frequency ranges, measured for isotopically diluted crystals. Model calculations, performed within the limits of the 'strong-coupling' model, allowed for quantitative interpretation and for understanding of the basic properties of the hydrogen bond IR spectra of cinnamic acid crystals, H/D isotopic, temperature and dichroic effects included. In the scope of our studies the mechanism of H/D isotopic 'self-organization' processes, taking place in the crystal hydrogen bond lattices, was also recognized. It was proved that for isotopically diluted crystalline samples of cinnamic acid, a non-random distribution of protons and deuterons occurs exclusively in the hydrogen bond dimers. Nevertheless, these co-operative interactions between the hydrogen bonds do not involve the adjacent hydrogen bond dimers in each unit cell. The two-branch fine structure pattern of the νO-H and νO-D bands was ascribed to the vibronic mechanism of vibrational dipole selection rule breaking in centrosymmetric hydrogen bond dimers. The observed in the spectra very high intensity of the forbidden transition sub-band in the analyzed νO-H and νO-D bands is a manifestation of an extremely effective symmetry rule breaking mechanism. It correlates with a relatively large excess electron charge on the cinnamic aid dimer carboxyl groups. This effect is a result of a partial withdrawal of the electron charge, from the conjugated π-bond systems of the styryl substituents, by the carboxyl groups. This statement has been supported by ab initio calculations.

Fingerprints for main varieties of argentinean wines: terroir differentiation by inorganic, organic, and stable isotopic analyses coupled to chemometrics.

PubMed

Di Paola-Naranjo, Romina D; Baroni, Maria V; Podio, Natalia S; Rubinstein, Hector R; Fabani, Maria P; Badini, Raul G; Inga, Marcela; Ostera, Hector A; Cagnoni, Mariana; Gallegos, Ernesto; Gautier, Eduardo; Peral-Garcia, Pilar; Hoogewerff, Jurian; Wunderlin, Daniel A

2011-07-27

Our main goal was to investigate if robust chemical fingerprints could be developed for three Argentinean red wines based on organic, inorganic, and isotopic patterns, in relation to the regional soil composition. Soils and wines from three regions (Mendoza, San Juan, and Córdoba) and three varieties (Cabernet Sauvignon, Malbec, and Syrah) were collected. The phenolic profile was determined by HPLC-MS/MS and multielemental composition by ICP-MS; (87)Sr/(86)Sr and δ(13)C were determined by TIMS and IRMS, respectively. Chemometrics allowed robust differentiation between regions, wine varieties, and the same variety from different regions. Among phenolic compounds, resveratrol concentration was the most useful marker for wine differentiation, whereas Mg, K/Rb, Ca/Sr, and (87)Sr/(86)Sr were the main inorganic and isotopic parameters selected. Generalized Procrustes analysis (GPA) using two studied matrices (wine and soil) shows consensus between them and clear differences between studied areas. Finally, we applied a canonical correlation analysis, demonstrating significant correlation (r = 0.99; p < 0.001) between soil and wine composition. To our knowledge this is the first report combining independent variables, constructing a fingerprint including elemental composition, isotopic, and polyphenol patterns to differentiate wines, matching part of this fingerprint with the soil provenance.

An oxygen isotope record from Lake Xiarinur in Inner Mongolia since the last deglaciation and its implication for tropical monsoon change

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Sediment Sources, Depositional Environment, and Diagenetic Alteration of the Marcellus Shale, Appalachian Basin, USA: Nd, Sr, Li and U Isotopic Constraints

NASA Astrophysics Data System (ADS)

Phan, T. T.; Capo, R. C.; Gardiner, J. B.; Stewart, B. W.

2017-12-01

The organic-rich Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, is a major target of natural gas exploration. Constraints on local and regional sediment sources, depositional environments, and post-depositional processes are essential for understanding the evolution of the basin. In this study, multiple proxies, including trace metals, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U and Li isotopes were applied to bulk rocks and authigenic fractions of the Marcellus Shale and adjacent limestone/sandstone units from two locations separated by 400 km. The range of ɛNd values (-7.8 to -6.4 at 390 Ma) is consistent with a clastic sedimentary component derived from a well-mixed source of fluvial and eolian material of the Grenville orogenic belt. The Sm-Nd isotope system and bulk REE distributions appear to have been minimally affected by post-depositional processes, while the Rb-Sr isotope system shows evidence of limited post-depositional redistribution. While REE are primarily associated with silicate minerals (80-95%), REE patterns of sequentially extracted fractions reflect post-depositional alteration at the intergranular scale. Although the chemical index of alteration (CIA = 54 to 60) suggests the sediment source was not heavily weathered, Li isotope data are consistent with progressively increasing weathering of the source region during Marcellus Shale deposition. δ238U values in bulk shale and reduced phases (oxidizable fraction) are higher than those of modern seawater and upper crust. The isotopically heavy U accumulated in these authigenic phases can be explained by the precipitation of insoluble U in anoxic/euxinic bottom water. Unlike carbonate cement within the shale, the similarity between δ238U values and REE patterns of the limestone units and those of modern seawater indicates that the limestone formed under open ocean (oxic) conditions.

Inferring Foraging Areas of Nesting Loggerhead Turtles Using Satellite Telemetry and Stable Isotopes

PubMed Central

Ceriani, Simona A.; Roth, James D.; Evans, Daniel R.; Weishampel, John F.; Ehrhart, Llewellyn M.

2012-01-01

In recent years, the use of intrinsic markers such as stable isotopes to link breeding and foraging grounds of migratory species has increased. Nevertheless, several assumptions still must be tested to interpret isotopic patterns found in the marine realm. We used a combination of satellite telemetry and stable isotope analysis to (i) identify key foraging grounds used by female loggerheads nesting in Florida and (ii) examine the relationship between stable isotope ratios and post-nesting migration destinations. We collected tissue samples for stable isotope analysis from 14 females equipped with satellite tags and an additional 57 untracked nesting females. Telemetry identified three post-nesting migratory pathways and associated non-breeding foraging grounds: (1) a seasonal continental shelf–constrained migratory pattern along the northeast U.S. coastline, (2) a non-breeding residency in southern foraging areas and (3) a residency in the waters adjacent to the breeding area. Isotopic variability in both δ13C and δ15N among individuals allowed identification of three distinct foraging aggregations. We used discriminant function analysis to examine how well δ13C and δ15N predict female post-nesting migration destination. The discriminant analysis classified correctly the foraging ground used for all but one individual and was used to predict putative feeding areas of untracked turtles. We provide the first documentation that the continental shelf of the Mid- and South Atlantic Bights are prime foraging areas for a large number (61%) of adult female loggerheads from the largest loggerhead nesting population in the western hemisphere and the second largest in the world. Our findings offer insights for future management efforts and suggest that this technique can be used to infer foraging strategies and residence areas in lieu of more expensive satellite telemetry, enabling sample sizes that are more representative at the population level. PMID:23028943

Trophic ecology and vertical patterns of carbon and nitrogen stable isotopes in zooplankton from oxygen minimum zone regions

NASA Astrophysics Data System (ADS)

Williams, Rebecca L.; Wakeham, Stuart; McKinney, Rick; Wishner, Karen F.

2014-08-01

The unique physical and biogeochemical characteristics of oxygen minimum zones (OMZs) influence plankton ecology, including zooplankton trophic webs. Using carbon and nitrogen stable isotopes, this study examined zooplankton trophic webs in the Eastern Tropical North Pacific (ETNP) OMZ. δ13C values were used to indicate zooplankton food sources, and δ15N values were used to indicate zooplankton trophic position and nitrogen cycle pathways. Vertically stratified MOCNESS net tows collected zooplankton from 0 to 1000 m at two stations along a north-south transect in the ETNP during 2007 and 2008, the Tehuantepec Bowl and the Costa Rica Dome. Zooplankton samples were separated into four size fractions for stable isotope analyses. Particulate organic matter (POM), assumed to represent a primary food source for zooplankton, was collected with McLane large volume in situ pumps. The isotopic composition and trophic ecology of the ETNP zooplankton community had distinct spatial and vertical patterns influenced by OMZ structure. The most pronounced vertical isotope gradients occurred near the upper and lower OMZ oxyclines. Material with lower δ13C values was apparently produced in the upper oxycline, possibly by chemoautotrophic microbes, and was subsequently consumed by zooplankton. Between-station differences in δ15N values suggested that different nitrogen cycle processes were dominant at the two locations, which influenced the isotopic characteristics of the zooplankton community. A strong depth gradient in zooplankton δ15N values in the lower oxycline suggested an increase in trophic cycling just below the core of the OMZ. Shallow POM (0-110 m) was likely the most important food source for mixed layer, upper oxycline, and OMZ core zooplankton, while deep POM was an important food source for most lower oxycline zooplankton (except for samples dominated by the seasonally migrating copepod Eucalanus inermis). There was no consistent isotopic progression among the four zooplankton size classes for these bulk mixed assemblage samples, implying overlapping trophic webs within the total size range considered.

Uranium isotopes as a potential global-ocean redox proxy: a test from the Upper Pennsylvanian Hushpuckney Shale (Kansas, U.S.A.)

NASA Astrophysics Data System (ADS)

Herrmann, A. D.; Algeo, T. J.; Gordon, G. W.; Anbar, A. D.

2015-12-01

Uranium (U) isotope variation in marine sediments has been proposed as a proxy for changes in average global-ocean redox conditions. Here, we investigate U isotope variation in the black shale (BS) member of the Hushpuckney Shale (Swope Formation) at two sites ~400 km apart within the Late Paleozoic Midcontinent Sea (LPMS) of North America, with the goal of testing whether sediment δ238U records a global-ocean redox signal or local environmental influences. Our results document a spatial gradient of at least 0.25‰ in δ238U within the LPMS, demonstrating that local (probably redox) controls have overprinted any global U-isotope signal. Furthermore, the pattern of stratigraphic variation in δ238U in both study cores, with low values (‒0.4 to ‒0.2‰) at the base and top and peak values (+0.4 to +0.65‰) in the middle of the BS, is inconsistent with dominance of a global-ocean redox signal because (1) the middle of the BS was deposited at maximum eustatic highstand when euxinic conditions existed most widely within the LPMS and coeval epicontinental seas, and (2) more extensive euxinia should have shifted global-ocean seawater δ238U to lower values based on mass-balance principles. On the other hand, the observed δ238U pattern is consistent with a dominant local redox control, with larger U-isotope fractionations associated with more reducing bottom waters. We therefore conclude that U was not removed quantitatively to euxinic facies of the LPMS, and that sediment U-isotope compositions were controlled mainly by local redox and hydrographic factors. Our results imply that U-isotope signals from epicontinental-sea sections must be vetted carefully through analysis of high-resolution datasets at multiple sites in order to validate their potential use as a global-seawater redox proxy.

In Situ Carbon Stable Isotope Tracer Experiments Elucidate Carbon Translocation Rates and Allocation Patterns in Zostera marina L. (eelgrass)

EPA Science Inventory

The intertidal seagrass Zostera marina is an important species that provides critical habitat for a number of estuarine species. Despite its widespread distribution, there is limited information on seasonal patterns of carbon dynamics of plants growing in situ, particularly esti...

From hilltop to kettle hole: what trends across the terrestrial-aquatic transition zone are revealed by organic matter stable isotope (δ13C and δ15N) composition?

NASA Astrophysics Data System (ADS)

Kayler, Z. E.; Nitzsche, K. N.; Gessler, A.; Kaiser, M. L.; Hoffmann, C.; Premke, K.; Ellerbrock, R.

2016-12-01

Steep environmental gradients develop across the interface between terrestrial and aquatic domains that influence organic matter (OM) retention. In NE Germany, kettle holes are small water bodies found in high density across managed landscapes. Kettle hole water budgets are generally fed through precipitation and overland flow and are temporarily connected to groundwater resulting in distinct hydroperiods. We took advantage of the range of environmental conditions created by the fluctuating shoreline to investigate patterns of OM stability along transects spanning from hilltops to sediments within a single kettle hole. We physically and chemically separated OM fractions that are expected to be loosely bound, such as particulate organic matter, to those that are tightly bound, such as OM associated with mineral or metal surfaces. The study design allowed us to investigate stabilization processes at the aggregate, transect, and kettle hole catchment scale. At the aggregate scale, we analyzed soil characteristics (texture, pH, extractable Al, Fe, Ca) to contribute to our understanding of OM stabilization. At the transect scale, we compared isotopic trends in the different fractions against a simple Rayleigh distillation model to infer disruption of the transfer of material, for example erosion, by land management such as tillage or the addition of OM through fertilization. At the kettle hole catchment scale, we correlated our findings with plant productivity, landform properties, and soil wetness proxies. Aggregate scale patterns of OM 13C and 15N were fraction dependent; however, we observed a convergence in isotopic patterns with soil properties from OM of more stabilized fractions. At the transect scale, loosely bound fractions did not conform to the simple model, suggesting these fractions are more dynamic and influenced by land management. The stabilized fractions did follow the Rayleigh model, which implies that transfer processes play a larger role in these fractions. At the kettle hole catchment scale, we found that the terrestrial-aquatic transition zone and other areas with high soil moisture correlated with isotopic patterns of the OM fractions. Kettle hole sediment OM fraction patterns were consistently different despite receiving substantial material from the surrounding landscape.

A cross-shelf gradient in δ15N stable isotope values of krill and pollock indicates seabird foraging patterns in the Bering Sea

NASA Astrophysics Data System (ADS)

Jones, Nathan M.; Hoover, Brian A.; Heppell, Scott A.; Kuletz, Kathy J.

2014-11-01

Concurrent measurements of predator and prey δ15N isotope values demonstrated that a cross-shelf isotopic gradient can propagate through a marine food web from forage species to top-tier predators and indicate foraging areas at a scale of tens of kilometers. We measured δ13C and δ15N in muscle tissues of thick-billed murres (Uria lomvia) and black-legged kittiwakes (Rissa tridactyla), and in whole body tissues of walleye pollock (Gadus chalcogrammus) and krill (Thysanoessa spp), sampled across the continental shelf break in the Bering Sea in 2008 and in 2009. We found significant basin-shelf differences at fine scales (<100 km) in δ15N among murres but not kittiwakes, and no such differences in δ13C in either seabird species at that scale. We then quantified the multi-trophic signal and spatial structure of a basin-shelf δ15Nitrogen gradient in the central and southern Bering Sea, and used it to contrast foraging patterns of thick-billed murres and kittiwakes on the open ocean. Seabird muscle δ15N values were compared to baselines created from measurements in krill and pollock tissues sampled concurrently throughout the study area. Krill, pollock, and murre tissues from northern, shallow, shelf habitat (<200 m) were enriched 1-2‰ in δ15N relative to samples taken from deeper habitats (>200 m) to the south and west. Krill δ15N baseline values predicted 35-42% of the variability in murre tissue values. Patterns between kittiwakes and prey were less coherent. The persistence of strong spatial autocorrelation among sample values, and a congruence of geospatial patterns in δ15N among murre and prey tissues, suggest that murres forage repeatedly in specific areas. Murre isotope values showed distinct geospatial stratification, coincident with the spatial distribution of three colonies: St. Paul, St. George, and Bogoslof. This suggests some degree of foraging habitat partitioning among colonies.

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

The equilibrium isotope fractionation factor αeq is a fundamental parameter in the study of stable isotope effects. Experimentally, it has been difficult to establish that a system has attained equilibrium. The three-isotope method, using the initial trajectory of changing isotope ratios (e.g. 16O, 17O, and 18O) to deduce the final equilibrium point of isotope exchange, has long been hailed as the most rigorous experimental approach. However, over the years some researchers have cautioned on the limitations of this method, but the foundation of three-isotope method has not been properly examined and the method is still widely used in calibrating αeq for both traditional and increasingly non-traditional isotope systems today. Here, using water-water and dissolved CO2-water oxygen exchange as model systems, we conduct an isotopologues-specific kinetic analysis of the exchange processes and explore the underlying assumptions and validity of the three-isotope method. We demonstrate that without knowing the detailed exchange kinetics a priori the three-isotope method cannot lead to a reliable αeq. For a two-reservoir exchanging system, α determined by this method may be αeq, kinetic isotope effect, or apparent kinetic isotope effect, which can all bear different values. When multiple reservoirs exist during exchange, the evolving trajectory can be complex and hard to predict. Instead of being a tool for αeq determination, three-isotope method should be used as a tool for studying kinetic isotope effect, apparent kinetic isotope effect, and detailed exchange kinetics in diverse systems.

Seasonality of Leaf Carbon Isotopic Composition and Leaf Water Isotopic Enrichment in a Mixed Evergreen Forest in Southern California

NASA Astrophysics Data System (ADS)

Santiago, L. S.; Sickman, J. O.; Goulden, M.; DeVan, C.; Pasquini, S. C.; Pivovaroff, A. L.

2011-12-01

Leaf carbon isotopic composition and leaf water isotopic enrichment reflect physiological processes and are important for linking local and regional scale processes to global patterns. We investigated how seasonality affects the isotopic composition of bulk leaf carbon, leaf sugar carbon, and leaf water hydrogen under a Mediterranean climate. Leaf and stem samples were collected monthly from four tree species (Calocedrus decurrens, Pinus lambertiana, Pinus ponderosa, and Quercus chrysolepis) at the James San Jacinto Mountain Reserve in southern California. Mean monthly bulk leaf carbon isotopic composition varied from -34.5 % in P. ponderosa to -24.7 % in P. lambertiana and became more depleted in 13C from the spring to the summer. Mean monthly leaf sugar varied from -29.3 % in P. ponderosa to -21.8 % in P. lambertiana and was enriched in 13C during the winter, spring and autumn, but depleted during the mid-summer. Leaf water hydrogen isotopic composition was 28.4 to 68.8 % more enriched in deuterium than source water and this enrichment was greater as seasonal drought progressed. These data indicate that leaf carbon and leaf water hydrogen isotopic composition provide sensitive measures that connect plant physiological processes to short-term climatic variability.

An isotope hydrology study of the Kilauea volcano area, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Ingebritsen, S.E.; Janik, C.J.; Kauahikaua, J.P.

1995-01-01

Isotope tracer methods were used to determine flow paths, recharge areas, and relative age for ground water in the Kilauea volcano area on the Island of Hawaii. Stable isotopes in rainfall show three distinct isotopic gradients with elevation, which are correlated with trade-wind, rain shadow, and high-elevation climatological patterns. Temporal variations in isotopic composition of precipitation are controlled more by the frequency of large storms than b.y seasonal temperature fluctuations. Consistency in results between two separate areas with rainfall caused by tradewinds and thermally-driven upslope airflow suggests that isotopic gradients with elevation may be similar on other islands in the tradewind belt, especially the other Hawaiian Islands, which have similar climatology and temperature lapse rates. Areal contrasts in ground-water stable isotopes and tritium indicate that the volcanic ri~ zones compartmentalize the regional ground-water system. Tritium levels in ground water within and downgradient of Kilauea's ri~ zones indicate relatively long residence times. Part of Kilauea's Southwest Ri~ Zone appears to act as a conduit for water from higher elevation, but there is no evidence for extensive down-ri~ flow in the lower East Ri~ Zone.

Application of Stable Isotope-Assisted Metabolomics for Cell Metabolism Studies

PubMed Central

You, Le; Zhang, Baichen; Tang, Yinjie J.

2014-01-01

The applications of stable isotopes in metabolomics have facilitated the study of cell metabolisms. Stable isotope-assisted metabolomics requires: (1) properly designed tracer experiments; (2) stringent sampling and quenching protocols to minimize isotopic alternations; (3) efficient metabolite separations; (4) high resolution mass spectrometry to resolve overlapping peaks and background noises; and (5) data analysis methods and databases to decipher isotopic clusters over a broad m/z range (mass-to-charge ratio). This paper overviews mass spectrometry based techniques for precise determination of metabolites and their isotopologues. It also discusses applications of isotopic approaches to track substrate utilization, identify unknown metabolites and their chemical formulas, measure metabolite concentrations, determine putative metabolic pathways, and investigate microbial community populations and their carbon assimilation patterns. In addition, 13C-metabolite fingerprinting and metabolic models can be integrated to quantify carbon fluxes (enzyme reaction rates). The fluxome, in combination with other “omics” analyses, may give systems-level insights into regulatory mechanisms underlying gene functions. More importantly, 13C-tracer experiments significantly improve the potential of low-resolution gas chromatography-mass spectrometry (GC-MS) for broad-scope metabolism studies. We foresee the isotope-assisted metabolomics to be an indispensable tool in industrial biotechnology, environmental microbiology, and medical research. PMID:24957020

Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean.

PubMed

Prasanna, K; Ghosh, Prosenjit; Bhattacharya, S K; Mohan, K; Anilkumar, N

2016-02-23

Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45°E and 80°E and 10°N to 53°S) were analysed and compared with the equilibrium δ(18)O and δ(13)C values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within ~0.25‰ for the region between 10°N and 40°S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40°S to 55°S), however, the measured δ(18)O and δ(13)C values are higher than the expected values by ~2‰ and ~1‰ respectively. These enrichments can be attributed to either a 'vital effect' or a higher calcification rate. An interesting pattern of increase in the δ(13)C(DIC) value of the surface water with latitude is observed between 35°S and~ 60°S, with a peak at~ 42°S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the δ(13)C(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.

"Anticlumping" and Other Combinatorial Effects on Clumped Isotopes: Implications for Tracing Biogeochemical Cycling

NASA Astrophysics Data System (ADS)

Yeung, L.

2015-12-01

I present a mode of isotopic ordering that has purely combinatorial origins. It can be important when identical rare isotopes are paired by coincidence (e.g., they are neighbors on the same molecule), or when extrinsic factors govern the isotopic composition of the two atoms that share a chemical bond. By itself, combinatorial isotope pairing yields products with isotopes either randomly distributed or with a deficit relative to a random distribution of isotopes. These systematics arise because of an unconventional coupling between the formation of singly- and multiply-substituted isotopic moieties. In a random distribution, rare isotopes are symmetrically distributed: Single isotopic substitutions (e.g., H‒D and D‒H in H2) occur with equal probability, and double isotopic substitutions (e.g., D2) occur according to random chance. The absence of symmetry in a bond-making complex can yield unequal numbers of singly-substituted molecules (e.g., more H‒D than D‒H in H2), which is recorded in the product molecule as a deficit in doubly-substituted moieties and an "anticlumped" isotope distribution (i.e., Δn < 0). Enzymatic isotope pairing reactions, which can have site-specific isotopic fractionation factors and atom reservoirs, should express this class of combinatorial isotope effect. Chemical-kinetic isotope effects, which are related to the bond-forming transition state, arise independently and express second-order combinatorial effects. In general, both combinatorial and chemical factors are important for calculating and interpreting clumped-isotope signatures of individual reactions. In many reactions relevant to geochemical oxygen, carbon, and nitrogen cycling, combinatorial isotope pairing likely plays a strong role in the clumped isotope distribution of the products. These isotopic signatures, manifest as either directly bound isotope clumps or as features of a molecule's isotopic anatomy, could be exploited as tracers of biogeochemistry that can relate molecular mechanisms to signals observable at environmentally relevant spatial scales.

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

Isotopic constraints on global atmospheric methane sources and sinks: a critical assessment of recent findings and new data

NASA Astrophysics Data System (ADS)

Schwietzke, S.; Sherwood, O.; Michel, S. E.; Bruhwiler, L.; Dlugokencky, E. J.; Tans, P. P.

2017-12-01

Methane isotopic data have increasingly been used in recent studies to help constrain global atmospheric methane sources and sinks. The added scientific contributions to this field include (i) careful comparisons and merging of atmospheric isotope measurement datasets to increase spatial coverage, (ii) in-depth analyses of observed isotopic spatial gradients and seasonal patterns, and (iii) improved datasets of isotopic source signatures. Different interpretations have been made regarding the utility of the isotopic data on the diagnosis of methane sources and sinks. Some studies have found isotopic evidence of a largely microbial source causing the renewed growth in global atmospheric methane since 2007, and underestimated global fossil fuel methane emissions compared to most previous studies. However, other studies have challenged these conclusions by pointing out substantial spatial variability in isotopic source signatures as well as open questions in atmospheric sinks and biomass burning trends. This presentation will review and contrast the main arguments and evidence for the different conclusions. The analysis will distinguish among the different research objectives including (i) global methane budget source attribution in steady-state, (ii) source attribution of recent global methane trends, and (iii) identifying specific methane sources in individual plumes during field campaigns. Additional comparisons of model experiments with atmospheric measurements and updates on isotopic source signature data will complement the analysis.

Free-ranging domestic cats (Felis catus) on public lands: estimating density, activity, and diet in the Florida Keys

USGS Publications Warehouse

Cove, Michael V.; Gardner, Beth; Simons, Theodore R.; Kays, Roland; O'Connell, Allan F.

2017-01-01

Feral and free-ranging domestic cats (Felis catus) can have strong negative effects on small mammals and birds, particularly in island ecosystems. We deployed camera traps to study free-ranging cats in national wildlife refuges and state parks on Big Pine Key and Key Largo in the Florida Keys, USA, and used spatial capture–recapture models to estimate cat abundance, movement, and activities. We also used stable isotope analyses to examine the diet of cats captured on public lands. Top population models separated cats based on differences in movement and detection with three and two latent groups on Big Pine Key and Key Largo, respectively. We hypothesize that these latent groups represent feral, semi-feral, and indoor/outdoor house cats based on the estimated movement parameters of each group. Estimated cat densities and activity varied between the two islands, with relatively high densities (~4 cats/km2) exhibiting crepuscular diel patterns on Big Pine Key and lower densities (~1 cat/km2) exhibiting nocturnal diel patterns on Key Largo. These differences are most likely related to the higher proportion of house cats on Big Pine relative to Key Largo. Carbon and nitrogen isotope ratios from hair samples of free-ranging cats (n = 43) provided estimates of the proportion of wild and anthropogenic foods in cat diets. At the population level, cats on both islands consumed mostly anthropogenic foods (>80% of the diet), but eight individuals were effective predators of wildlife (>50% of the diet). We provide evidence that cat groups within a population move different distances, exhibit different activity patterns, and that individuals consume wildlife at different rates, which all have implications for managing this invasive predator.

The size-isotopic evolution connection among layered mafic instrusions: Clues from a Sr-Nd isotopic study of a small complex

NASA Astrophysics Data System (ADS)

Poitrasson, Franck; Pin, Christian; Duthou, Jean-Louis; Platevoet, Bernard

1994-05-01

Several theoretical and experimental works have focused on the processes occuring in continental mafic magma chambers. In contrast, systematic isotopic studies of natural remnants of these latter remain scarce, although they can give fundamental constraints for theoretical studies. This is especially true if different layered complex with contrasting characteristics (e.g., different size) are compared. For this reason, we present the results of a Sr-Nd isotopic profile across a small layered mafic intrusion of Permian age exposed near Fozzano (SW Corsica). In the main zone of the layered section, decreasing Sr-87/Sr(sub i)-86 and increasing Nd-143/Nd(sub i)-144 are observed from less evolved (bottom) to more evolved (top) rocks. This peculiar pattern precludes assimilation and fractional crystallization (AFC) as a dominant mechanism in the petrogenesis of this body. Instead, we interpret this trend as reflecting the dilution of an early stage contaminated magma by several reinjections of fresh basalt in the chamber. In agreement with mineralogical and structural data, every cyclic unit is interpreted as a new magmatic input. On the basis of rough refill and fractional crystallization (RFC) calculations, the average volume for each reinjection is estimated to have been about 0.04 cu km. The cumulative volume of these injections would amount to about 75% of the total volume of the layered complex. This implies that reinjections were accompanied by an important increase of the volume of the chamber or by magma withdrawal by surface eruptions. The RFC mechanism documented within this small layered body constrasts with the isotopic pattern observed between several intrusions at the regional scale in SW Corsica, and within large continental mafic magma chambers elsewhere. In these cases the isotopic evolution is dominated by AFC processes, and there is no clear isotopic evidence for reinjections, unless major influx of fresh magma occurred. It is suggested that there is a close relationship between the assimilation rate and the magma chamber volume. Small magma chambers are quickly isolated from their country rocks and better preserve the subtle isotopic signature of reinjection processes.

Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking

USGS Publications Warehouse

Vander Zanden, Hannah B.; Tucker, Anton D.; Hart, Kristen M.; Lamont, Margaret M.; Fujisaki, Ikuko; Addison, David S.; Mansfield, Katherine L.; Phillips, Katrina F.; Wunder, Michael B.; Bowen, Gabriel J.; Pajuelo, Mariela; Bolten, Alan B.; Bjorndal, Karen A.

2015-01-01

Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: 1) a nominal approach through discriminant analysis and 2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively determine geographic origin for large numbers of untracked individuals. Regular monitoring of sea turtle nesting aggregations with stable isotope sampling can be used to fill critical data gaps regarding habitat use and migration patterns. Probabilistic assignment to origin with isoscapes has not been previously used in the marine environment, but the methods presented here could also be applied to other migratory marine species.

Soil water stable isotopes reveal evaporation dynamics at the soil-plant-atmosphere interface of the critical zone

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Tetzlaff, Doerthe; Soulsby, Chris

2017-07-01

Understanding the influence of vegetation on water storage and flux in the upper soil is crucial in assessing the consequences of climate and land use change. We sampled the upper 20 cm of podzolic soils at 5 cm intervals in four sites differing in their vegetation (Scots Pine (Pinus sylvestris) and heather (Calluna sp. and Erica Sp)) and aspect. The sites were located within the Bruntland Burn long-term experimental catchment in the Scottish Highlands, a low energy, wet environment. Sampling took place on 11 occasions between September 2015 and September 2016 to capture seasonal variability in isotope dynamics. The pore waters of soil samples were analyzed for their isotopic composition (δ2H and δ18O) with the direct-equilibration method. Our results show that the soil waters in the top soil are, despite the low potential evaporation rates in such northern latitudes, kinetically fractionated compared to the precipitation input throughout the year. This fractionation signal decreases within the upper 15 cm resulting in the top 5 cm being isotopically differentiated to the soil at 15-20 cm soil depth. There are significant differences in the fractionation signal between soils beneath heather and soils beneath Scots pine, with the latter being more pronounced. But again, this difference diminishes within the upper 15 cm of soil. The enrichment in heavy isotopes in the topsoil follows a seasonal hysteresis pattern, indicating a lag time between the fractionation signal in the soil and the increase/decrease of soil evaporation in spring/autumn. Based on the kinetic enrichment of the soil water isotopes, we estimated the soil evaporation losses to be about 5 and 10 % of the infiltrating water for soils beneath heather and Scots pine, respectively. The high sampling frequency in time (monthly) and depth (5 cm intervals) revealed high temporal and spatial variability of the isotopic composition of soil waters, which can be critical, when using stable isotopes as tracers to assess plant water uptake patterns within the critical zone or applying them to calibrate tracer-aided hydrological models either at the plot to the catchment scale.

Determining origin in a migratory marine vertebrate: a novel method to integrate stable isotopes and satellite tracking.

PubMed

Zanden, Hannah B Vander; Tucker, Anton D; Hart, Kristen M; Lamont, Margaret M; Fuisaki, Ikuko; Addison, David; Mansfield, Katherine L; Phillips, Katrina F; Wunder, Michael B; Bowen, Gabriel J; Pajuelo, Mariela; Bolten, Alan B; Bjorndal, Karen A

2015-03-01

Stable isotope analysis is a useful tool to track animal movements in both terrestrial and marine environments. These intrinsic markers are assimilated through the diet and may exhibit spatial gradients as a result of biogeochemical processes at the base of the food web. In the marine environment, maps to predict the spatial distribution of stable isotopes are limited, and thus determining geographic origin has been reliant upon integrating satellite telemetry and stable isotope data. Migratory sea turtles regularly move between foraging and reproductive areas. Whereas most nesting populations can be easily accessed and regularly monitored, little is known about the demographic trends in foraging populations. The purpose of the present study was to examine migration patterns of loggerhead nesting aggregations in the Gulf of Mexico (GoM), where sea turtles have been historically understudied. Two methods of geographic assignment using stable isotope values in known-origin samples from satellite telemetry were compared: (1) a nominal approach through discriminant analysis and (2) a novel continuous-surface approach using bivariate carbon and nitrogen isoscapes (isotopic landscapes) developed for this study. Tissue samples for stable isotope analysis were obtained from 60 satellite-tracked individuals at five nesting beaches within the GoM. Both methodological approaches for assignment resulted in high accuracy of foraging area determination, though each has advantages and disadvantages. The nominal approach is more appropriate when defined boundaries are necessary, but up to 42% of the individuals could not be considered in this approach. All individuals can be included in the continuous-surface approach, and individual results can be aggregated to identify geographic hotspots of foraging area use, though the accuracy rate was lower than nominal assignment. The methodological validation provides a foundation for future sea turtle studies in the region to inexpensively determine geographic origin for large numbers of untracked individuals. Regular monitoring of sea turtle nesting aggregations with stable isotope sampling can be used to fill critical data gaps regarding habitat use and migration patterns. Probabilistic assignment to origin with isoscapes has not been previously used in the marine environment, but the methods presented here could also be applied to other migratory marine species.

Compound-specific isotope analysis as a tool to characterize biodegradation of ethylbenzene.

PubMed

Dorer, Conrad; Vogt, Carsten; Kleinsteuber, Sabine; Stams, Alfons J M; Richnow, Hans-Hermann

2014-08-19

This study applied one- and two-dimensional compound-specific isotope analysis (CSIA) for the elements carbon and hydrogen to assess different means of microbial ethylbenzene activation. Cultures incubated under nitrate-reducing conditions showed significant carbon and highly pronounced hydrogen isotope fractionation of comparable magnitudes, leading to nearly identical slopes in dual-isotope plots. The results imply that Georgfuchsia toluolica G5G6 and an enrichment culture dominated by an Azoarcus species activate ethylbenzene by anaerobic hydroxylation catalyzed by ethylbenzene dehydrogenase, similar to Aromatoleum aromaticum EbN1. The isotope enrichment pattern in dual plots from two strictly anaerobic enrichment cultures differed considerably from those for benzylic hydroxylation, indicating an alternative anaerobic activation step, most likely fumarate addition. Large hydrogen fractionation was quantified using a recently developed Rayleigh-based approach considering hydrogen atoms at reactive sites. Data from nine investigated microbial cultures clearly suggest that two-dimensional CSIA in combination with the magnitude of hydrogen isotope fractionation is a valuable tool to distinguish ethylbenzene degradation and may be of practical use for monitoring natural or technological remediation processes at field sites.

Isotopic evidence bearing on Late Triassic extinction events, Queen Charlotte Islands, British Columbia, and implications for the duration and cause of the Triassic/Jurassic mass extinction

USGS Publications Warehouse

Ward, P.D.; Garrison, G.H.; Haggart, J.W.; Kring, D.A.; Beattie, M.J.

2004-01-01

Stable isotope analyses of Late Triassic to earliest Jurassic strata from Kennecott Point in the Queen Charlotte Islands, British Columbia, Canada shows the presence of two distinct and different organic carbon isotope anomalies at the Norian/Rhaetian and Rhaetian/Hettangian (=Triassic/Jurassic) stage boundaries. At the older of these boundaries, which is marked by the disappearance of the bivalve Monotis, the isotope record shows a series of short-lived positive excursions toward heavier values. Strata approaching this boundary show evidence of increasing anoxia. At the higher boundary, marked by the disappearance of the last remaining Triassic ammonites and over 50 species of radiolarians, the isotopic pattern consists of a series of short duration negative anomalies. The two events, separated by the duration of the Rhaetian age, comprise the end-Triassic mass extinction. While there is no definitive evidence as to cause, the isotopic record does not appear similar to that of the impact-caused Cretaceous/Tertiary boundary extinction. ?? 2004 Published by Elsevier B.V.

Stable Isotope Applications for Understanding Shark Ecology in the Northeast Pacific Ocean.

PubMed

Reum, Jonathan C P; Williams, Gregory D; Harvey, Chris J

Stable isotopes are used to address a wide range of ecological questions and can help researchers and managers better understand the movement and trophic ecology of sharks. Here, we review how shark studies from the Northeast Pacific Ocean (NEP) have employed stable isotopes to estimate trophic level and diet composition and infer movement and habitat-use patterns. To date, the number of NEP shark studies that have used stable isotopes is limited, suggesting that the approach is underutilized. To aid shark researchers in understanding the strengths and limitations of the approach, we provide a brief overview of carbon and nitrogen stable isotope trophic discrimination properties (e.g., change in δ 15 N between predator and prey), tissue sample preparation methods specific to elasmobranchs, and methodological considerations for the estimation of trophic level and diet composition. We suggest that stable isotopes are a potentially powerful tool for addressing basic questions about shark ecology and are perhaps most valuable when combined and analysed with other data types (e.g., stomach contents, tagging data, or other intrinsic biogeochemical markers). © 2017 Elsevier Ltd. All rights reserved.

Reaction paths and host phases of uranium isotopes (235U; 238U), Saanich Inlet

NASA Astrophysics Data System (ADS)

Amini, M.; Holmden, C. E.; Francois, R. H.

2009-12-01

In recent times, Uranium has become increasingly the focus of stable isotope fractionation studies. Variations in 238U/235U have been reported as a result of redox reactions [1,2] from the nuclear field shift effect [3], and a mass-dependent, microbially-mediated, kinetic isotope effect [4]. The 238U/235U variability caused by changes in environmental redox conditions leads to an increase in the 238U/235U ratios of the reduced U species sequestered into marine sediments. This points to U isotope variability as a new tool to study ancient ocean redox changes. However, the process by which reduced sediments become enriched in the heavy isotopes of U is not yet known, and hence the utility of 238U/235U as a redox tracer remains to be demonstrated. In order to further constrain sedimentary U enrichment and related isotope effect, we are investigating U isotopic compositions of water samples and fresh surface sediment grab samples over a range of redox conditions in the seasonally anoxic Saanich Inlet, on the east coast of Vancouver Island. U was sequentially extracted from sediments in order to characterize specific fractions for their isotopic composition. The measurements were carried out by MC-ICPMS using 233U/236U-double spike technique. The data are reported as δ238U relative to NBL 112a with a 238U/235U ratio of 137.88 (2sd). External precision is better than 0.10‰ (2sd). Fifteeen analyses of seawater yielded δ238U of -0.42±0.08‰ (2sd). The results for the water samples indicate a homogenous δ238U value throughout the Saanich Inlet water column that matches the global seawater signature. All of the water samples from above and below average -0.42±0.05‰ (2sd). In contrast, a plankton net sample yielded a distinctly different, (about 0.5‰ lighter) isotope value. Bacterial reduction experiments [4] have also shown isotope enrichment factors of about -0.3‰. In addition, metal isotope fractionation occurs during adsorption with the light isotope being preferentially adsorbed [5]. Whether plankton mediated chemical reduction or scavenging causes this fractionation will be further investigated by leaching experiments on sediment trap samples. By contrast, weak acidic leachates (at pH 6) of suboxic bottom sediments, tend towards higher δ238U values. For oxic sediments, U contents of this fraction were below detection limit. Stronger leaching at pH 3 removed most of the uranium from suboxic and oxic sediments. For oxic sediments, this fraction yields the seawater δ238U signature, while the U released from the suboxic sample is about 0.2‰ heavier. This matches the value for previously reported bulk analyses of suboxic sediments [1] implying that the reduced sedimentary U is released by this treatment,. Major and trace element analyses and XRD patterns will help relating this fraction to a specific mineral or reactive phase. [1] Weyer et al. (2007) GCA 72, 345-399. [2] Stirling et al. (2007) EPSL 264, 208-225. [3] Schauble (2007) GCA 71, 2170-2189. [4] Rademacher et al. (2006) Environ. Sci. Technol. 40,6943-6948. [5] Wasylenki (2009) GCA A1419.

Natural isotope correction of MS/MS measurements for metabolomics and (13)C fluxomics.

PubMed

Niedenführ, Sebastian; ten Pierick, Angela; van Dam, Patricia T N; Suarez-Mendez, Camilo A; Nöh, Katharina; Wahl, S Aljoscha

2016-05-01

Fluxomics and metabolomics are crucial tools for metabolic engineering and biomedical analysis to determine the in vivo cellular state. Especially, the application of (13)C isotopes allows comprehensive insights into the functional operation of cellular metabolism. Compared to single MS, tandem mass spectrometry (MS/MS) provides more detailed and accurate measurements of the metabolite enrichment patterns (tandem mass isotopomers), increasing the accuracy of metabolite concentration measurements and metabolic flux estimation. MS-type data from isotope labeling experiments is biased by naturally occurring stable isotopes (C, H, N, O, etc.). In particular, GC-MS(/MS) requires derivatization for the usually non-volatile intracellular metabolites introducing additional natural isotopes leading to measurements that do not directly represent the carbon labeling distribution. To make full use of LC- and GC-MS/MS mass isotopomer measurements, the influence of natural isotopes has to be eliminated (corrected). Our correction approach is analyzed for the two most common applications; (13)C fluxomics and isotope dilution mass spectrometry (IDMS) based metabolomics. Natural isotopes can have an impact on the calculated flux distribution which strongly depends on the substrate labeling and the actual flux distribution. Second, we show that in IDMS based metabolomics natural isotopes lead to underestimated concentrations that can and should be corrected with a nonlinear calibration. Our simulations indicate that the correction for natural abundance in isotope based fluxomics and quantitative metabolomics is essential for correct data interpretation. © 2015 Wiley Periodicals, Inc.

Stable Isotope Analysis of Precipitation Samples Obtained via Crowdsourcing Reveals the Spatiotemporal Evolution of Superstorm Sandy

PubMed Central

Good, Stephen P.; Mallia, Derek V.; Lin, John C.; Bowen, Gabriel J.

2014-01-01

Extra-tropical cyclones, such as 2012 Superstorm Sandy, pose a significant climatic threat to the northeastern United Sates, yet prediction of hydrologic and thermodynamic processes within such systems is complicated by their interaction with mid-latitude water patterns as they move poleward. Fortunately, the evolution of these systems is also recorded in the stable isotope ratios of storm-associated precipitation and water vapor, and isotopic analysis provides constraints on difficult-to-observe cyclone dynamics. During Superstorm Sandy, a unique crowdsourced approach enabled 685 precipitation samples to be obtained for oxygen and hydrogen isotopic analysis, constituting the largest isotopic sampling of a synoptic-scale system to date. Isotopically, these waters span an enormous range of values (21‰ for O, 160‰ for H) and exhibit strong spatiotemporal structure. Low isotope ratios occurred predominantly in the west and south quadrants of the storm, indicating robust isotopic distillation that tracked the intensity of the storm's warm core. Elevated values of deuterium-excess (25‰) were found primarily in the New England region after Sandy made landfall. Isotope mass balance calculations and Lagrangian back-trajectory analysis suggest that these samples reflect the moistening of dry continental air entrained from a mid-latitude trough. These results demonstrate the power of rapid-response isotope monitoring to elucidate the structure and dynamics of water cycling within synoptic-scale systems and improve our understanding of storm evolution, hydroclimatological impacts, and paleo-storm proxies. PMID:24618882

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

NASA Astrophysics Data System (ADS)

Chen, Guo; Schnyder, Hans; Auerswald, Karl

2017-04-01

Oxygen isotopes in animal and human tissues are expected to be good recorders of geographical origin and migration histories based on the isotopic relationship between hair oxygen and annual precipitation and the well-known spatial pattern of oxygen isotope composition in meteoric water. However, seasonal variation of oxygen isotope composition may diminish the origin information in the tissues. Here the seasonality of oxygen isotope composition in tail hair was investigated in a domestic suckler cow (Bos taurus) that underwent different ambient conditions, physiological states, and keeping and feeding strategies during five years. A detailed mechanistic model involving in ambient conditions, soil properties and animal physiology was built to explain this variation. The measured oxygen isotope composition in hair was significantly related (p<0.05) to the isotope composition in meteoric water in a regression analysis. Modelling suggested that this relation was only partly derived from the direct influence of feed moisture. Ambient conditions (temperature, moisture) did not only influence the isotopic signal of precipitation but also affected the animal itself (drinking water demand, transcutaneous vapor etc.). The clear temporal variation thus resulted from complex interactions with multiple influences. The twofold influence of ambient conditions via the feed and via the animal itself is advantageous for tracing the geographic origin because the oxygen isotope composition is then less influenced by variations in moisture uptake; however, it is unfavorable for indicating the production system, e.g. to distinguish between milk produced from fresh grass or from silage.

Molybdenum isotope fractionation during adsorption to organic matter

NASA Astrophysics Data System (ADS)

King, E. K.; Perakis, S. S.; Pett-Ridge, J. C.

2018-02-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2-170 h) and pH (2-7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (±0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

PubMed

Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

2014-05-20

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

Determination of the mechanism of demethylenation of (methylenedioxy)phenyl compounds by cytochrome P450 using deuterium isotope effects

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

Fukuto, J.M.; Kumagai, Y.; Cho, A.K.

1991-09-01

The mechanism of demethylenation of (methylenedioxy)benzene (MDB), (methylenedioxy)amphetamine (MDA), and (methylenedioxy)methamphetamine (MDMA) by purified rabbit liver cytochrome P450IIB4 has been investigated by using deuterium isotope effects. A comparison of the magnitude and direction of the observed kinetic isotope effects indicates that the three compounds are demethylenated by different mechanisms. The different mechanisms of demethylenation have been proposed on the basis of comparisons of the observed biochemical isotope effects with the isotope effects from purely chemical systems.

Differentiated stable isotopes signatures between pre- and post-flexion larvae of Atlantic bluefin tuna (Thunnus thynnus) and of its associated tuna species of the Balearic Sea (NW Mediterranean)

NASA Astrophysics Data System (ADS)

García, Alberto; Laiz-Carrión, Raúl; Uriarte, Amaya; Quintanilla, José M.; Morote, Elvira; Rodríguez, José M.; Alemany, Francisco

2017-06-01

The trophic ecology of bluefin tuna larvae (Thunnus thynnus) from the Balearic Sea, together with its co-existing tuna species such as albacore (T. alalunga), bullet (Auxis rochei) and little tunny (Euthynnus alletteratus) were examined by nitrogen and carbon stable isotope analyses. A total of 286 larvae were analyzed for this study, of which 72 larvae corresponded to bluefin, 57 to albacore, 81 to bullet tuna and 76 to little tunny. Tuna larvae were separated into the pre-flexion and post-flexion developmental stages. Within the size 3-9 mm standard length (SL), the stable isotope of nitrogen (δ15N) showed significant differences between species where bluefin tuna larvae ranked highest. Pre-flexion bluefin tuna and little tunny larvae showed significantly higher δ15N signatures than the post-flexion larvae. This effect is attributed to a biochemical trace of maternal δ15N signatures. However, neither albacore nor bullet tuna larvae showed this pattern in δ15N signatures, possibly owing to a compensation effect between lower maternal δ15N values transmitted to pre-flexion larvae and the early increase of δ15N values in post-flexion stages. One way ANOVA showed significant differences between species in the stable isotope ratio of carbon (δ13C) values, which suggests specific differences of carbon sources. Furthermore, a similar significant ontogenic effect between δ13C signatures of pre-flexion and post-flexion larvae is also evidenced in all four species. At pre-flexion stages, all species except bullet tuna larvae showed significant negative relationships between δ15N and larval standard length. At post-flexion stages, a significant linear relationship with larval size was only observed in albacore and bullet tuna larvae indicating a possible trophic shift towards early piscivory. With respect to δ13C values with larval size, all four species showed significant linear decreases. It may be explained by the metabolism of growth of somatic mass subject to modification of the relative carbon isotopic sources. In conclusion, the species' signatures of δ15N and δ13C indicate differentiated early life trophic niches. In addition, it is worth remarking the potential use of transgenerational isotopic transmission in future research applications.

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusion of quantum effects, such as zero-point energy and tunneling, on the transferring particle. Though previous studies have used TPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. The calculated primary H/D kinetic isotope effect agrees with previously reported experimental results, within experimental error. The kinetic isotope effects calculated with this method correspond to the kinetic isotope effect of the transfer event itself. The results reported here show that the kinetic isotope effects calculated from first-principles, purely for barrier passage, can be used to predict experimental kinetic isotope effects in enzymatic systems.

Rb-Sr isotopic studies of postorogenic granites from the eastern Arabian Shield, Kingdom of Saudi Arabia

USGS Publications Warehouse

Stuckless, J.S.; Futa, Kiyoto

1987-01-01

Available data indicate that postorogenic granites tend to be older in the southern part of the Arabian Shield. This suggests that plutonism started in the south and progressed to the north. Initial 87Sr/86Sr values also form a regional pattern. These ratios tend to be higher in the eastern part of the Arabian Shield, and suggest one source of continental affinity to the east and one of oceanic affinity to the west. The distribution of initial strontium isotope ratios does not clearly discriminate between the various models for Shield evolution; however, a sedimentary source region of mixed end members seems more compatible with the data pattern than models based on discrete boundaries between unrelated accreted blocks.

A method for screening of plant species for space use

NASA Technical Reports Server (NTRS)

Goeschl, J. D.; Sauer, R. L.; Scheld, H. W.

1986-01-01

A cost-effective methodology which monitors numerous dynamic aspects of carbon assimilation and allocation kinetics in live, intact plants is discussed. Analogous methods can apply to nitrogen uptake and allocation. This methodology capitalizes on the special properties of the short-lived, positron-gamma emitting isotope C-11 especially when applied as CO2-11 in a special extended square wave (ESW) pattern. The 20.4 minute half-life allows for repeated or continuous experiments on the same plant over periods of minutes, hours, days, or weeks. The steady-state isotope equilibrium approached during the ESW experiments, and the parameters which can be analyzed by this technique are also direct results of that short half-life. Additionally, the paired .511 MeV gamma rays penetrate any amount of tissue and their 180 deg opposite orientation provides good collimation and allows coincidence counting which nearly eliminates background.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

Biogenic minerals such as dental apatite have become commonly analysed archives preserving geochemical indicators of past environmental conditions and palaeoecologies. However, post-mortem, biogenic minerals are modified due to the alteration/replacement of labile components, and recent moves to utilise micro-mammal tooth δ18O signatures for refined Cenozoic terrestrial palaeoclimate reconstructions has lacked consideration of the chemical effects of predator digestion. Here, the physical and chemical condition of laboratory-raised mouse (Mus musculus) teeth have been investigated in conjunction with their bulk phosphate and tissue-specific δ18O values prior, and subsequent, to ingestion and excretion by various predator species (owls, mammals and a reptile). Substantial variability (up to 2‰) in the δ18O values of both undigested teeth and those ingested by specific predators suggests significant natural heterogeneity of individual prey δ18O. Statistically distinct, lower δ18O values (∼0.7‰) are apparent in teeth ingested by barn owls compared to undigested controls as a result of the chemically and enzymatically active digestive and waste-pellet environments. Overall, dentine tissues preserve lower δ18O values than enamel, while the greatest modification of oxygen isotope signals is exhibited in the basal enamel of ingested teeth as a result of its incompletely mineralised state. However, recognition of 18O-depletion in chemically purified phosphate analyses demonstrates that modification of original δ18O values is not restricted to labile oxygen-bearing carbonate and organic phases. The style and magnitude of digestive-alteration varies with predator species and no correlation was identified between specific physical or minor/trace-element (patterns or concentrations) modification of ingested teeth and disruption of their primary oxygen isotope values. Therefore, there is a current lack of any screening tool for oxygen isotope disruption as a result of predation. These results point to the need for careful application of the micro-mammal oxygen isotope palaeoenvironmental proxy in future studies.

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

USGS Publications Warehouse

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

2011-01-01

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

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

PubMed

English, Nathan B; McDowell, Nate G; Allen, Craig D; Mora, Claudia

2011-10-30

Tree-ring carbon and oxygen isotope ratios from live and recently dead trees may reveal important mechanisms of tree mortality. However, wood decay in dead trees may alter the δ(13)C and δ(18)O values of whole wood obscuring the isotopic signal associated with factors leading up to and including physiological death. We examined whole sapwood and α-cellulose from live and dead specimens of ponderosa pine (Pinus ponderosa), one-seed juniper (Juniperous monosperma), piñon pine (Pinus edulis) and white fir (Abies concolor), including those with fungal growth and beetle frass in the wood, to determine if α-cellulose extraction is necessary for the accurate interpretation of isotopic compositions in the dead trees. We found that the offset between the δ(13)C or δ(18)O values of α-cellulose and whole wood was the same for both live and dead trees across a large range of inter-annual and regional climate differences. The method of α-cellulose extraction, whether Leavitt-Danzer or Standard Brendel modified for small samples, imparts significant differences in the δ(13)C (up to 0.4‰) and δ(18) O (up to 1.2‰) of α-cellulose, as reported by other studies. There was no effect of beetle frass or blue-stain fungus (Ophiostoma) on the δ(13)C and δ(18)O of whole wood or α-cellulose. The relationships between whole wood and α-cellulose δ(13)C for ponderosa, piñon and juniper yielded slopes of ~1, while the relationship between δ(18)O of whole wood and α-cellulose was less clear. We conclude that there are few analytical or sampling obstacles to retrospective studies of isotopic patterns of tree mortality in forests of the western United States. Published in 2011 by John Wiley & Sons, Ltd.

Archival processes of the water stable isotope signal in East Antarctic ice cores

NASA Astrophysics Data System (ADS)

Casado, Mathieu; Landais, Amaelle; Picard, Ghislain; Münch, Thomas; Laepple, Thomas; Stenni, Barbara; Dreossi, Giuliano; Ekaykin, Alexey; Arnaud, Laurent; Genthon, Christophe; Touzeau, Alexandra; Masson-Delmotte, Valerie; Jouzel, Jean

2018-05-01

The oldest ice core records are obtained from the East Antarctic Plateau. Water isotopes are key proxies to reconstructing past climatic conditions over the ice sheet and at the evaporation source. The accuracy of climate reconstructions depends on knowledge of all processes affecting water vapour, precipitation and snow isotopic compositions. Fractionation processes are well understood and can be integrated in trajectory-based Rayleigh distillation and isotope-enabled climate models. However, a quantitative understanding of processes potentially altering snow isotopic composition after deposition is still missing. In low-accumulation sites, such as those found in East Antarctica, these poorly constrained processes are likely to play a significant role and limit the interpretability of an ice core's isotopic composition. By combining observations of isotopic composition in vapour, precipitation, surface snow and buried snow from Dome C, a deep ice core site on the East Antarctic Plateau, we found indications of a seasonal impact of metamorphism on the surface snow isotopic signal when compared to the initial precipitation. Particularly in summer, exchanges of water molecules between vapour and snow are driven by the diurnal sublimation-condensation cycles. Overall, we observe in between precipitation events modification of the surface snow isotopic composition. Using high-resolution water isotopic composition profiles from snow pits at five Antarctic sites with different accumulation rates, we identified common patterns which cannot be attributed to the seasonal variability of precipitation. These differences in the precipitation, surface snow and buried snow isotopic composition provide evidence of post-deposition processes affecting ice core records in low-accumulation areas.

Compound-specific isotopic analyses: a novel tool for reconstruction of ancient biogeochemical processes

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Freeman, K. H.; Popp, B. N.; Hoham, C. H.

1990-01-01

Patterns of isotopic fractionation in biogeochemical processes are reviewed and it is suggested that isotopic fractionations will be small when substrates are large. If so, isotopic compositions of biomarkers will reflect those of their biosynthetic precursors. This prediction is tested by consideration of results of analyses of geoporphyrins and geolipids from the Greenhorn Formation (Cretaceous, Western Interior Seaway of North America) and the Messel Shale (Eocene, lacustrine, southern Germany). It is shown (i) that isotopic compositions of porphyrins that are related to a common source, but which have been altered structurally, cluster tightly and (ii) that isotopic differences between geolipids and porphyrins related to a common source are equal to those observed in modern biosynthetic products. Both of these observations are consistent with preservation of biologically controlled isotopic compositions during diagenesis. Isotopic compositions of individual compounds can thus be interpreted in terms of biogeochemical processes in ancient depositional environments. In the Cretaceous samples, isotopic compositions of n-alkanes are covariant with those of total organic carbon, while delta values for pristane and phytane are covariant with those of porphyrins. In this unit representing an open marine environment, the preserved acyclic polyisoprenoids apparently derive mainly from primary material, while the extractable, n-alkanes derive mainly from lower levels of the food chain. In the Messel Shale, isotopic compositions of individual biomarkers range from -20.9 to -73.4% vs PDB. Isotopic compositions of specific compounds can be interpreted in terms of origin from methylotrophic, chemautotrophic, and chemolithotrophic microorganisms as well as from primary producers that lived in the water column and sediments of this ancient lake.

Changes in the Circum-Alpine Climate as a Function of the Alpine Upliftment: Constraints from Isotopic Compositions of Fossils, Sediments, and Vein Quartz

NASA Astrophysics Data System (ADS)

Vennemann, T. W.; Tutken, T.; Kocsis, L.; Mullis, J.

2005-12-01

The Tertiary circum-Alpine Molasse sediments were deposited during major periods of Alpine tectonism but also at a time of large global climatic change. They are well suited to study the effects of tectonic forcing on climate, because the sediments were deposited in marginal basins, partly to completely isolated from other major oceanic basins. Hence, a comparison of the past climatic and oceanographic evolution indicated by the sediments to those on a global scale, does allow for a qualitative evaluation of the relationship between tectonism and regional climate. Much is known about the geological-geochronological framework of alpine tectonism, including associated erosional rates and sediment volumes. Estimates of changes in paleoelevation and its direct influence on climate have, however, been less well constrained. Three independent lines of evidence indicate significant altitudes of the Alps during the Miocene: 1) H isotope compositions of clay minerals, formed as weathering products and subsequently deposited as part of the Alpine Molasse, have δD reaching values as low as -97‰. 2) O isotope compositions of retrograde metamorphic vein and fissure quartz and H isotope composition of its included fluids have δ18O values as low as -3.5‰ and δD values of -140‰, respectively. 3) ``Exotic" shark teeth from Swiss Upper Marine Molasse sediments that have δ18O values (VSMOW) around 11‰ (n=2), values unlike those from other teeth of the same locality (20.7 to 21.8‰; n=6), but for which the REE patterns support the same diagenetic history, hence supporting a freshwater formation of the low δ18O teeth (also supported by distinct Sr isotope compositions). Using these three approaches as a basis for estimating the isotopic composition of past precipitation and applying the present-day altitude effects on the compositions, it can be concluded that the Miocene Alps had mean altitudes of about 1500 to 2000 m, that is elevations similar to those of today. Paleoclimatic reconstructions from North Alpine Molasse sediments are based on oxygen isotope compositions of fossil mammalian tooth enamel for freshwater molasse deposits, and shark teeth, marine ostracoda, foraminifera, and mammalian phosphatic fossils for the Upper Marine Molasse deposits. The δ18O values (VPDB) of carbonate in phosphate from Oligocene and Miocene large mammal teeth (n=270), for example, vary over a large range from -11.9‰ to -0.5‰, but these variations parallel the composite O isotope curve of Tertiary benthic foraminifera, thus reflecting major global climatic changes such as the Late Oligocene warming, Mid-Miocene climate optimum, and Middle to Late Miocene cooling trends. The δ18O values (VSMOW) of phosphate in shark teeth (19.8 to 23.3‰; n=130) from Miocene marine molasse sediments as well as those of ostracods and foraminifera from these sediments all have variations that parallel those of composite curves for global changes. Collectively, the data support a Neogene paleogeography with a high mountain belt adjacent to marginal marine or freshwater depositional basins but with a regional climate, at least for the northern Molasse realm, that was strongly coupled to the global climate. The Alps thus appear not have influenced the local climate and/or atmospheric circulation patterns significantly.

Weathering fluxes to the Gulf of Mexico from the Pliocene to Holocene based on radiogenic isotopes

NASA Astrophysics Data System (ADS)

Portier, A. M.; Martin, E. E.; Hemming, S. R.; Thierens, M. M.; Raymo, M. E.

2014-12-01

Chemical weathering of the continents plays a key role in the global carbon cycle and delivers solutes to the ocean. Past studies, documented using radiogenic isotopes of detrital and seawater samples, show the intensity of weathering varies with climate over a range of time scales.. We analyzed Pb and Nd isotopic values of seawater extracted from dispersed Fe-Mn oxides, <2μm (clay) and <63μm (silt) detrital fractions of Pliocene to Holocene sediment from Gulf of Mexico ODP Site 625B to evaluate long term variations in weathering fluxes for three time slices: the Pliocene/early Pleistocene, Mid Pleistocene Transition (MPT), and late Pleistocene/Holocene. We also examine short term glacial/interglacial variations. Little variation is seen in Nd isotopes of detrital fractions with age, suggesting little change in the average age of material delivered to the Gulf. Seawater Nd values become less radiogenic over the Pleistocene, consistent with observed changes in Caribbean seawater. Pb isotopes of silt fractions are also relatively constant through time, but clay fractions are more radiogenic at the MPT and dispersed Fe-Mn oxides trend to more radiogenic values in the late Pleistocene. Consequently, the Pb isotopes of dispersed Fe-Mn oxides tend to be less radiogenic than the detrital fractions in samples older than 2000 ka and more radiogenic than the detrital fractions, particularly clays, at the MPT. This may reflect greater incongruent silicate weathering during the MPT, a change in weathering conditions that could be consistent with the Regolith Hypothesis. Over glacial/interglacial timescales, dispersed Fe-Mn oxides Pb isotopes become more radiogenic than detrital fractions, and clay fractions become more radiogenic than silt fractions, during glacial periods. However, all fractions have similar values during interglacials. This pattern is distinct from previous studies that found enhanced incongruent silicate weathering during warm intervals, but is consistent with recent work finding a correlation with carbonate content, whereby low carbonate during glacials at Site 625 corresponds to a greater offset between leachate and detrital Pb isotopes. Biases from "heavy mineral effects" and changes in circulation during periods of lower sea level also need to be considered.

Investigations of the Hydrologic Cycle in the Arctic Climate System Using Water Isotopes

NASA Astrophysics Data System (ADS)

Kopec, Ben Gordon

Warming has caused widespread changes to the Arctic hydrologic cycle, indicated by sea ice reductions, the Greenland Ice Sheet (GIS) mass loss, and permafrost degradation. Understanding Arctic hydrologic processes is essential for quantifying hydrological responses to climate change. A valuable tool to study these responses is the hydrogen and oxygen isotope ratios of water. Studies presented here aim to both innovatively apply water isotopes with existing understanding, and gain new knowledge in isotope systematics. I present several studies here. First, I show that Arctic precipitation increases with enhanced evaporation due to sea ice reduction; each 100,000 km2 loss in sea ice area increases the fraction of Arctic sourced moisture in total precipitation by 11 to 18%. Second, I argue that vapor sublimated from the GIS significantly contributes to summer precipitation at Summit, Greenland. This conclusion is first supported by isotopic variations in the daily precipitation collected at Summit for three years, and then further verified by 30 annual isotopic cycles in a shallow ice core. The result is not only important for quantifying the current ice sheet mass balance, but also for inferences of paleoclimate from ice cores. Third, I demonstrate that local scale atmospheric circulation in the glacier-free strip of West Greenland is dominated by convergence of dry glacial air masses from the east and moist marine air masses from the west. The dynamics of this convergence are affected by both regional radiation balance differences and broader circulation patterns such as the North Atlantic Oscillation. Humidity variations associated with these air masses control local precipitation and lake evaporation. Finally, along the east-west moisture gradient in West Greenland, lake evaporation also exhibits systematic changes in rate and isotopic enrichment, a result that is important for lake sediment core research. I have made advances in understanding water isotope systematics, mostly related to deuterium excess. In particular, variations in the deltaD-delta 18O slope, both for meteoric water and for lake water, are shown to contain interpretable environmental information. I also show that simple equilibrium Rayleigh distillation alters deuterium excess, an effect that was underappreciated in previous work.

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

On the influence of anharmonicity on the isotope effect

NASA Astrophysics Data System (ADS)

Galbaatar, T.; Drechsler, S. L.; Plakida, N. M.; Vujicic, G. M.

1991-12-01

The effect of double-well type lattice anharmonicity on the superconducting temperature and its isotope effect is investigated beyond the two-level approximation (TLA) within the Eliashberg theory. It is shown that anharmonicity can greatly modify the isotope effect; In particular anomalously large as well as negative values of the isotope effect exponent α are obtained in the strong and weak coupling limits, respectively.

Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

NASA Technical Reports Server (NTRS)

Kaufman, A. J.; Hayes, J. M.; Knoll, A. H.; Germs, G. J.

1991-01-01

The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

Rainfall and cave water isotopic relationships in two South-France sites

NASA Astrophysics Data System (ADS)

Genty, D.; Labuhn, I.; Hoffmann, G.; Danis, P. A.; Mestre, O.; Bourges, F.; Wainer, K.; Massault, M.; Van Exter, S.; Régnier, E.; Orengo, Ph.; Falourd, S.; Minster, B.

2014-04-01

This article presents isotopic measurements (δ18O and δD) of precipitation and cave drip water from two sites in southern France in order to investigate the link between rainfall and seepage water, and to characterize regional rainfall isotopic variability. These data, which are among the longest series in France, come from two rainfall stations in south-west France (Le Mas 1996-2012, and Villars 1998-2012; typically under Atlantic influence), and from one station in the south-east (Orgnac 2000-2012; under both Mediterranean and Atlantic influence). Rainfall isotopic composition is compared to drip water collected under stalactites from the same sites: Villars Cave (four drip stations 1999-2012) in the south-west, and Chauvet Cave (two drip stations 2000-2012) in the south-east, near Orgnac. The study of these isotopic data sets allows the following conclusions to be drawn about the rainfall/drip water relationships and about rainfall variability: (1) the cave drip water isotopic composition does not show any significant changes since the beginning of measurements; in order to explain its isotopic signature it is necessary to integrate weighted rainfall δ18O of all months during several years, which demonstrates that, even at shallow depths (10-50 m), cave drip water is a mixture of rain water integrated over relatively long periods, which give an apparent time residence from several months to up to several years. These results have important consequences on the interpretation of proxies like speleothem fluid inclusions and tree-ring cellulose isotopic composition, which are used for paleoclimatic studies; (2) in the Villars Cave, where drip stations at two different depths were studied, lower δ18O values were observed in the lower galleries, which might be due to winter season overflows during infiltration and/or to older rain water with a different isotopic composition that reaches the lower galleries after years; (3) local precipitation is characterized by local meteoric water lines, LMWL, with δ18O/δD slopes close to 7 in both areas, and correlations between air temperature and precipitation δ18O are low at both monthly and annual scales, even with temperature weighted by the amount of precipitation; (4) the mesoscale climate model REMOiso, equipped with a water isotope module, allows the direct comparison of modeled and observed long term water isotope records. The model slightly overestimates rainfall δ18O at the respective sampling stations. However, it simulates very well not only the seasonal rainfall isotopic signal but also some intra-seasonal patterns such as a typical double-peak δ18O pattern in winter time.

Isotope effects on the optical spectra of semiconductors

NASA Astrophysics Data System (ADS)

Cardona, Manuel; Thewalt, M. L. W.

2005-10-01

Since the end of the cold war, macroscopic amounts of separated stable isotopes of most elements have been available “off the shelf” at affordable prices. Using these materials, single crystals of many semiconductors have been grown and the dependence of their physical properties on isotopic composition has been investigated. The most conspicuous effects observed have to do with the dependence of phonon frequencies and linewidths on isotopic composition. These affect the electronic properties of solids through the mechanism of electron-phonon interaction, in particular, in the corresponding optical excitation spectra and energy gaps. This review contains a brief introduction to the history, availability, and characterization of stable isotopes, including their many applications in science and technology. It is followed by a concise discussion of the effects of isotopic composition on the vibrational spectra, including the influence of average isotopic masses and isotopic disorder on the phonons. The final sections deal with the effects of electron-phonon interaction on energy gaps, the concomitant effects on the luminescence spectra of free and bound excitons, with particular emphasis on silicon, and the effects of isotopic composition of the host material on the optical transitions between the bound states of hydrogenic impurities.

Dendritic network models: Improving isoscapes and quantifying influence of landscape and in-stream processes on strontium isotopes in rivers

USGS Publications Warehouse

Brennan, Sean R.; Torgersen, Christian E.; Hollenbeck, Jeff P.; Fernandez, Diego P.; Jensen, Carrie K; Schindler, Daniel E.

2016-01-01

A critical challenge for the Earth sciences is to trace the transport and flux of matter within and among aquatic, terrestrial, and atmospheric systems. Robust descriptions of isotopic patterns across space and time, called “isoscapes,” form the basis of a rapidly growing and wide-ranging body of research aimed at quantifying connectivity within and among Earth's systems. However, isoscapes of rivers have been limited by conventional Euclidean approaches in geostatistics and the lack of a quantitative framework to apportion the influence of processes driven by landscape features versus in-stream phenomena. Here we demonstrate how dendritic network models substantially improve the accuracy of isoscapes of strontium isotopes and partition the influence of hydrologic transport versus local geologic features on strontium isotope ratios in a large Alaska river. This work illustrates the analytical power of dendritic network models for the field of isotope biogeochemistry, particularly for provenance studies of modern and ancient animals.

Carbon isotope fractionation by thermophilic phototrophic sulfur bacteria: evidence for autotrophic growth in natural populations

NASA Technical Reports Server (NTRS)

Madigan, M. T.; Takigiku, R.; Lee, R. G.; Gest, H.; Hayes, J. M.

1989-01-01

Purple phototrophic bacteria of the genus Chromatium can grow as either photoautotrophs or photoheterotrophs. To determine the growth mode of the thermophilic Chromatium species, Chromatium tepidum, under in situ conditions, we have examined the carbon isotope fractionation patterns in laboratory cultures of this organism and in mats of C. tepidum which develop in sulfide thermal springs in Yellowstone National Park. Isotopic analysis (13C/12C) of total carbon, carotenoid pigments, and bacteriochlorophyll from photoautotrophically grown cultures of C. tepidum yielded 13C fractionation factors near -20%. Cells of C. tepidum grown on excess acetate, wherein synthesis of the Calvin cycle enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase ribulose bisphosphate carboxylase) was greatly repressed, were isotopically heavier, fractionation factors of ca. -7% being observed. Fractionation factors determined by isotopic analyses of cells and pigment fractions of natural populations of C. tepidum growing in three different sulfide thermal springs in Yellowstone National Park were approximately -20%, indicating that this purple sulfur bacterium grows as a photoautotroph in nature.

Nitrogen isotope fractionation during archaeal ammonia oxidation: Coupled estimates from isotopic measurements of ammonium and nitrite

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Stieglmeier, Michaela; Bayer, Barbara; Jochum, Lara; Melcher, Michael; Wanek, Wolfgang

2014-05-01

Ammonia-oxidizing archaea (AOA) are ubiquitous in marine and terrestrial environments and knowledge about the nitrogen (N) isotope effect associated with their ammonia oxidation activity will allow a better understanding of natural abundance isotope ratios, and therefore N transformation processes, in the environment. Here we examine the kinetic isotope effect for ammonia oxidation in a pure soil AOA culture (Ca. Nitrososphaera viennensis) and a marine AOA enrichment culture. We estimated the isotope effect from both isotopic signatures of ammonium and nitrite over the course of ammonia oxidation. Estimates of the isotope effect based on the change in the isotopic signature of ammonium give valuable insight, because these estimates are not subject to the same concerns (e.g., accumulation of an intermediate) as estimates based on isotopic measurements of nitrite. Our results show that both the pure soil AOA culture and a marine AOA enrichment culture have similar but substantial isotope effect during ammonia consumption (31-34 per mill; based on ammonium) and nitrite production (43-45 per mill; based on nitrite). The 15N fractionation factors of both cultures tested fell in the upper range of the reported isotope effects for archaeal and bacterial ammonia oxidation (10-41 per mill) or were even higher than those. The isotope fractionation for nitrite production was significantly larger than for ammonium consumption, indicating that (1) some intermediate (e.g., hydroxylamine) of ammonia oxidation accumulates, allowing for a second 15N fractionation step to be expressed, (2) a fraction of ammonia oxidized is lost via gaseous N forms (e.g., NO or N2O), which is 15N-enriched or (3) a fraction of ammonium is assimilated into AOA biomass, biomass becoming 15N-enriched. The significance of these mechanisms will be explored in more detail for the soil AOA culture, based on isotope modeling and isotopic measurements of biomass and N2O.

Determining the N and O isotope effects of microbial nitrite reduction: the global N cycle implications of an enzyme-dependent isotope effect

NASA Astrophysics Data System (ADS)

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

2014-12-01

The marine nitrogen (N) cycle is a dynamic system of critical importance, since nitrogen is the limiting nutrient in over half of the world's oceans. Denitrification and anammox, the main N loss processes from the ocean, have different effects on carbon cycling and greenhouse gas emission. Understanding the balance between the two processes is vital to understanding the role of the N cycle in global climate change. One approach for investigating these processes is by using stable isotope analysis to estimate the relative magnitudes of N fluxes, particularly for biologically mediated processes. In order to make the most of the currently available isotope analysis techniques, it is necessary to know the isotope effects for each processes occurring in the environment. Nitrite reduction is an important step in denitrification. Previous work had begun to explore the N isotope effects for nitrite reduction, but no oxygen (O) isotope effect has been measured. Additionally, no consideration has been given to the type of nitrite reductase carrying out the reaction. There are two main types of respiratory nitrite reductase, one that is Cu-based and another that is Fe-based. We performed batch culture experiments with denitrifier strains possessing either a Cu-type or Fe-type nitrite reductase. Both N and O isotope effects for nitrite reduction were determined for each of these experiments by measuring the NO2- concentration, as well as the N and O isotopes of nitrite and applying a Rayleigh fractionation model. Both the N and O isotope effects were found to be significantly different between the two types of enzymes. This enzyme-linked difference in isotope effects emphasizes the importance of microbial community composition within the global N cycle.

Carbon and hydrogen isotopic effects of stomatal density in Arabidopsis thaliana

NASA Astrophysics Data System (ADS)

Lee, Hyejung; Feakins, Sarah J.; Sternberg, Leonel da S. L.

2016-04-01

Stomata are key gateways mediating carbon uptake and water loss from plants. Varied stomatal densities in fossil leaves raise the possibility that isotope effects associated with the openness of exchange may have mediated plant wax biomarker isotopic proxies for paleovegetation and paleoclimate in the geological record. Here we use Arabidopsis thaliana, a widely used model organism, to provide the first controlled tests of stomatal density on carbon and hydrogen isotopic compositions of cuticular waxes. Laboratory grown wildtype and mutants with suppressed and overexpressed stomatal densities allow us to directly test the isotope effects of stomatal densities independent of most other environmental or biological variables. Hydrogen isotope (D/H) measurements of both plant waters and plant wax n-alkanes allow us to directly constrain the isotopic effects of leaf water isotopic enrichment via transpiration and biosynthetic fractionations, which together determine the net fractionation between irrigation water and n-alkane hydrogen isotopic composition. We also measure carbon isotopic fractionations of n-alkanes and bulk leaf tissue associated with different stomatal densities. We find offsets of +15‰ for δD and -3‰ for δ13C for the overexpressed mutant compared to the suppressed mutant. Since the range of stomatal densities expressed is comparable to that found in extant plants and the Cenozoic fossil record, the results allow us to consider the magnitude of isotope effects that may be incurred by these plant adaptive responses. This study highlights the potential of genetic mutants to isolate individual isotope effects and add to our fundamental understanding of how genetics and physiology influence plant biochemicals including plant wax biomarkers.

Food web heterogeneity and succession in created saltmarshes

USGS Publications Warehouse

Nordstrom, M C; Demopoulos, Amanda W.J.; Whitcraft, CR; Rismondo, A.; McMillan, P.; Gonzales, J P; Levin, L A

2015-01-01

1. Ecological restoration must achieve functional as well as structural recovery. Functional metrics for reestablishment of trophic interactions can be used to complement traditional monitoring of structural attributes. In addition, topographic effects on food web structure provide added information within a restoration context; often, created sites may require spatial heterogeneity to effectively match structure and function of natural habitats. 2. We addressed both of these issues in our study of successional development of benthic food web structure, with focus on bottom–up driven changes in macroinvertebrate consumer assemblages in the salt marshes of the Venice Lagoon, Italy. We combined quantified estimates of the changing community composition with stable isotope data (13C:12C and 15N:14N) to compare the general trophic structure between created (2–14 years) marshes and reference sites and along topographic elevation gradients within salt marshes. 3. Macrofaunal invertebrate consumers exhibited local, habitat-specific trophic patterns. Stable isotope-based trophic structure changed with increasing marsh age, in particular with regards to mid-elevation (Salicornia) habitats. In young marshes, the mid-elevation consumer signatures resembled those of unvegetated ponds. The mid elevation of older and natural marshes had a more distinct Salicornia-zone food web, occasionally resembling that of the highest (Sarcocornia-dominated) elevation. In summary, this indicates that primary producers and availability of vascular plant detritus structure consumer trophic interactions and the flow of carbon. 4. Functionally different consumers, subsurface-feeding detritivores (Oligochaeta) and surface grazers (Hydrobia sp.), showed distinct but converging trajectories of isotopic change over time, indicating that successional development may be asymmetric between ‘brown’ (detrital) guilds and ‘green’ (grazing) guilds in the food web. 5. Synthesis and applications. Created marsh food webs converged into a natural state over about a decade, with successional shifts seen in both consumer community composition and stable isotope space. Strong spatial effects were noted, highlighting the utility of stable isotopes to evaluate functional equivalence in spatially heterogeneous systems. Understanding the recovery of functional properties such as food web support, and their inherent spatial variability, is key to planning and managing successful habitat restoration.

The First New Zealanders: Patterns of Diet and Mobility Revealed through Isotope Analysis

PubMed Central

Kinaston, Rebecca L.; Walter, Richard K.; Jacomb, Chris; Brooks, Emma; Tayles, Nancy; Halcrow, Sian E.; Stirling, Claudine; Reid, Malcolm; Gray, Andrew R.; Spinks, Jean; Shaw, Ben; Fyfe, Roger; Buckley, Hallie R.

2013-01-01

Direct evidence of the environmental impact of human colonization and subsequent human adaptational responses to new environments is extremely rare anywhere in the world. New Zealand was the last Polynesian island group to be settled by humans, who arrived around the end of the 13th century AD. Little is known about the nature of human adaptation and mobility during the initial phase of colonization. We report the results of the isotopic analysis (carbon, nitrogen and strontium) of the oldest prehistoric skeletons discovered in New Zealand to assess diet and migration patterns. The isotope data show that the culturally distinctive burials, Group 1, had similar diets and childhood origins, supporting the assertion that this group was distinct from Group 2/3 and may have been part of the initial colonizing population at the site. The Group 2/3 individuals displayed highly variable diets and likely lived in different regions of the country before their burial at Wairau Bar, supporting the archaeological evidence that people were highly mobile in New Zealand since the initial phase of human settlement. PMID:23691250

Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

PubMed

Thiemens, Mark H

2013-10-29

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

Mixed fluid sources involved in diamond growth constrained by Sr-Nd-Pb-C-N isotopes and trace elements

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Cartigny, Pierre

2010-01-01

Sub-micrometer inclusions in diamonds carry high-density fluids (HDF) from which the host diamonds have precipitated. The chemistry of these fluids is our best opportunity of characterizing the diamond-forming environment. The trace element patterns of diamond fluids vary within a limited range and are similar to those of carbonatitic/kimberlitic melts that originate from beneath the lithospheric mantle. A convecting mantle origin for the fluid is also implied by C isotopic compositions and by a preliminary Sr isotopic study (Akagi, T., Masuda, A., 1988. Isotopic and elemental evidence for a relationship between kimberlite and Zaire cubic diamonds. Nature 336, 665-667.). Nevertheless, the major element chemistry of HDFs is very different from that of kimberlites and carbonatites, varying widely and being characterized by extreme K enrichment (up to ˜ 39 wt.% on a water and carbonate free basis) and high volatile contents. The broad spectrum of major element compositions in diamond-forming fluids has been related to fluid-rock interaction and to immiscibility processes. Elemental signatures can be easily modified by a variety of mantle processes whereas radiogenic isotopes give a clear fingerprint of the time-integrated evolution of the fluid source region. Here we present the results of the first multi radiogenic-isotope (Sr, Nd, Pb) and trace element study on fluid-rich diamonds, implemented using a newly developed off-line laser sampling technique. The data are combined with N and C isotope analysis of the diamond matrix to better understand the possible sources of fluid involved in the formation of these diamonds. Sr isotope ratios vary significantly within single diamonds. The highly varied but unsupported Sr isotope ratios cannot be explained by immiscibility processes or fluid-mineral elemental fractionations occurring at the time of diamond growth. Our results demonstrate the clear involvement of a mixed fluid, with one component originating from ancient incompatible element-enriched parts of the lithospheric mantle while the trigger for releasing this fluid source was probably carbonatitic/kimberlitic melts derived from greater depths. We suggest that phlogopite mica was an integral part of the enriched lithospheric fluid source and that breakdown of this mica releases K and radiogenic Sr into a fluid phase. The resulting fluids operate as a major metasomatic agent in the sub-continental lithospheric mantle as reflected by the isotopic composition and trace element patterns of G10 garnets.

Understanding trophic interactions in host-parasite associations using stable isotopes of carbon and nitrogen.

PubMed

Nachev, Milen; Jochmann, Maik A; Walter, Friederike; Wolbert, J Benjamin; Schulte, S Marcel; Schmidt, Torsten C; Sures, Bernd

2017-02-17

Stable isotope analysis of carbon and nitrogen can deliver insights into trophic interactions between organisms. While many studies on free-living organisms are available, the number of those focusing on trophic interactions between hosts and their associated parasites still remains scarce. In some cases information about taxa (e.g. acanthocephalans) is completely missing. Additionally, available data revealed different and occasionally contrasting patterns, depending on the parasite's taxonomic position and its degree of development, which is most probably determined by its feeding strategy (absorption of nutrients through the tegument versus active feeding) and its localization in the host. Using stable isotope analysis of carbon and nitrogen we provided first data on the trophic position of an acanthocephalan species with respect to its fish host. Barbels (Barbus barbus) infected only with adult acanthocephalans Pomphorhynchus laevis as well as fish co-infected with the larval (L4) nematodes Eustrongylides sp. from host body cavity were investigated in order to determine the factors shaping host-parasite trophic interactions. Fish were collected in different seasons, to study also potential isotopic shifts over time, whereas barbels with single infection were obtained in summer and co-infected ones in autumn. Acanthocephalans as absorptive feeders showed lower isotope discrimination values of δ 15 N than the fish host. Results obtained for the acanthocephalans were in line with other parasitic taxa (e.g. cestodes), which exhibit a similar feeding strategy. We assumed that they feed mainly on metabolites, which were reprocessed by the host and are therefore isotopically lighter. In contrast, the nematodes were enriched in the heavier isotope δ 15 N with respect to their host and the acanthocephalans, respectively. As active feeders they feed on tissues and blood in the body cavity of the host and thus showed isotope discrimination patterns resembling those of predators. We also observed seasonal differences in the isotope signatures of fish tissues and acanthocephalans, which were attributed to changes in food composition of the host and to seasonality in the transmission and development of acanthocephalans. This study provided first data on trophic interaction between an acanthocephalan species and its associated host, which support the tendency already described for other taxa with similar nutrition strategy (e.g. cestodes). Actively feeding taxa such as larval Eustrongylides sp., appear to act like predators as it can be seen from their isotope discrimination values. However, future research on additional host-parasite systems and especially on acanthocephalans is needed in order to corroborate these conclusions.

Migration stopover ecology of western avian populations: A southwestern migration workshop

USGS Publications Warehouse

Skagen, Susan K.; Melcher, Cynthia P.; Hazelwood, Rob

2004-01-01

Workshop participants discussed a coordinated approach for addressing immediate research needs regarding migration patterns and crucial stopover sites and types. They envisioned a three­-tiered, coordinated approach: (1) long-term research to address effects of climate change and other large-scale patterns, (2) intensive, short-term survey and monitoring efforts using a stratified random design within habitats of interest to elucidate regional patterns of distribution and habitat use, and (3) research conducted at existing survey and banding sites to address more in-depth questions (e.g., rates of lipid deposition, microhabitat use, isotope analyses). There was considerable interest in developing common research proposals to blend the broad expertise represented at this workshop. A second meeting is recommended to build on the momentum of these discussions, to facilitate collaborations, and further the goals of integrated approaches to broadscale research on migration stopover ecology. 

The influence of leaf-atmosphere NH3(g ) exchange on the isotopic composition of nitrogen in plants and the atmosphere.

PubMed

Johnson, Jennifer E; Berry, Joseph A

2013-10-01

The distribution of nitrogen isotopes in the biosphere has the potential to offer insights into the past, present and future of the nitrogen cycle, but it is challenging to unravel the processes controlling patterns of mixing and fractionation. We present a mathematical model describing a previously overlooked process: nitrogen isotope fractionation during leaf-atmosphere NH3(g ) exchange. The model predicts that when leaf-atmosphere exchange of NH3(g ) occurs in a closed system, the atmospheric reservoir of NH3(g ) equilibrates at a concentration equal to the ammonia compensation point and an isotopic composition 8.1‰ lighter than nitrogen in protein. In an open system, when atmospheric concentrations of NH3(g ) fall below or rise above the compensation point, protein can be isotopically enriched by net efflux of NH3(g ) or depleted by net uptake. Comparison of model output with existing measurements in the literature suggests that this process contributes to variation in the isotopic composition of nitrogen in plants as well as NH3(g ) in the atmosphere, and should be considered in future analyses of nitrogen isotope circulation. The matrix-based modelling approach that is introduced may be useful for quantifying isotope dynamics in other complex systems that can be described by first-order kinetics. © 2013 John Wiley & Sons Ltd.

A new approach to aid the characterisation and identification of metabolites of a model drug; partial isotope enrichment combined with novel formula elucidation software.

PubMed

Hobby, Kirsten; Gallagher, Richard T; Caldwell, Patrick; Wilson, Ian D

2009-01-01

This work describes the identification of 'isotopically enriched' metabolites of 4-cyanoaniline using the unique features of the software package 'Spectral Simplicity'. The software is capable of creating the theoretical mass spectra for partially isotope-enriched compounds, and subsequently performing an elemental composition analysis to give the elemental formula for the 'isotopically enriched' metabolite. A novel mass spectral correlation method, called 'FuzzyFit', was employed. 'FuzzyFit' utilises the expected experimental distribution of errors in both mass accuracy and isotope pattern and enables discrimination between statistically probable and improbable candidate formulae. The software correctly determined the molecular formulae of ten previously described metabolites of 4-cyanoaniline confirming the technique of partial isotope enrichment can produce results analogous to standard methodologies. Six previously unknown species were also identified, based on the presence of the unique 'designer' isotope ratio. Three of the unknowns were tentatively identified as N-acetylglutamine, O-methyl-N acetylglucuronide and a putative fatty acid conjugate. The discovery of a significant number of unknown species of a model drug with a comprehensive history of investigation highlights the potential for enhancement to the analytical process by the use of 'designer' isotope ratio compounds. The 'FuzzyFit' methodology significantly aided the elucidation of candidate formulae, by provision of a vastly simplified candidate formula data set. Copyright (c) 2008 John Wiley & Sons, Ltd.

Lipid Extraction and the Fugacity of Stable Isotope Values

NASA Astrophysics Data System (ADS)

Padula, V.; Causey, D.; Wolf, N.; Welker, J. M.

2013-12-01

Stable isotope analysis of blood, feathers, and other tissues are often used to infer migration patterns, diet composition and trophic status of seabirds. Tissues contain variable amounts of lipids that are depleted in the heavy carbon isotope (13C) and may introduce a bias in these values. There is evidence that lipid extraction may affect other stable isotope ratios, such as δ15N. Consequently, correction factors need to be applied to appropriately interpret δ13C and δ15N values for individual species and tissue type. In this study, we collected seven species of seabirds from the Near Islands, the western most group of islands in the Aleutian Island archipelago. We sampled kidney, liver, heart and muscle samples from each bird and after freeze drying, individual tissue samples were divided into two subsamples. We left one subsample unaltered and extracted lipids from the other subsample using a 2:1 chloroform-methanol solution. We found that the change in δ13C values after lipid extraction (Δδ13C) varied widely among categories (eg., species, tissue type) from 0 - 4 ‰, while Δδ15N values ranged from 0 to 2‰. Notably, within category variation was nonsignificant and the Δδ values were linear against the covariant C:N ratio of the isotopic data, which allows us to use arithmetic corrections for categorical values. Our data strongly indicate that the effects of lipid extraction on stable isotopic values, while linear within category, vary widely by species, tissue, geographic area, year of collection, and isotope. Fugacity is usually employed as a thermodynamic quantity related to the chemical potential or activity that characterizes the escaping tendency from a phase (eg. Mackay & Paterson 1982). Here we use fugacity in the earlier, broader sense of fleeting, transitory, or instable states (eg., S. Johnson 1751), and its measure may be approximated by the higher order variance of Δδ13C and Δδ15N among data categories. Clearly, understanding the nature of variation and the physiological processes responsible for stable isotope values from biological tissues are critical for their interpretation. Change in carbon and nitrogen stable isotopes (ΔδC13, Δδ15N) after lipid extraction for Tufted Puffins (Fratercula cirrhata) collected July 2010 at Attu Island, Aleutians.

Constraining Holocene hydrological changes in the Carpathian-Balkan region using speleothem δ18O and pollen-based temperature reconstructions

NASA Astrophysics Data System (ADS)

Drăguşin, V.; Staubwasser, M.; Hoffmann, D. L.; Ersek, V.; Onac, B. P.; Veres, D.

2014-07-01

Here we present a speleothem isotope record (POM2) from Ascunsă Cave (Romania) that provides new data on past climate changes in the Carpathian-Balkan region from 8.2 ka until the present. This paper describes an approach to constrain the effect of temperature changes on calcite δ18O values in stalagmite POM2 over the course of the middle Holocene (6-4 ka), and across the 8.2 and 3.2 ka rapid climate change events. Independent pollen temperature reconstructions are used to this purpose. The approach combines the temperature-dependent isotope fractionation of rain water during condensation and fractionation resulting from calcite precipitation at the given cave temperature. The only prior assumptions are that pollen-derived average annual temperature reflects average cave temperature, and that pollen-derived coldest and warmest month temperatures reflect the range of condensation temperatures of rain above the cave site. This approach constrains a range of values between which speleothem δ18O changes should be found if controlled only by surface temperature variations at the cave site. Deviations of the change in δ18Ocspel values from the calculated temperature-constrained range of change are interpreted towards large-scale variability of climate-hydrology. Following this approach, we show that an additional ∼0.6‰ enrichment of δ18Oc in the POM2 stalagmite was caused by changing hydrological patterns in SW Romania across the middle Holocene, most likely comprising local evaporation from the soil and an increase in Mediterranean moisture δ18O. Further, by extending the calculations to other speleothem records from around the entire Mediterranean basin, it appears that all eastern Mediterranean speleothems recorded a similar isotopic enrichment due to changing hydrology, whereas all changes recorded in speleothems from the western Mediterranean are fully explained by temperature variation alone. This highlights a different hydrological evolution between the two sides of the Mediterranean. Our results also demonstrate that during the 8.2 ka event, POM2 stable isotope data essentially fit the temperature-constrained isotopic variability. In the case of the 3.2 ka event, an additional climate-related hydrological factor is more evident. This implies a different rainfall pattern in the Southern Carpathian region during this event at the end of the Bronze Age.

Temperature dependence of the isotope chemistry of the heavy elements.

PubMed Central

Bigeleisen, J

1996-01-01

The temperature coefficient of equilibrium isotope fractionation in the heavy elements is shown to be larger at high temperatures than that expected from the well-studied vibrational isotope effects. The difference in the isotopic behavior of the heavy elements as compared with the light elements is due to the large nuclear isotope field shifts in the heavy elements. The field shifts introduce new mechanisms for maxima, minima, crossovers, and large mass-independent isotope effects in the isotope chemistry of the heavy elements. The generalizations are illustrated by the temperature dependence of the isotopic fractionation in the redox reaction between U(VI) and U(IV) ions. PMID:8790340

Stable isotope (2H, 17O, 18O) and hydro chemical patterns of precipitation collected in weekly resolution at Hannover, Germany

NASA Astrophysics Data System (ADS)

Koeniger, Paul; Himmelsbach, Thomas

2016-04-01

Long-term observations of stable isotopes (δ18O and δ2H) in precipitation were initiated in May 2008 at the Federal Institute of Geosciences and Natural Resources (BGR) in Hannover, Germany. In 2014 all precipitation samples were re-analyzed because a purchase of a new laser spectrometer (Picarro L2140-i) now allowed measurements of δ17O and a calculation of the 17O-excess parameter. Starting in October 2015 a routine analysis of hydro chemical parameters was added whenever enough sample aliquot was available (major ions, trace elements). A discussion of the stable isotope data of the seven year series of weekly precipitation samples (n = 370) will be presented. Beneath general patterns (seasonality and trends) we also focus on importance of amount weighing procedures, corrections for minor rain amounts, aspects of sample storage and re-analyzes, as well as impacts through changes in analytical equipment (IRMS, CRD spectroscopy) which is visible from the data. For stable isotopes a Thermo Fisher delta plus IRMS (Gasbench and H-Device) was used until 2011 and from 2012 on a Picarro L2120-i water vapor analyzer with long-term accuracies for quality check samples better than 0.2‰ and 0.8‰ for δ18O and δ2H, respectively.

Coupled Soil-Plant Water Dynamics During Drought-Rewetting Transitions

NASA Astrophysics Data System (ADS)

Volkmann, T. H.; Haberer, K.; Gessler, A.; Weiler, M.

2013-12-01

The predicted climate and land-use changes could have dramatic effects on the water balance of the soil-vegetation system, particularly under frequent drought and subsequent rewetting conditions. Yet, estimation of these effects and associated consequences for the structure and functioning of ecosystems, groundwater recharge, drinking water availability, and the water cycle is currently impeded by gaps in our understanding of the spatiotemporal dynamics of soil water in the rooted soil horizons, the dynamics and driving physiological processes of plant water acquisition, and the transpiration from plant leaves under changing environmental conditions. Combining approaches from the disciplines of plant ecophysiology and soil and isotope hydrology, this work aims to fill this gap by quantitatively characterizing the interaction between plant water use - as affected by rooting patterns and ecophysiology of different plant functional groups - and the water balance of variably complex ecosystems with emphasis on drought and rewetting phases. Results from artificial drought and subsequent rewetting in field experiments using isotopically and dye (Brilliant Blue FCF) labeled water conducted on plots of various surface cover (bare soil, grass, beech, oak, vine) established on luvisol on loess in southwestern Germany are presented. Detailed spatiotemporal insights into the coupled short-term (hours to days) dynamics of soil and plant water during the experiments is facilitated by the application of newly developed techniques for high-frequency in-situ monitoring of stable isotope signatures in both pore water and transpired water using commercial laser-based spectrometers in conjunction with plant ecophysiological, soil physical state, and dye staining observations. On the one hand, the spatiotemporal patterns of plant water uptake are assessed and related to morphological and physiological traits driving plant water uptake, functional adaptations of plants to changes of soil water availability, and intra- and interspecies competition for water resources access. On the other hand, the effects of vegetation cover on infiltration, preferential flow paths characteristics, and soil water storage in the rooted soil horizons are investigated. The results of the experiments and the developed methodology will contribute to an improved understanding of ecosystem response and adaptation to drought and short-term changes in environmental conditions.

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Molybdenum isotope fractionation during adsorption to organic matter

USGS Publications Warehouse

King, Elizabeth K.; Perakis, Steven; Pett-Ridge, Julie C.

2018-01-01

Organic matter is of emerging interest as a control on molybdenum (Mo) biogeochemistry, and information on isotope fractionation during adsorption to organic matter can improve interpretations of Mo isotope variations in natural settings. Molybdenum isotope fractionation was investigated during adsorption onto insolubilized humic acid (IHA), a surrogate for organic matter, as a function of time (2–170 h) and pH (2–7). For the time series experiment performed at pH 4.2, the average Mo isotope fractionation between the solution and the IHA (Δ98Mosolution-IHA) was 1.39‰ (± 0.16‰, 2σ, based on 98Mo/95Mo relative to the NIST 3134 standard) at steady state. For the pH series experiment, Mo adsorption decreased as pH increased from 2.0 to 6.9, and the Δ98Mosolution-IHA increased from 0.82‰ to 1.79‰. We also evaluated natural Mo isotope patterns in precipitation, foliage, organic horizon, surface mineral soil, and bedrock from 12 forested sites in the Oregon Coast Range. The average Mo isotope offset observed between precipitation and organic (O) horizon soil was 2.1‰, with light Mo isotopes adsorbing preferentially to organic matter. Fractionation during adsorption to organic matter is similar in magnitude and direction to prior observations of Mo fractionation during adsorption to Fe- and Mn- (oxyhydr)oxides. Our finding that organic matter influences Mo isotope composition has important implications for the role of organic matter as a driver of trace metal retention and isotopic fractionation.

Nitrogen isotopic baselines and implications for estimating foraging habitat and trophic position of yellowfin tuna in the Indian and Pacific Oceans

NASA Astrophysics Data System (ADS)

Lorrain, Anne; Graham, Brittany S.; Popp, Brian N.; Allain, Valérie; Olson, Robert J.; Hunt, Brian P. V.; Potier, Michel; Fry, Brian; Galván-Magaña, Felipe; Menkes, Christophe E. R.; Kaehler, Sven; Ménard, Frédéric

2015-03-01

Assessment of isotopic compositions at the base of food webs is a prerequisite for using stable isotope analysis to assess foraging locations and trophic positions of marine organisms. Our study represents a unique application of stable-isotope analyses across multiple trophic levels (primary producer, primary consumer and tertiary consumer) and over a large spatial scale in two pelagic marine ecosystems. We found that δ15N values of particulate organic matter (POM), barnacles and phenylalanine from the muscle tissue of yellowfin tuna all showed similar spatial patterns. This consistency suggests that isotopic analysis of any of these can provide a reasonable proxy for isotopic variability at the base of the food web. Secondly, variations in the δ15N values of yellowfin tuna bulk-muscle tissues paralleled the spatial trends observed in all of these isotopic baseline proxies. Variation in isotopic composition at the base of the food web, rather than differences in tuna diet, explained the 11‰ variability observed in the bulk-tissue δ15N values of yellowfin tuna. Evaluating the trophic position of yellowfin tuna using amino-acid isotopic compositions across the western Indian and equatorial Pacific Oceans strongly suggests these tuna occupy similar trophic positions, albeit absolute trophic positions estimated by this method were lower than expected. This study reinforces the importance of considering isotopic baseline variability for diet studies, and provides new insights into methods that can be applied to generate nitrogen isoscapes for worldwide comparisons of top predators in marine ecosystems.

Regional pattern of snow characteristics around Antarctic Lake Vostok

NASA Astrophysics Data System (ADS)

Vladimirova, Diana; Ekaykin, Alexey; Popov, Sergey; Shibaev, Yuriy; Kozachek, Anna; Lipenkov, Vladimir

2015-04-01

Since 1998 Russian Antarctic Expedition has organized several scientific traverses in the region of subglacial Lake Vostok mainly devoted to the radar echo and seismic sounding of the glacier and water (the results have been published elsewhere). Along with the geophysical studies, a number of glaciological investigations have been carried out: snow pit digging, installation of accumulation stakes, snow sampling to study the stable water isotope content. Here we for the first time present a synthesis of these works and demonstrate a series of maps that characterize the snow density, isotope content and accumulation rate the studied region. A general tendency of the snow accumulation rate and isotope content is a significant increase from south (south-west) to north (north-east) from 35 to 23 mm w.e. per year and from -53,3 ‰ to -57,3 ‰ for delta oxygen-18 respectively, which likely reflects the continental-scale pattern, i.e., increase from inland to the coast. Deuterium excess varies from 11,7 ‰ to 16,3 ‰ is negatively correlated with the isotope content, which is typical for central Antarctica. The snow density demonstrate different pattern: higher values offshore the lake (up to 0,356 g/cm^3), and lower values within the lake's shoreline (lower limit is 0,328 g/cm^3). We suggest that this is related to the katabatic wind activity: very flat nearly horizontal surface of the glacier above the lake is not favorable for the strong winds, which leads to lower surface snow density. Superimposed on the main trend is the regional pattern, namely, curved contour lines in the middle part of the lake. We suggest that it may be related to the local anomalies of the snow drift by wind. Indeed, on the satellite images of the lake one can easily see a snowdrift stretching from the lake's western shore downwind in the middle part of the lake. The isolines of delta oxygen-18 and deuterium excess become perpendicular to each other in the north part of the lake which also could be related to wind activity and different time of exposition snow on the surface which potentially leads to changing in d-excess and water isotopes ratio relation. Another interesting feature is the minimum values of snow accumulation rate and isotope content to the south-east from Vostok station. Before present, the Vostok's close vicinity was the record-holder, but now it is obvious that the pole of the lowest values of these parameters is somewhere else. This finding may be important in terms of the search of the oldest ice in frames of the IPICS "1.5Ma" project.

Changes in fish diets and food web mercury bioaccumulation induced by an invasive planktivorous fish

USGS Publications Warehouse

Eagles-Smith, Collin A.; Suchanek, Thomas H.; Colwell, Arthur E.; Anderson, Norman L.; Moyle, Peter B.

2008-01-01

The invasion, boom, collapse, and reestablishment of a population of the planktivorous threadfin shad in Clear Lake, California, USA, were documented over a 20-year period, as were the effects of changing shad populations on diet and mercury (Hg) bioaccumulation in nearshore fishes. Threadfin shad competitively displaced other planktivorous fish in the lake, such as inland silversides, young-of-year (YOY) largemouth bass, and YOY bluegill, by reducing zooplankton abundance. As a result, all three species shifted from a diet that was dominated by zooplankton to one that was almost entirely zoobenthos. Stable carbon isotopes corroborated this pattern with each species becoming enriched in δ13C, which is elevated in benthic vs. pelagic organisms. Concomitant with these changes, Hg concentrations increased by ∼50% in all three species. In contrast, obligate benthivores such as prickly sculpin showed no relationship between diet or δ13C and the presence of threadfin shad, suggesting that effects of the shad were not strongly linked to the benthic fish community. There were also no changes in Hg concentrations of prickly sculpin. The temporary extirpation of threadfin shad from the lake resulted in zooplankton densities, foraging patterns, isotope ratios, and Hg concentrations in pelagic fishes returning to pre-shad values. These results indicate that even transient perturbations of the structure of freshwater food webs can result in significant alterations in the bioaccumulation of Hg and that food webs in lakes can be highly resilient.

Assessing the groundwater fortunes of aquifers in the White Volta Basin, Ghana: An application of numerical groundwater flow modeling and isotopic studies

NASA Astrophysics Data System (ADS)

Oteng, F. M.; Yidana, S. M.; Alo, C. A.

2012-12-01

Effective development and informed management of groundwater resources represent a critical opportunity for improved rural water supply in Ghana and enhanced livelihoods particularly in the northern part of the White Volta Basin, a region already prone to a myriad of water-related infirmities. If adequately developed, the resource will form a sufficient buffer against the effects of climate change/variability and foster food security and sustainable livelihoods among the largely peasant communities in the region. This research presents the results of a preliminary assessment of the hydrogeological conditions and recharge regimes of the aquifers in the Northern parts of the White Volta Basin, Ghana. Results of estimates of groundwater recharge through the conventional isotopic and mass balance techniques are presented. Details of the groundwater flow pattern and preliminary delineation of local and regional groundwater recharge areas are presented from initial simulations of the hydrogeological system with a robust groundwater flow simulation code, MODFLOW, in the Groundwater Modeling System, GMS, version 7.1. The stream flow and evapotranspiration components of the program were activated to incorporate surface flow processes, so that the resulting model represents the conditions of the entire hydrological system. The results of this study form a platform for detailed numerical assessment of the conditions of the aquifers in the area under transient conditions of fluctuating rainfall patterns in the face of climate change/variability.

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI-two types of X grains

NASA Astrophysics Data System (ADS)

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; Pellin, Michael J.; Rost, Detlef; Savina, Michael R.; Jadhav, Manavi; Kelly, Christopher H.; Gyngard, Frank; Hoppe, Peter; Dauphas, Nicolas

2018-01-01

We used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grains was fortuitous, because only ∼1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. While one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.

Effects of must concentration techniques on wine isotopic parameters.

PubMed

Guyon, Francois; Douet, Christine; Colas, Sebastien; Salagoïty, Marie-Hélène; Medina, Bernard

2006-12-27

Despite the robustness of isotopic methods applied in the field of wine control, isotopic values can be slightly influenced by enological practices. For this reason, must concentration technique effects on wine isotopic parameters were studied. The two studied concentration techniques were reverse osmosis (RO) and high-vacuum evaporation (HVE). Samples (must and extracted water) have been collected in various French vineyards. Musts were microfermented at the laboratory, and isotope parameters were determined on the obtained wine. Deuterium and carbon-13 isotope ratios were studied on distilled ethanol by nuclear magnetic resonance (NMR) and isotope ratio mass spectrometry (IRMS), respectively. The oxygen-18 ratio was determined on extracted and wine water using IRMS apparatus. The study showed that the RO technique has a very low effect on isotopic parameters, indicating that this concentration technique does not create any isotopic fractionation, neither at sugar level nor at water level. The effect is notable for must submitted to HVE concentration: water evaporation leads to a modification of the oxygen-18 ratio of the must and, as a consequence, ethanol deuterium concentration is also modified.

Mesophyll conductance and leaf carbon isotope composition of two high elevation conifers along an altitudinal gradient

NASA Astrophysics Data System (ADS)

Guo, J.; Beverly, D.; Cook, C.; Ewers, B.; Williams, D. G.

2016-12-01

Carbon isotope ratio values (δ13C) of conifer leaf material generally increases with elevation, potentially reflecting decreases in the leaf internal to ambient CO2 concentration ratio (Ci/Ca) during photosynthesis. Reduced stomatal conductance or increased carboxylation capacity with increasing elevation could account for these patterns. But some studies reported conifers δ13C increased with altitude consistently, but Ci/Ca did not significantly decrease and leaf nitrogen content remained constant with increasing of altitude in Central Rockies. Variation in leaf mesophyll conductance to CO2 diffusion, which influences leaf δ13C independently of effects related to stomatal conductance and carboxylation demand, might reconcile these conflicting observations. Leaf mass per unit area (LMA) increases with altitude and often correlates with δ13C and mesophyll conductance. Therefore, we hypothesized that increases in δ13C of conifers with altitude are controlled mainly by changes in mesophyll conductance. To test this hypothesis, leaf δ13C, photosynthetic capacity, leaf nitrogen content, LMA, and mesophyll conductance were determined on leaves of two dominant conifers (Pinus contorta and Picea engelmannii) along a 90-km transect in SE Wyoming at altitudes ranging from 2400 to 3200 m above sea level. Mesophyll conductance was determined by on-line 13C discrimination using isotope laser spectroscopy. We expected to observe relatively small differences in stomatal conductance and decreases in mesophyll conductance from lower and higher altitude sites. Such a pattern would have important implications for how differences in leaf δ13C values across altitude are interpreted in relation to forest water use and productivity from scaling of leaf-level water-use efficiency.

Mesoarchean melting and Neoarchean to Paleoproterozoic metasomatism during the formation of the cratonic mantle keel beneath West Greenland

NASA Astrophysics Data System (ADS)

van Acken, D.; Luguet, A.; Pearson, D. G.; Nowell, G. M.; Fonseca, R. O. C.; Nagel, T. J.; Schulz, T.

2017-04-01

Highly siderophile element (HSE) concentration and 187Os/188Os isotopic heterogeneity has been observed on various scales in the Earth's mantle. Interaction of residual mantle peridotite with infiltrating melts has been suggested to overprint primary bulk rock HSE signatures originating from partial melting, contributing to the heterogeneity seen in the global peridotite database. Here we present a detailed study of harzburgitic xenolith 474527 from the Kangerlussuaq suite, West Greenland, coupling the Re-Os isotope geochemistry with petrography of both base metal sulfides (BMS) and silicates to assess the impact of overprint induced by melt-rock reaction on the Re-Os isotope system. Garnet harzburgite sample 474527 shows considerable heterogeneity in the composition of its major phases, most notably olivine and Cr-rich garnet, suggesting formation through multiple stages of partial melting and subsequent metasomatic events. The major BMS phases show a fairly homogeneous pentlandite-rich composition typical for BMS formed via metasomatic reaction, whereas the 187Os/188Os compositions determined for 17 of these BMS are extremely heterogeneous ranging between 0.1037 and 0.1981. Analyses by LA-ICP-MS reveal at least two populations of BMS grains characterized by contrasting HSE patterns. One type of pattern is strongly enriched in the more compatible HSE Os, Ir, and Ru over the typically incompatible Pt, Pd, and Re, while the other type shows moderate enrichment of the more incompatible HSE and has overall lower compatible HSE/incompatible HSE composition. The small-scale heterogeneity observed in these BMS highlights the need for caution when utilizing the Re-Os system to date mantle events, as even depleted harzburgite samples such as 474527 are likely to have experienced a complex history of metasomatic overprinting, with uncertain effects on the HSE.

Carbonic Anhydrase, Calcification Dynamics and Stable Isotope Vital Effects: Deep Sea Corals and Beyond

NASA Astrophysics Data System (ADS)

Chen, S.; Gagnon, A. C.; Adkins, J. F.

2017-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Spatial and Temporal Patterns In Ecohydrological Separation

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.

2017-12-01

The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our results show that (1) diffusive isotopic fractionations depend on the direction of diffusion in composition space, (2) diffusive isotopic fractionations scale with effective binary diffusion coefficient, as previously noted by Watkins et al. (2011), (3) self-diffusion is not decoupled from chemical diffusion, (4) self diffusion can be faster than or slower than chemical diffusion and (5) off-diagonal terms in the chemical diffusion matrix have isotopic mass-dependence. The results imply that relatively large isotopic fractionations can be generated by multicomponent diffusion even in the absence of large concentration gradients of the diffusing element. The new formulations for isotope diffusion can be tested with further experimentation and provide an improved framework for interpreting mass-dependent isotopic variations in natural liquids.

Automatic measurements and computations for radiochemical analyses

USGS Publications Warehouse

Rosholt, J.N.; Dooley, J.R.

1960-01-01

In natural radioactive sources the most important radioactive daughter products useful for geochemical studies are protactinium-231, the alpha-emitting thorium isotopes, and the radium isotopes. To resolve the abundances of these thorium and radium isotopes by their characteristic decay and growth patterns, a large number of repeated alpha activity measurements on the two chemically separated elements were made over extended periods of time. Alpha scintillation counting with automatic measurements and sample changing is used to obtain the basic count data. Generation of the required theoretical decay and growth functions, varying with time, and the least squares solution of the overdetermined simultaneous count rate equations are done with a digital computer. Examples of the complex count rate equations which may be solved and results of a natural sample containing four ??-emitting isotopes of thorium are illustrated. These methods facilitate the determination of the radioactive sources on the large scale required for many geochemical investigations.

Mixing ratio and carbon isotopic composition investigation of atmospheric CO2 in Beijing, China.

PubMed

Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin

2016-01-01

The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ(13)C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ(13)C and the isotopic composition of source CO2 (δ(13)CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ(13)C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ(13)C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83±14.11% and 86.84±12.27% and that natural gas had average contributions of 16.17±14.11% and 13.16±12.27%, respectively. The δ(13)C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ(13)C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing. Copyright © 2015 Elsevier B.V. All rights reserved.

Triple-element compound-specific stable isotope analysis of 1,2-dichloroethane for characterization of the underlying dehalogenation reaction in two Dehalococcoides mccartyi strains.

PubMed

Franke, Steffi; Lihl, Christina; Renpenning, Julian; Elsner, Martin; Nijenhuis, Ivonne

2017-12-01

Chlorinated ethanes belong to the most common groundwater and soil contaminants. Of these, 1,2-dichloroethane (1,2-DCA) is a man-made, persistent and toxic contaminant, released due to improper waste treatment at versatile production sites. This study investigated the anaerobic transformation of 1,2-DCA by Dehalococcoides mccartyi strain 195 and strain BTF08 using triple-element compound-specific stable isotope analysis of carbon, chlorine and hydrogen for the first time. Isotope fractionation patterns for carbon (εCBTF08 = -28.4 ± 3.7‰; εC195 = -30.9 ± 3.6‰) and chlorine (εClBTF08 = -4.6 ± 0.7‰; εCl195 = -4.2 ± 0.5‰) within both investigated D. mccartyi strains, as well as the dual-element analysis (ΛBTF08 = 6.9 ± 1.2; Λ195 = 7.1 ± 0.2), supported identical reaction mechanisms for dehalogenation of 1,2-DCA. Hydrogen isotope fractionation analysis revealed dihaloelimination as prevalent reaction mechanism. Vinyl chloride as major intermediate could be excluded by performing the experiment in deuterated aqueous media. Furthermore, evaluation of the derived apparent kinetic isotope effects (AKIECBTF08 = 1.029/AKIEC195 = 1.031; AKIEClBTF08 = 1.005/AKIECl195 = 1.004) pointed towards simultaneous abstraction of both involved chlorine-substituents in a concerted matter. It was shown that D. mccartyi strain BTF08 and strain 195 are capable of complete, direct dihaloelimination of 1,2-DCA to ethene. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Mixing ratio and carbon isotopic composition investigation of atmospheric CO2 in Beijing, China

NASA Astrophysics Data System (ADS)

Pang, J.; Wen, X.; Sun, X.

2016-12-01

The stable isotope composition of atmospheric CO2 can be used as a tracer in the study of urban carbon cycles, which are affected by anthropogenic and biogenic CO2 components. Continuous measurements of the mixing ratio and δ13C of atmospheric CO2 were conducted in Beijing from Nov. 15, 2012 to Mar. 8, 2014 including two heating seasons and a vegetative season. Both δ13C and the isotopic composition of source CO2 (δ13CS) were depleted in the heating seasons and enriched in the vegetative season. The diurnal variations in the CO2 mixing ratio and δ13C contained two peaks in the heating season, which are due to the effects of morning rush hour traffic. Seasonal and diurnal patterns of the CO2 mixing ratio and δ13C were affected by anthropogenic emissions and biogenic activity. Assuming that the primary CO2 sources at night (22:00-04:00) were coal and natural gas combustion during heating seasons I and II, an isotopic mass balance analysis indicated that coal combustion had average contributions of 83.83 ± 14.11% and 86.84 ± 12.27% and that natural gas had average contributions of 16.17 ± 14.11% and 13.16 ± 12.27%, respectively. The δ13C of background CO2 in air was the main error source in the isotopic mass balance model. Both the mixing ratio and δ13C of atmospheric CO2 had significant linear relationships with the air quality index (AQI) and can be used to indicate local air pollution conditions. Energy structure optimization, for example, reducing coal consumption, will improve the local air conditions in Beijing.

Fractionation of Hydrogen Isotopes by Sulfate- and Nitrate-Reducing Bacteria.

PubMed

Osburn, Magdalena R; Dawson, Katherine S; Fogel, Marilyn L; Sessions, Alex L

2016-01-01

Hydrogen atoms from water and food are incorporated into biomass during cellular metabolism and biosynthesis, fractionating the isotopes of hydrogen-protium and deuterium-that are recorded in biomolecules. While these fractionations are often relatively constant in plants, large variations in the magnitude of fractionation are observed for many heterotrophic microbes utilizing different central metabolic pathways. The correlation between metabolism and lipid δ(2)H provides a potential basis for reconstructing environmental and ecological parameters, but the calibration dataset has thus far been limited mainly to aerobes. Here we report on the hydrogen isotopic fractionations of lipids produced by nitrate-respiring and sulfate-reducing bacteria. We observe only small differences in fractionation between oxygen- and nitrate-respiring growth conditions, with a typical pattern of variation between substrates that is broadly consistent with previously described trends. In contrast, fractionation by sulfate-reducing bacteria does not vary significantly between different substrates, even when autotrophic and heterotrophic growth conditions are compared. This result is in marked contrast to previously published observations and has significant implications for the interpretation of environmental hydrogen isotope data. We evaluate these trends in light of metabolic gene content of each strain, growth rate, and potential flux and reservoir-size effects of cellular hydrogen, but find no single variable that can account for the differences between nitrate- and sulfate-respiring bacteria. The emerging picture of bacterial hydrogen isotope fractionation is therefore more complex than the simple correspondence between δ(2)H and metabolic pathway previously understood from aerobes. Despite the complexity, the large signals and rich variability of observed lipid δ(2)H suggest much potential as an environmental recorder of metabolism.

Introduction to Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

PubMed Central

Thiemens, Mark H.

2013-01-01

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented. PMID:24167299

Iron isotope fractionation among magnetite, pyrrhotite, chalcopyrite, rhyolite melt and aqueous fluid at magmatic-hydrothermal conditions

NASA Astrophysics Data System (ADS)

Bilenker, L. D.; Simon, A.; Lundstrom, C.; Gajos, N.

2012-12-01

Fractionation of non-traditional stable isotopes (NTSI) such as Fe in magmatic systems is a relatively understudied subject. The fractionation of Fe stable isotopes has been quantified in some natural igneous samples, but there is a paucity of experimental data that could provide further insight into the causative processes of the observed fractionation. Substantial experimental work has been performed at higher temperatures pertaining to the formation of chondrites and the Earth's core, but only a handful of studies have addressed crustal rocks. To fill this knowledge gap, we performed isothermal, isobaric experiments containing mineral (e.g., magnetite, Fe-sulfides) and fluid, or mineral, rhyolite melt, and fluid assemblages to quantify equilibrium fractionation factors (α). These data, to our knowledge, are the first data that quantify the effect of a fluid phase on iron isotope fractionation at conditions appropriate for evolving magmatic systems. Charges were run inside gold capsules held in a René-41 cold seal vessel, and heated to 400, 600, or 800°C at 150 MPa for mineral-fluid, and 800°C and 100 MPa for mineral-melt-fluid runs. Use of the René vessel fixed the fO2 at the NNO buffer, an oxidation state consistent with arc magmas. The isotopic compositions of the starting and quenched phases were obtained by using a Multi-Collector Plasma Mass Spectrometer (MC-ICP-MS). Equilibrium was assessed by performing time-series runs and the three-isotope method, used only once before in a similar Fe isotope study. Correlation between Fe isotope mass and oxidation state is also being explored. Magnetite-fluid results indicate enrichment of heavy Fe isotopes in the mineral relative to the fluid, consistent with measurements of felsic igneous rocks. Magnetite-melt-fluid relationships are also consistent with measurements of natural samples. In the latter assemblage, over the course of the run, the rhyolite melt becomes heavy relative to the fluid while magnetite takes on a heavier Fe isotope signature than the starting value. These data corroborate the hypothesis that fluid exsolution caused the isotopic patterns observed in highly-differentiated igneous rocks. Further, owing to the ubiquitous importance of melt degassing as a critical process for the formation of magmatic-hydrothermal ore deposits, these data may be potentially serve as an exploration tool. This work contributes to our overall understanding of igneous processes by elucidating the Fe isotope fingerprints observed in the field as well as develop the laboratory techniques needed to study NTSI fractionation in magmatic systems and build a reliable dataset for interpretation of natural systems.

Preliminary Earth System Modeling (cGENIE) of Paired Organic and Inorganic Carbon Isotope Records to Investigate Carbon Cycle Behavior During the Triassic-Jurassic Transition

NASA Astrophysics Data System (ADS)

Yager, J. A.; Stellmann, J. L.; West, A. J.; Corsetti, F. A.; Berelson, W.; Bottjer, D. J.; Rosas, S.

2016-12-01

The stable C isotope composition of marine carbonate and organic C yields information regarding major changes in global carbon cycling over geologic time. Excursions from baseline C isotope compositions during the Late Triassic and early Jurassic coincide with the end-Triassic mass extinction. Much remains to be understood about the global extent of these excursions, and about their causes. Here, we use observations from a record from Northern Peru (Levanto) to generate hypotheses concerning C cycle changes, focusing on comparison to other sections spanning the Triassic-Jurassic boundary. Our observations include a decoupling between organic and inorganic C isotopes in some records, broad similarities in the pattern of excursions between sections, and a potential offset between the major ocean basins (Tethys and Panthalassa) in both inorganic and organic C isotope records. We are currently adapting a spatially resolved Earth System Model (cGENIE) for this time period with the goal of using this model to explore possible mechanistic causes of these observations, aiming to tie the C isotope records to changes in global carbon cycle dynamics at the time.

Chemical and isotopic evolution of a layered eastern U.S. snowpack and its relation to stream-water composition

USGS Publications Warehouse

Shanley, J.B.; Kendall, C.; Albert, M.R.; Hardy, J.P.

1995-01-01

The chemical, isotopic, and morphologic evolution of a layered snowpack was investigated during the winter of 1993-94 at Sleepers River Research Watershed in Danville, Vermont. The snowpack was monitored at two small basins: a forested basin at 525 m elevation, and an agricultural basin at 292 m elevation. At each site, the snowpack morphology was characterized and individual layers were sampled seven times during the season. Nitrate and 8d18O profiles in the snowpack remained relatively stable until peak accumulation in mid-March, except near the snow surface, where rain-on-snow events caused water and nitrate movement down to impeding ice layers. Subsequently, water and nitrate moved more readily through the ripening snowpack. As the snowpack evolved, combined processes of preferential ion elution, isotopic fractionation, and infiltration of isotopically heavy rainfall caused the pack to become depleted in solutes and isotopically enriched. The release of nitrate and isotopically depleted water was reflected in patterns of nitrate concentrations and ??18O of meltwater and stream water. Results supported data from the previous year which suggested that streamflow in the forested basin during snowmelt was dominated by groundwater discharge.

Stable isotopic records of bleaching and endolithic algae blooms in the skeleton of the boulder forming coral Montastraea faveolata

NASA Astrophysics Data System (ADS)

Hartmann, A. C.; Carilli, J. E.; Norris, R. D.; Charles, C. D.; Deheyn, D. D.

2010-12-01

Within boulder forming corals, fixation of dissolved inorganic carbon is performed by symbiotic dinoflagellates within the coral tissue and, to a lesser extent, endolithic algae within the coral skeleton. Endolithic algae produce distinctive green bands in the coral skeleton, and their origin may be related to periods of coral bleaching due to complete loss of dinoflagellate symbionts or “paling” in which symbiont populations are patchily reduced in coral tissue. Stable carbon isotopes were analyzed in coral skeletons across a known bleaching event and 12 blooms of endolithic algae to determine whether either of these types of changes in photosynthesis had a clear isotopic signature. Stable carbon isotopes tended to be enriched in the coral skeleton during the initiation of endolith blooms, consistent with enhanced photosynthesis by endoliths. In contrast, there were no consistent δ13C patterns directly associated with bleaching, suggesting that there is no unique isotopic signature of bleaching. On the other hand, isotopic values after bleaching were lighter 92% of the time when compared to the bleaching interval. This marked drop in skeletal δ13C may reflect increased kinetic fractionation and slow symbiont recolonization for several years after bleaching.

Extreme Monsoon Rainfall Signatures Preserved in the Invasive Terrestrial Gastropod Lissachatina fulica

NASA Astrophysics Data System (ADS)

Ghosh, Prosenjit; Rangarajan, Ravi; Thirumalai, Kaustubh; Naggs, Fred

2017-11-01

Indian summer monsoon (ISM) rainfall lasts for a period of 4 months with large variations recorded in terms of rainfall intensity during its period between June and September. Proxy reconstructions of past ISM rainfall variability are required due to the paucity of long instrumental records. However, reconstructing subseasonal rainfall is extremely difficult using conventional hydroclimate proxies due to inadequate sample resolution. Here, we demonstrate the utility of the stable oxygen isotope composition of gastropod shells in reconstructing past rainfall on subseasonal timescales. We present a comparative isotopic study on present day rainwater and stable isotope ratios of precipitate found in the incremental growth bands of giant African land snail Lissachatina fulica (Bowdich) from modern day (2009) and in the historical past (1918). Isotopic signatures present in the growth bands allowed for the identification of ISM rainfall variability in terms of its active and dry spells in the modern as well as past gastropod record. Our results demonstrate the utility of gastropod growth band stable isotope ratios in semiquantitative reconstructions of seasonal rainfall patterns. High resolution climate records extracted from gastropod growth band stable isotopes (museum and archived specimens) can expand the scope for understanding past subseasonal-to-seasonal climate variability.

A terrestrial record of water isotopes reveals the Eocene-Oligoene transition in southern Argentina

NASA Astrophysics Data System (ADS)

Auerbach, D. J.; Hren, M. T.; Pacini, A.; Breen, P.

2015-12-01

The Eocene-Oligocene transition (EOT) from a greenhouse to icehouse climate state and the onset of large-scale Antarctic glaciation has been widely documented geochemically in both the marine realm (e.g., Zachos et al., 2001) and the terrestrial realm (e.g., Zanazzi et al., 2007). However, existing terrestrial records from Patagonia show negligible change in the water isotope record (Kohn et al., 2010; Kohn et al., 2015), despite the proximity of South America to Antarctica. Analyses of volcanic glasses from the Vera Member of the Sarmiento Formation in the well-dated (Dunn et al., 2013) sedimentary section at Gran Barranca allow us to reconstruct water isotope record in central Patagonia during the EOT. These data show a drop in precipitation δD of ~20‰ over ~100-200 kyr followed by a recovery of ~15‰ over the next 0.5-1.0 Myr. This pattern of a rapid shift and a more gradual recovery fits the shape and time scale of the marine record, although the magnitude of the isotopic excursion is different. Such a record could potentially be explained by large changes in source (seawater) δD, temperature, paleolatitude, or orographic effect. As the latter two possibilities are geologically improbable, these data suggest large, rapid climatic changes accompanying the EOT in Patagonia. If corroborated by other data, this would suggest that the evolution of hypsodonty in grazers in Patagonia was not driven by or sensitive to the global climate.

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere.

PubMed

Gorski, Galen; Strong, Courtenay; Good, Stephen P; Bares, Ryan; Ehleringer, James R; Bowen, Gabriel J

2015-03-17

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. We show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration of water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. Our findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry.

Chlorine isotopic composition of perchlorate in human urine as a means of distinguishing among exposure sources.

PubMed

Poghosyan, Armen; Morel-Espinosa, Maria; Valentin-Blasini, Liza; Blount, Benjamin C; Ferreccio, Catterina; Steinmaus, Craig M; Sturchio, Neil C

2016-01-01

Perchlorate (ClO4(-)) is a ubiquitous environmental contaminant with high human exposure potential. Natural perchlorate forms in the atmosphere from where it deposits onto the surface of Earth, whereas synthetic perchlorate is manufactured as an oxidant for industrial, aerospace, and military applications. Perchlorate exposure can potentially cause adverse health effects in humans by interfering with the production of thyroid hormones through competitively blocking iodide uptake. To control and reduce perchlorate exposure, the contributions of different sources of perchlorate exposure need to be quantified. Thus, we demonstrate a novel approach for determining the contribution of different perchlorate exposure sources by quantifying stable and radioactive chlorine isotopes of perchlorate extracted from composite urine samples from two distinct populations: one in Atlanta, USA and one in Taltal, Chile (Atacama region). Urinary perchlorate from the Atlanta region resembles indigenous natural perchlorate from the western USA (δ(37)Cl=+4.1±1.0‰; (36)Cl/Cl=1 811 (±136) × 10(-15)), and urinary perchlorate from the Taltal, Chile region is similar to natural perchlorate in nitrate salt deposits from the Atacama Desert of northern Chile (δ(37)Cl=-11.0±1.0‰; (36)Cl/Cl=254 (±40) × 10(-15)). Neither urinary perchlorate resembled the isotopic pattern found in synthetic perchlorate. These results indicate that natural perchlorate of regional provenance is the dominant exposure source for the two sample populations, and that chlorine isotope ratios provide a robust tool for elucidating perchlorate exposure pathways.

Vapor hydrogen and oxygen isotopes reflect water of combustion in the urban atmosphere

PubMed Central

Gorski, Galen; Strong, Courtenay; Good, Stephen P.; Bares, Ryan; Ehleringer, James R.; Bowen, Gabriel J.

2015-01-01

Anthropogenic modification of the water cycle involves a diversity of processes, many of which have been studied intensively using models and observations. Effective tools for measuring the contribution and fate of combustion-derived water vapor in the atmosphere are lacking, however, and this flux has received relatively little attention. We provide theoretical estimates and a first set of measurements demonstrating that water of combustion is characterized by a distinctive combination of H and O isotope ratios. We show that during periods of relatively low humidity and/or atmospheric stagnation, this isotopic signature can be used to quantify the concentration of water of combustion in the atmospheric boundary layer over Salt Lake City. Combustion-derived vapor concentrations vary between periods of atmospheric stratification and mixing, both on multiday and diurnal timescales, and respond over periods of hours to variations in surface emissions. Our estimates suggest that up to 13% of the boundary layer vapor during the period of study was derived from combustion sources, and both the temporal pattern and magnitude of this contribution were closely reproduced by an independent atmospheric model forced with a fossil fuel emissions data product. Our findings suggest potential for water vapor isotope ratio measurements to be used in conjunction with other tracers to refine the apportionment of urban emissions, and imply that water vapor emissions associated with combustion may be a significant component of the water budget of the urban boundary layer, with potential implications for urban climate, ecohydrology, and photochemistry. PMID:25733906

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Linking low-level stable isotope fractionation to expression of the cytochrome P450 monooxygenase-encoding ethB gene for elucidation of methyl tert-butyl ether biodegradation in aerated treatment pond systems.

PubMed

Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H

2011-02-01

Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ε(C)] of -0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ε(H)]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ε(C) of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ε(H) of -5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem.

Linking Low-Level Stable Isotope Fractionation to Expression of the Cytochrome P450 Monooxygenase-Encoding ethB Gene for Elucidation of Methyl tert-Butyl Ether Biodegradation in Aerated Treatment Pond Systems▿ †

PubMed Central

Jechalke, Sven; Rosell, Mònica; Martínez-Lavanchy, Paula M.; Pérez-Leiva, Paola; Rohwerder, Thore; Vogt, Carsten; Richnow, Hans H.

2011-01-01

Multidimensional compound-specific stable isotope analysis (CSIA) was applied in combination with RNA-based molecular tools to characterize methyl tertiary (tert-) butyl ether (MTBE) degradation mechanisms occurring in biofilms in an aerated treatment pond used for remediation of MTBE-contaminated groundwater. The main pathway for MTBE oxidation was elucidated by linking the low-level stable isotope fractionation (mean carbon isotopic enrichment factor [ɛC] of −0.37‰ ± 0.05‰ and no significant hydrogen isotopic enrichment factor [ɛH]) observed in microcosm experiments to expression of the ethB gene encoding a cytochrome P450 monooxygenase able to catalyze the oxidation of MTBE in biofilm samples both from the microcosms and directly from the ponds. 16S rRNA-specific primers revealed the presence of a sequence 100% identical to that of Methylibium petroleiphilum PM1, a well-characterized MTBE degrader. However, neither expression of the mdpA genes encoding the alkane hydroxylase-like enzyme responsible for MTBE oxidation in this strain nor the related MTBE isotope fractionation pattern produced by PM1 could be detected, suggesting that this enzyme was not active in this system. Additionally, observed low inverse fractionation of carbon (ɛC of +0.11‰ ± 0.03‰) and low fractionation of hydrogen (ɛH of −5‰ ± 1‰) in laboratory experiments simulating MTBE stripping from an open surface water body suggest that the application of CSIA in field investigations to detect biodegradation may lead to false-negative results when volatilization effects coincide with the activity of low-fractionating enzymes. As shown in this study, complementary examination of expression of specific catabolic genes can be used as additional direct evidence for microbial degradation activity and may overcome this problem. PMID:21148686

Stable Isotope Tracking of Endangered Sea Turtles: Validation with Satellite Telemetry and δ15N Analysis of Amino Acids

PubMed Central

Seminoff, Jeffrey A.; Benson, Scott R.; Arthur, Karen E.; Eguchi, Tomoharu; Dutton, Peter H.; Tapilatu, Ricardo F.; Popp, Brian N.

2012-01-01

Effective conservation strategies for highly migratory species must incorporate information about long-distance movements and locations of high-use foraging areas. However, the inherent challenges of directly monitoring these factors call for creative research approaches and innovative application of existing tools. Highly migratory marine species, such as marine turtles, regularly travel hundreds or thousands of kilometers between breeding and feeding areas, but identification of migratory routes and habitat use patterns remains elusive. Here we use satellite telemetry in combination with compound-specific isotope analysis of amino acids to confirm that insights from bulk tissue stable isotope analysis can reveal divergent migratory strategies and within-population segregation of foraging groups of critically endangered leatherback sea turtles (Dermochelys coriacea) across the Pacific Ocean. Among the 78 turtles studied, we found a distinct dichotomy in δ15N values of bulk skin, with distinct “low δ15N” and “high δ15N” groups. δ15N analysis of amino acids confirmed that this disparity resulted from isotopic differences at the base of the food chain and not from differences in trophic position between the two groups. Satellite tracking of 13 individuals indicated that their bulk skin δ15N value was linked to the particular foraging region of each turtle. These findings confirm that prevailing marine isoscapes of foraging areas can be reflected in the isotopic compositions of marine turtle body tissues sampled at nesting beaches. We use a Bayesian mixture model to show that between 82 and 100% of the 78 skin-sampled turtles could be assigned with confidence to either the eastern Pacific or western Pacific, with 33 to 66% of all turtles foraging in the eastern Pacific. Our forensic approach validates the use of stable isotopes to depict leatherback turtle movements over broad spatial ranges and is timely for establishing wise conservation efforts in light of this species’ imminent risk of extinction in the Pacific. PMID:22666354

Nitrogen sources and cycling revealed by dual isotopes of nitrate in a complex urbanized environment.

PubMed

Archana, Anand; Thibodeau, Benoit; Geeraert, Naomi; Xu, Min Nina; Kao, Shuh-Ji; Baker, David M

2018-06-05

Elevated nutrient inputs have led to increased eutrophication in coastal marine ecosystems worldwide. An understanding of the relative contribution of different nutrient sources is imperative for effective water quality management. Stable isotope values of nitrate (δ 15 N NO3- , δ 18 O NO3- ) can complement conventional water quality monitoring programs to help differentiate natural sources of NO 3 - from anthropogenic inputs and estimate the processes involved in N cycling within an ecosystem. We measured nutrient concentrations, δ 15 N NO3- , and δ 18 O NO3- in 76 locations along a salinity gradient from the lower end of the Pearl River Estuary, one of China's largest rivers discharging into the South China Sea, towards the open ocean. NO 3 - concentrations decreased with increasing salinity, indicative of conservative mixing of eutrophic freshwater and oligotrophic seawater. However, our data did not follow conservative mixing patterns. At salinities <20 psu, samples exhibited decreasing NO 3 - concentrations with almost unchanged NO 3 - isotope values, indicating simple dilution. At salinities >20 psu, NO 3 - concentrations decreased, while dual NO 3 - isotopes increased, suggesting mixing and/or other transformation processes. Our analysis yielded mean estimates for isotope enrichment factors ( 15 ε = -2.02‰ and 18 ε = -3.37‰), Δ(15,18) = -5.5‰ and δ 15 N NO3- - δ 15 N NO2-  = 12.3‰. After consideration of potential alternative sources (sewage, atmospheric deposition and groundwater) we concluded that there are three plausible interpretations for deviations from conservative mixing behaviour (1) NO 3 - uptake by assimilation (2) in situ NO 3 - production (from fixation-derived nitrogen and nitrification of sewage-derived effluents) and (3) input of groundwater nitrate carrying a denitrification signal. Through this study, we propose a simple workflow that incorporates a synthesis of numerous isotope-based studies to constrain sources and behaviour of NO 3 - in urbanized marine environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Stable isotope tracking of endangered sea turtles: validation with satellite telemetry and δ15N analysis of amino acids.

PubMed

Seminoff, Jeffrey A; Benson, Scott R; Arthur, Karen E; Eguchi, Tomoharu; Dutton, Peter H; Tapilatu, Ricardo F; Popp, Brian N

2012-01-01

Effective conservation strategies for highly migratory species must incorporate information about long-distance movements and locations of high-use foraging areas. However, the inherent challenges of directly monitoring these factors call for creative research approaches and innovative application of existing tools. Highly migratory marine species, such as marine turtles, regularly travel hundreds or thousands of kilometers between breeding and feeding areas, but identification of migratory routes and habitat use patterns remains elusive. Here we use satellite telemetry in combination with compound-specific isotope analysis of amino acids to confirm that insights from bulk tissue stable isotope analysis can reveal divergent migratory strategies and within-population segregation of foraging groups of critically endangered leatherback sea turtles (Dermochelys coriacea) across the Pacific Ocean. Among the 78 turtles studied, we found a distinct dichotomy in δ(15)N values of bulk skin, with distinct "low δ(15)N" and "high δ(15)N" groups. δ(15)N analysis of amino acids confirmed that this disparity resulted from isotopic differences at the base of the food chain and not from differences in trophic position between the two groups. Satellite tracking of 13 individuals indicated that their bulk skin δ(15)N value was linked to the particular foraging region of each turtle. These findings confirm that prevailing marine isoscapes of foraging areas can be reflected in the isotopic compositions of marine turtle body tissues sampled at nesting beaches. We use a Bayesian mixture model to show that between 82 and 100% of the 78 skin-sampled turtles could be assigned with confidence to either the eastern Pacific or western Pacific, with 33 to 66% of all turtles foraging in the eastern Pacific. Our forensic approach validates the use of stable isotopes to depict leatherback turtle movements over broad spatial ranges and is timely for establishing wise conservation efforts in light of this species' imminent risk of extinction in the Pacific.

Understanding key drivers controlling daily stable isotope variations in precipitation of Costa Rica, Central America

NASA Astrophysics Data System (ADS)

Sanchez-Murillo, Ricardo; Welsh, Kristin; Birkel, Christian; Esquivel-Hernández, Germain; Corrales-Salazar, Jose; Boll, Jan; Brooks, Erin; Roupsard, Olivier; Katchan, Irina; Arce-Mesén, Rafael; Soulsby, Chris; Araguás-Araguás, Luis

2015-04-01

Costa Rica is located on the Central American Isthmus, which receives direct moisture inputs from the Caribbean Sea and the Pacific Ocean. The relatively narrow, but high relief Central American land bridge is characterized by unique mountainous and lowland microclimates. However, only limited knowledge exists about the impact of relief and regional atmospheric circulation patterns on precipitation origin, transport, and isotopic composition in this tropical region. Therefore, the main scope of this study is to identify the key drivers controlling variations in meteoric waters of Costa Rica using stable isotopes based on daily sample collection for the year 2013. The monitoring sites comprise three strategic locations across Costa Rica: Heredia (Central Valley), Turrialba (Caribbean slope), and Caño Seco (South Pacific slope). Sporadic dry season rain is mostly related to isolated enriched events ranging from -5.8‰ d18O up to -0.9‰ d18O. By mid-May, the Intertropical Convergence Zone reaches Costa Rica resulting in a notable depletion in isotope ratios (up to -18.5‰ d18O). HYSPLIT back air mass trajectories indicate the strong influence on the origin and transport of precipitation of two main moisture transport mechanisms, the Caribbean Low Level Jet and the Colombian Low Level Jet as well as localized convection events. Multiple linear regression models constructed based on Random Forests of surface meteorological information and atmospheric sounding profiles suggest that Lifted Condensation Level and surface relative humidity are the main factors controlling isotopic variations. These findings diverge from the recognized 'amount effect' in monthly composite samples across the tropics. Understanding of stable isotope dynamics in tropical precipitation can be used to enhance catchment and groundwater modeling efforts in ungauged basins where scarcity of long-term monitoring data drastically limit current and future water resources management.

Application of sulphur isotope ratios to examine weaning patterns and freshwater fish consumption in Roman Oxfordshire, UK

NASA Astrophysics Data System (ADS)

Nehlich, Olaf; Fuller, Benjamin T.; Jay, Mandy; Mora, Alice; Nicholson, Rebecca A.; Smith, Colin I.; Richards, Michael P.

2011-09-01

This study investigates the application of sulphur isotope ratios (δ 34S) in combination with carbon (δ 13C) and nitrogen (δ 15N) ratios to understand the influence of environmental sulphur on the isotopic composition of archaeological human and faunal remains from Roman era sites in Oxfordshire, UK. Humans ( n = 83), terrestrial animals ( n = 11), and freshwater fish ( n = 5) were analysed for their isotope values from four locations in the Thames River Valley, and a broad range of δ 34S values were found. The δ 34S values from the terrestrial animals were highly variable (-13.6‰ to +0.5‰), but the δ 34S values of the fish were clustered and 34S-depleted (-20.9‰ to -17.3‰). The results of the faunal remains suggest that riverine sulphur influenced the terrestrial sulphur isotopic signatures. Terrestrial animals were possibly raised on the floodplains of the River Thames, where highly 34S-depleted sulphur influenced the soil. The humans show the largest range of δ 34S values (-18.8‰ to +9.6‰) from any archaeological context to date. No differences in δ 34S values were found between the males (-7.8 ± 6.0‰) and females (-5.3 ± 6.8‰), but the females had a linear correlation ( R2 = 0.71; p < 0.0001) between their δ 15N and δ 34S compositions. These δ 34S results suggest a greater dietary variability for the inhabitants of Roman Oxfordshire than previously thought, with some individuals eating solely terrestrial protein resources and others showing a diet almost exclusively based on freshwater protein such as fish. Such large dietary variability was not visible by analysing only the carbon and nitrogen isotope ratios, and this research represents the largest and most detailed application of δ 34S analysis to examine dietary practices (including breastfeeding and weaning patterns) during the Romano-British Period.

Hafnium isotope evidence for a transition in the dynamics of continental growth 3.2 Gyr ago.

PubMed

Næraa, T; Scherstén, A; Rosing, M T; Kemp, A I S; Hoffmann, J E; Kokfelt, T F; Whitehouse, M J

2012-05-30

Earth's lithosphere probably experienced an evolution towards the modern plate tectonic regime, owing to secular changes in mantle temperature. Radiogenic isotope variations are interpreted as evidence for the declining rates of continental crustal growth over time, with some estimates suggesting that over 70% of the present continental crustal reservoir was extracted by the end of the Archaean eon. Patterns of crustal growth and reworking in rocks younger than three billion years (Gyr) are thought to reflect the assembly and break-up of supercontinents by Wilson cycle processes and mark an important change in lithosphere dynamics. In southern West Greenland numerous studies have, however, argued for subduction settings and crust growth by arc accretion back to 3.8 Gyr ago, suggesting that modern-day tectonic regimes operated during the formation of the earliest crustal rock record. Here we report in situ uranium-lead, hafnium and oxygen isotope data from zircons of basement rocks in southern West Greenland across the critical time period during which modern-like tectonic regimes could have initiated. Our data show pronounced differences in the hafnium isotope-time patterns across this interval, requiring changes in the characteristics of the magmatic protolith. The observations suggest that 3.9-3.5-Gyr-old rocks differentiated from a >3.9-Gyr-old source reservoir with a chondritic to slightly depleted hafnium isotope composition. In contrast, rocks formed after 3.2 Gyr ago register the first additions of juvenile depleted material (that is, new mantle-derived crust) since 3.9 Gyr ago, and are characterized by striking shifts in hafnium isotope ratios similar to those shown by Phanerozoic subduction-related orogens. These data suggest a transitional period 3.5-3.2 Gyr ago from an ancient (3.9-3.5 Gyr old) crustal evolutionary regime unlike that of modern plate tectonics to a geodynamic setting after 3.2 Gyr ago that involved juvenile crust generation by plate tectonic processes.

Early mantle heterogeneities in the Réunion hotspot source inferred from highly siderophile elements in cumulate xenoliths

NASA Astrophysics Data System (ADS)

Peters, Bradley J.; Day, James M. D.; Taylor, Lawrence A.

2016-08-01

Ultramafic cumulate rocks form during intrusive crystallization of high-MgO magmas, incorporating relatively high abundances of compatible elements, including Cr and Ni, and high abundances of the highly siderophile elements (HSE: Os, Ir, Ru, Pt, Pd, Re). Here, we utilize a suite of cumulate xenoliths from Piton de la Fournaise, La Réunion (Indian Ocean), to examine the mantle source composition of the Réunion hotspot using HSE abundances and Os isotopes. Dunite and wherlite xenoliths and associated lavas from the Piton de la Fournaise volcanic complex span a range of MgO contents (46 to 7 wt.%), yet exhibit remarkably homogeneous 187Os/188Os (0.1324 ± 0.0014, 2σ), representing the Os-isotopic composition of Réunion hotspot primary melts. A significant fraction of the xenoliths also have primitive upper-mantle (PUM) normalized HSE patterns with elevated Ru and Pd (PUM-normalized Ru/Ir and Pd/Ir of 0.8-6.3 and 0.2-7.2, respectively). These patterns are not artifacts of alteration, fractional crystallization, or partial melting processes, but rather require a primary magma with similar relative enrichments. Some highly olivine-phyric (>40 modal percent olivine) Piton de la Fournaise lavas also preserve these relative Ru and Pd enrichments, while others preserve a pattern that is likely related to sulfur saturation in evolved melts. The estimate of HSE abundances in PUM indicates high Ru/Ir and Pd/Pt values relative to carbonaceous, ordinary and enstatite chondrite meteorite groups. Thus, the existence of cumulate rocks with even more fractionated HSE patterns relative to PUM suggests that the Réunion hotspot samples a yet unrecognized mantle source. The origin of fractionated HSE patterns in Réunion melts may arise from sampling of a mantle source that experienced limited late accretion (<0.2% by mass) compared with PUM (0.5-0.8%), possibly involving impactors that were distinct from present-day chondrites, or limited core-mantle interactions. Given the remarkably homogeneous Os, Pb, and noble-gas isotopic signatures of Réunion, which plot near the convergence point of isotopic data for many hotspots, such a conclusion provides evidence for an early differentiated and subsequently isolated mantle domain that may be partially sampled by some ocean island basalts.

Safety of stable isotope use.

PubMed

Koletzko, B; Sauerwald, T; Demmelmair, H

1997-08-01

The increased employment of stable isotope tracers for diagnostic and research purposes frequently raises questions on potential risks associated with their use, which is of particular importance in the paediatric age group. Biological effects and the potential of adverse events has been evaluated in a large number of animal and, in part, also human studies. Possible differences in physical, chemical and biochemical behaviour resulting in kinetic and thermodynamic isotope effects between stable isotopes of the same element are related to the relative differences in atomic weight. Deuterium (2H), which differs markedly in mass from the predominant hydrogen isotope 1H, may induce serious side-effects at high concentrations in body fluids. The threshold dose for the occurrence of side-effects lies well above the usual tracer dosages for clinical use. In contrast to deuterium, heavier stable isotopes such as 13C, 15N or 18O that differ relatively little in mass from the predominant isotopes such as 12C, does not show any adverse biological effects even at highest enrichments. The doses of stable isotope tracer substances that are used for clinical diagnostic and research purposes appear safe and without any adverse effects. Stable isotope tracers should only be used in children if the trace is safe at the doses applied, and tracer is chemically pure and stable. In the case of intravenous application, the tracer preparation must also be sterile and pyrogen free.

Stable carbon isotope fractionation in the search for life on early Mars

NASA Technical Reports Server (NTRS)

Rothschild, L. J.; Desmarais, D.

1989-01-01

The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

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.

Trace element profiles in modern horse molar enamel as tracers of seasonality: Evidence from micro-XRF, LA-ICP-MS and stable isotope analysis

NASA Astrophysics Data System (ADS)

de Winter, Niels; Goderis, Steven; van Malderen, Stijn; Vanhaecke, Frank; Claeys, Philippe

2016-04-01

A combination of laboratory micro-X-ray Fluorescence (μXRF) and stable carbon and oxygen isotope analysis shows that trace element profiles from modern horse molars reveal a seasonal pattern that co-varies with seasonality in the oxygen isotope records of enamel carbonate from the same teeth. A combination of six cheek teeth (premolars and molars) from the same individual yields a seasonal isotope and trace element record of approximately three years recorded during the growth of the molars. This record shows that reproducible measurements of various trace element ratios (e.g., Sr/Ca, Zn/Ca, Fe/Ca, K/Ca and S/Ca) lag the seasonal pattern in oxygen isotope records by 2-3 months. Laser Ablation-ICP-Mass Spectrometry (LA-ICP-MS) analysis on a cross-section of the first molar of the same individual is compared to the bench-top tube-excitation μXRF results to test the robustness of the measurements and to compare both methods. Furthermore, trace element (e.g. Sr, Zn, Mg & Ba) profiles perpendicular to the growth direction of the same tooth, as well as profiles parallel to the growth direction are measured with LA-ICP-MS and μXRF to study the internal distribution of trace element ratios in two dimensions. Results of this extensive complementary line-scanning procedure shows the robustness of state of the art laboratory micro-XRF scanning for the measurement of trace elements in bioapatite. The comparison highlights the advantages and disadvantages of both methods for trace element analysis and illustrates their complementarity. Results of internal variation within the teeth shed light on the origins of trace elements in mammal teeth and their potential use for paleo-environmental reconstruction.

Stable isotopes suggest differences in diet between historic and reintroduced Przewalskís horses in the Gobi desert

NASA Astrophysics Data System (ADS)

Burnik Šturm, Martina; Spasskaya, Natalia N.; Sablin, Mikhail V.; Voigt, Christian C.; Kaczensky, Petra

2016-04-01

In historic times, two wild equid species, the Przewalski᾽s horse (PH; Equus ferus przewalskii) and the Asiatic wild ass (khulan, KH; Equus hemionus), roamed the Eurasian steppes. By the end of the 1960s, PHs had been driven to extinction in the wild and the range of KHs became severely restricted to the least productive habitats. However, PHs survived in captivity and reintroductions since the 1990s have brought the species back to parts of its native range in Mongolia and northern China where they again overlap with KHs. Ecological research on PHs and KHs has increased in recent years, but very little information is available on the ecology of the original PHs prior to extinction in the wild. We applied stable isotope analysis (13C, 15N, and 2H) of segmentally cut tail hair of PHs and KHs, collected during expeditions in NW China and SW Mongolia in 1889-1899, to draw inferences about the species feeding ecology. We compared tail hair isotope patterns of historic individuals to those of their extant counterparts from the Mongolian Gobi. A previous study of isotopic tail hair signatures of extant PHs (N=6) and KHs (N=6) suggested species specific differences in diet, with PHs being year-round grazers, but KHs switching between being grazers in summer and mixed feeders in winter (Burnik Šturm et al., in prep.). The comparison of isotope patterns of extant with historic samples confirms diet seasonality in historic KHs (N=3), but detects the same seasonality in five out of six PHs, suggesting that historic PHs had a different isotopic dietary niche than extant PHs. While we are still unable to fully understand the underlying reasons for this change in PHs, our results clearly suggest that the isotopic dietary niche of PHs was wider in the past, suggesting a higher diet flexibility, and overlapped with that of KHs, suggesting a high competition potential over Gobi pastures between the two equid species in historic times. Reference: Burnik Šturm, M., Ganbaatar, O., Voigt, C.C., Kaczensky, P. Stable isotopes reveal differences in the feeding ecology of three sympatric equid species in Dzungarian Gobi, Mongolia (in prep.)

Isotope scattering and phonon thermal conductivity in light atom compounds: LiH and LiF

DOE PAGES

Lindsay, Lucas R.

2016-11-08

Engineered isotope variation is a pathway toward modulating lattice thermal conductivity (κ) of a material through changes in phonon-isotope scattering. The effects of isotope variation on intrinsic thermal resistance is little explored, as varying isotopes have relatively small differences in mass and thus do not affect bulk phonon dispersions. However, for light elements isotope mass variation can be relatively large (e.g., hydrogen and deuterium). Using a first principles Peierls-Boltzmann transport equation approach the effects of isotope variance on lattice thermal transport in ultra-low-mass compound materials LiH and LiF are characterized. The isotope mass variance modifies the intrinsic thermal resistance viamore » modulation of acoustic and optic phonon frequencies, while phonon-isotope scattering from mass disorder plays only a minor role. This leads to some unusual cases where values of isotopically pure systems ( 6LiH, 7Li 2H and 6LiF) are lower than the values from their counterparts with naturally occurring isotopes and phonon-isotope scattering. However, these differences are relatively small. The effects of temperature-driven lattice expansion on phonon dispersions and calculated κ are also discussed. This work provides insight into lattice thermal conductivity modulation with mass variation and the interplay of intrinsic phonon-phonon and phonon-isotope scattering in interesting light atom systems.« less

Influence of atmospheric transport patterns on xenon detections at the CTBTO radionuclide network

NASA Astrophysics Data System (ADS)

Krysta, Monika; Kusmierczyk-Michulec, Jolanta

2016-04-01

In order to fulfil its task of monitoring for signals emanating from nuclear explosions, Comprehensive Nuclear-Test-Ban Treaty Organization (CTBTO) operates global International Monitoring System (IMS) comprising seismic, infrasound, hydroacoustic and radionuclide measurement networks. At present, 24 among 80 radionuclide stations foreseen by the Comprehensive Nuclear-Test-Ban Treaty (CTBT) are equipped with certified noble gas measurement systems. Over a past couple of years these systems collected a rich set of measurements of radioactive isotopes of xenon. Atmospheric transport modelling simulations are crucial to an assessment of the origin of xenon detected at the IMS stations. Numerous studies undertaken in the past enabled linking these detections to non Treaty-relevant activities and identifying main contributors. Presence and quantity of xenon isotopes at the stations is hence a result of an interplay of emission patterns and atmospheric circulation. In this presentation we analyse the presence or absence of radioactive xenon at selected stations from an angle of such an interplay. We attempt to classify the stations according to similarity of detection patterns, examine seasonality in those patterns and link them to large scale or local meteorological phenomena. The studies are undertaken using crude hypotheses on emission patterns from known sources and atmospheric transport modelling simulations prepared with the FLEXPART model.

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.

Arctic Ocean Cyclostratigraphy: An Alternative to Marine Oxygen Isotope curves as measures of Cryospheric and Sea-Level History

NASA Astrophysics Data System (ADS)

Cronin, T. M.; Marzen, R.; O'Regan, M.; Dwyer, G. S.

2016-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

Assessing the potential of amino acid δ13C patterns as a carbon source tracer in marine sediments: effects of algal growth conditions and sedimentary diagenesis

NASA Astrophysics Data System (ADS)

Larsen, T.; Bach, L. T.; Salvatteci, R.; Wang, Y. V.; Andersen, N.; Ventura, M.; McCarthy, M. D.

2015-01-01

Burial of organic carbon in marine sediments has a profound influence in marine biogeochemical cycles, and provides a sink for greenhouse gases such as CO2 and CH4. However, tracing organic carbon from primary production sources as well as its transformations in the sediment record remains challenging. Here we examine a novel but growing tool for tracing biosynthetic origin of amino acid carbon skeletons, based on natural occurring stable carbon isotope patterns in individual amino acids (δ13CAA). We focus on two important aspects for δ13CAA utility in sedimentary paleoarchives: first, the fidelity of source diagnostic of algal δ13CAA patterns across different oceanographic growth conditions; and second, the ability of δ13CAA patterns to record the degree of subsequent microbial amino acid synthesis after sedimentary burial. Using the marine diatom Thalassiosira weissflogii, we tested under controlled conditions how δ13CAA patterns respond to changing environmental conditions, including light, salinity, temperature, and pH. Our findings show that while differing oceanic growth conditions can change macromolecular cellular composition, δ13CAA isotopic patterns remain largely invariant. These results underscore that δ13CAA patterns should accurately record biosynthetic sources across widely disparate oceanographic conditions. We also explored how δ13CAA patterns change as a function of age, total nitrogen and organic carbon content after burial, in a marine sediment core from a coastal upwelling area off Peru. Based on the four most informative amino acids for distinguishing between diatom and bacterial sources (i.e. isoleucine, lysine, leucine and tyrosine), bacterial derived amino acids ranged from 10-15% in the sediment layers from the last 5000 years to 35% during the last glacial period. The larger bacterial fractions in older sediments indicate that bacterial activity and amino acid resynthesis progressed, approximately as a function of sediment age, to a substantially larger degree than suggested by changes in total organic nitrogen and carbon content. Taken together, these culturing and sediment studies suggest that δ13CAA patterns in sediments represent a novel proxy for understanding both primary production sources, as well as direct bacterial role in the ultimate preservation of sedimentary organic matter.

Isotope effects associated with the anaerobic oxidation of sulfite and thiosulfate by the photosynthetic bacterium, Chromatium vinosum

NASA Technical Reports Server (NTRS)

Fry, B.; Gest, H.; Hayes, J. M.

1985-01-01

The purple photosynthetic bacterium Chromatium vinosum, strain D, catalyzes several oxidations of reduced sulfur compounds under anaerobic conditions in the light: e.g., sulfide --> sulfur --> sulfate, sulfite --> sulfate, and thiosulfate --> sulfur + sulfate. Here it is shown that no sulfur isotope effect is associated with the last of these processes; isotopic compositions of the sulfur and sulfate produced can differ, however, if the sulfane and sulfonate positions within the thiosulfate have different isotopic compositions. In the second process, an observed change from an inverse to a normal isotope effect during oxidation of sulfite may indicate the operation of 2 enzymatic pathways. In contrast to heterotrophic anaerobic reduction of oxidized sulfur compounds, anaerobic oxidations of inorganic sulfur compounds by photosynthetic bacteria are characterized by relatively small isotope effects.

Hydrogen isotope composition of leaf wax n-alkanes in Arabidopsis lines with different transpiration rates

NASA Astrophysics Data System (ADS)

Pedentchouk, N.; Lawson, T.; Eley, Y.; McAusland, L.

2012-04-01

Stable isotopic compositions of oxygen and hydrogen are used widely to investigate modern and ancient water cycles. The D/H composition of organic compounds derived from terrestrial plants has recently attracted significant attention as a proxy for palaeohydrology. However, the role of various plant physiological and biochemical factors in controlling the D/H signature of leaf wax lipids in extant plants remains unclear. The focus of this study is to investigate the effect of plant transpiration on the D/H composition of n-alkanes in terrestrial plants. This experiment includes 4 varieties of Arabidopsis thaliana that differ with respect to stomatal density and stomatal geometry. All 4 varieties were grown indoors under identical temperature, relative humidity, light and watering regimes and then sampled for leaf wax and leaf water stable isotopic measurements. During growth, stomatal conductance to carbon dioxide and water vapour were also determined. We found that the plants varied significantly in terms of their transpiration rates. Transpiration rates were significantly higher in Arabidopsis ost1 and ost1-1 varieties (2.4 and 3.2 mmol m-2 s-1, respectively) than in Arabidopsis RbohD and Col-0 (1.5 and 1.4). However, hydrogen isotope measurements of n-alkanes extracted from leaf waxes revealed a very different pattern. Varieties ost1, ost1-1, and RbohD have very similar deltaD values of n-C29 alkane (-125, -128, and -127 per mil), whereas the deltaD value of Col-0 is more negative (-137 per mil). The initial results of this work suggest that plant transpiration is decoupled from the D/H composition of n-alkanes. In other words, physical processes that affect water vapour movement between the plant and its environment apparently cannot account for the stable hydrogen isotope composition of organic compounds that comprise leaf waxes. Additional, perhaps biochemical, processes that affect hydrogen isotope fractionation during photosynthesis might need to be invoked to explain the reason for this decoupling. Our current work that also includes leaf water isotopic measurements will provide further details regarding the role of transpiration in controlling the deltaD values of leaf lipids.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Sources and drains: Major controls of hydrothermal fluid flow in the Kokanee Range, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Beaudoin, Georges; Therrien, René

1999-10-01

Vein fields are fractured domains of the lithosphere that have been infiltrated by hydrothermal fluids, which deposited minerals in response to changing physico-chemical conditions. Because oxygen is a major component of the infiltrating fluid and the surrounding rock matrix, the oxygen isotope composition of minerals found in veins is used to decipher ancient fluid flow within the lithosphere. We use a numerical model to simulate oxygen isotope transport in the Kokanee Range silver-lead-zinc vein field. The model considers advective, dispersive, and reactive transport in a three-dimensional porous rock matrix intersected by high-permeability planes representing fracture zones. Here we show that it is the geometrical configuration of the sources and of the drains of hydrothermal fluids, combined with the fracture pattern, that exerts the main control on the oxygen isotope distribution. Other factors that affect, to a lesser extent, the values and positions of oxygen isopleths are the fluids and rock-matrix isotopic compositions, the isotopic fractionation, the reaction rate constant, and hydraulic conductivities of the rock matrix and fracture zones.

Urban and nomadic isotopic niches reveal dietary connectivities along Central Asia's Silk Roads.

PubMed

Hermes, Taylor R; Frachetti, Michael D; Bullion, Elissa A; Maksudov, Farhod; Mustafokulov, Samariddin; Makarewicz, Cheryl A

2018-03-26

The ancient 'Silk Roads' formed a vast network of trade and exchange that facilitated the movement of commodities and agricultural products across medieval Central Asia via settled urban communities and mobile pastoralists. Considering food consumption patterns as an expression of socio-economic interaction, we analyse human remains for carbon and nitrogen isotopes in order to establish dietary intake, then model isotopic niches to characterize dietary diversity and infer connectivity among communities of urbanites and nomadic pastoralists. The combination of low isotopic variation visible within urban groups with isotopic distinction between urban communities irrespective of local environmental conditions strongly suggests localized food production systems provided primary subsistence rather than agricultural goods exchanged along trade routes. Nomadic communities, in contrast, experienced higher dietary diversity reflecting engagements with a wide assortment of foodstuffs typical for mobile communities. These data indicate tightly bound social connectivity in urban centres pointedly funnelled local food products and homogenized dietary intake within settled communities, whereas open and opportunistic systems of food production and circulation were possible through more mobile lifeways.

Stable isotope ratios of tap water in the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Ehleringer, James R.; Chesson, Lesley A.; Stange, Erik; Cerling, Thure E.

2007-03-01

Understanding links between water consumers and climatological (precipitation) sources is essential for developing strategies to ensure the long-term sustainability of water supplies. In pursing this understanding a need exists for tools to study and monitor complex human-hydrological systems that involve high levels of spatial connectivity and supply problems that are regional, rather than local, in nature. Here we report the first national-level survey of stable isotope ratios in tap water, including spatially and temporally explicit samples from a large number of cities and towns across the contiguous United States. We show that intra-annual ranges of tap water isotope ratios are relatively small (e.g., <10‰ for δ2H) at most sites. In contrast, spatial variation in tap water isotope ratios is very large, spanning ranges of 163‰ for δ2H and 23.6‰ for δ18O. The spatial distribution of tap water isotope ratios at the national level is similar to that of stable isotope ratios of precipitation. At the regional level, however, pervasive differences between tap water and precipitation isotope ratios can be attributed to hydrological factors in the water source to consumer chain. These patterns highlight the potential for monitoring of tap water isotope ratios to contribute to the study of regional water supply stability and provide warning signals for impending water resource changes. We present the first published maps of predicted tap water isotope ratios for the contiguous United States, which will be useful in guiding future research on human-hydrological systems and as a tool for applied forensics and traceability studies.

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.

Modeling the influence of a reduced equator-to-pole sea surface temperature gradient on the distribution of water isotopes in the Early/Middle Eocene

NASA Astrophysics Data System (ADS)

Speelman, Eveline N.; Sewall, Jacob O.; Noone, David; Huber, Matthew; von der Heydt, Anna; Damsté, Jaap Sinninghe; Reichart, Gert-Jan

2010-09-01

Proxy-based climate reconstructions suggest the existence of a strongly reduced equator-to-pole temperature gradient during the Azolla interval in the Early/Middle Eocene, compared to modern. Changes in the hydrological cycle, as a consequence of a reduced temperature gradient, are expected to be reflected in the isotopic composition of precipitation (δD, δ 18O). The interpretation of water isotopic records to quantitatively reconstruct past precipitation patterns is, however, hampered by a lack of detailed information on changes in their spatial and temporal distribution. Using the isotope-enabled version of the National Center for Atmospheric Research (NCAR) atmospheric general circulation model, Community Atmosphere Model v.3 (isoCAM3), relationships between water isotopes and past climates can be simulated. Here we examine the influence of an imposed reduced meridional sea surface temperature gradient on the spatial distribution of precipitation and its isotopic composition in an Early/Middle Eocene setting. As a result of the applied forcings, the Eocene simulation predicts the occurrence of less depleted high latitude precipitation, with δD values ranging only between 0 and -140‰ (compared to Present-day 0 to -300‰). Comparison with Early/Middle Eocene-age isotopic proxy data shows that the simulation accurately captures the main features of the spatial distribution of the isotopic composition of Early/Middle Eocene precipitation over land in conjunction with the aspects of the modeled Early/Middle Eocene climate. Hence, the included stable isotope module quantitatively supports the existence of a reduced meridional temperature gradient during this interval.

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

Individual-specific transgenerational marking of fish populations based on a barium dual-isotope procedure.

PubMed

Huelga-Suarez, Gonzalo; Moldovan, Mariella; Garcia-Valiente, America; Garcia-Vazquez, Eva; Alonso, J Ignacio Garcia

2012-01-03

The present study focuses on the development and evaluation of an individual-specific transgenerational marking procedure using two enriched barium isotopes, (135)Ba and (137)Ba, mixed at a given and selectable molar ratio. The method is based on the deconvolution of the isotope patterns found in the sample into four molar contribution factors: natural xenon (Xe nat), natural barium (Ba nat), Ba135, and Ba137. The ratio of molar contributions between Ba137 and Ba135 is constant and independent of the contribution of natural barium in the sample. This procedure was tested in brown trout ( Salmo trutta ) kept in captivity. Trout were injected with three different Ba137/Ba135 isotopic signatures ca. 7 months and 7 days before spawning to compare the efficiency of the marking procedure at long and short term, respectively. The barium isotopic profiles were measured in the offspring by means of inductively coupled plasma mass spectrometry. Each of the three different isotopic signatures was unequivocally identified in the offspring in both whole eggs and larvae. For 9 month old offspring, the characteristic barium isotope signatures could also be detected in the otoliths even in the presence of a high and variable amount of barium of natural isotope abundance. In conclusion, it can be stated that the proposed dual-isotope marking is inheritable and can be detected after both long-term and short-term marking. Furthermore, the dual-isotope marking can be made individual-specific, so that it allows identification of offspring from a single individual or a group of individuals within a given fish group. © 2011 American Chemical Society

Pb-, Sr- and Nd-Isotopic systematics and chemical characteristics of cenozoic basalts, Eastern China

USGS Publications Warehouse

Peng, Z.C.; Zartman, R.E.; Futa, K.; Chen, D.G.

1986-01-01

Forty-eight Paleogene, Neogene and Quaternary basaltic rocks from northeastern and east-central China have been analyzed for major-element composition, selected trace-element contents, and Pb, Sr and Nd isotopic systematics. The study area lies entirely within the marginal Pacific tectonic domain. Proceeding east to west from the continental margin to the interior, the basalts reveal an isotopic transition in mantle source material and/or degree of crustal interaction. In the east, many of the rocks are found to merge both chemically and isotopically with those previously reported from the Japanese and Taiwan island-arc terrains. In the west, clear evidence exists for component(s) of Late Archean continental lithosphere to be present in some samples. A major crustal structure, the Tan-Lu fault, marks the approximate boundary between continental margin and interior isotopic behaviors. Although the isotopic signature of the western basalts has characteristics of lower-crustal contamination, a subcrustal lithosphere, i.e. an attached mantle keel, is probably more likely to be the major contributor of their continental "flavor". The transition from continental margin to interior is very pronounced for Pb isotopes, although Sr and Nd isotopes also combine to yield correlated patterns that deviate strikingly from the mid-ocean ridge basalt (MORB) and oceanic-island trends. The most distinctive chemical attribute of this continental lithosphere component is its diminished U Pb as reflected in the Pb isotopic composition when compared to sources of MORB, oceanic-island and island-arc volcanic rocks. Somewhat diminished Sm Nd and elevated Rb Sr, especially in comparison to the depleted asthenospheric mantle, are also apparent from the Nd- and Sr-isotopic ratios. ?? 1986.

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

PubMed Central

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

2012-01-01

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

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.

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

PubMed

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

2012-07-01

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

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.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

Stable isotope analyses of feather amino acids identify penguin migration strategies at ocean basin scales.

PubMed

Polito, Michael J; Hinke, Jefferson T; Hart, Tom; Santos, Mercedes; Houghton, Leah A; Thorrold, Simon R

2017-08-01

Identifying the at-sea distribution of wide-ranging marine predators is critical to understanding their ecology. Advances in electronic tracking devices and intrinsic biogeochemical markers have greatly improved our ability to track animal movements on ocean-wide scales. Here, we show that, in combination with direct tracking, stable carbon isotope analysis of essential amino acids in tail feathers provides the ability to track the movement patterns of two, wide-ranging penguin species over ocean basin scales. In addition, we use this isotopic approach across multiple breeding colonies in the Scotia Arc to evaluate migration trends at a regional scale that would be logistically challenging using direct tracking alone. © 2017 The Author(s).

Comparison of the Mahalanobis distance and Pearson's χ² statistic as measures of similarity of isotope patterns.

PubMed

Zamanzad Ghavidel, Fatemeh; Claesen, Jürgen; Burzykowski, Tomasz; Valkenborg, Dirk

2014-02-01

To extract a genuine peptide signal from a mass spectrum, an observed series of peaks at a particular mass can be compared with the isotope distribution expected for a peptide of that mass. To decide whether the observed series of peaks is similar to the isotope distribution, a similarity measure is needed. In this short communication, we investigate whether the Mahalanobis distance could be an alternative measure for the commonly employed Pearson's χ(2) statistic. We evaluate the performance of the two measures by using a controlled MALDI-TOF experiment. The results indicate that Pearson's χ(2) statistic has better discriminatory performance than the Mahalanobis distance and is a more robust measure.

Comparison of the Mahalanobis Distance and Pearson's χ2 Statistic as Measures of Similarity of Isotope Patterns

NASA Astrophysics Data System (ADS)

Zamanzad Ghavidel, Fatemeh; Claesen, Jürgen; Burzykowski, Tomasz; Valkenborg, Dirk

2014-02-01

To extract a genuine peptide signal from a mass spectrum, an observed series of peaks at a particular mass can be compared with the isotope distribution expected for a peptide of that mass. To decide whether the observed series of peaks is similar to the isotope distribution, a similarity measure is needed. In this short communication, we investigate whether the Mahalanobis distance could be an alternative measure for the commonly employed Pearson's χ2 statistic. We evaluate the performance of the two measures by using a controlled MALDI-TOF experiment. The results indicate that Pearson's χ2 statistic has better discriminatory performance than the Mahalanobis distance and is a more robust measure.

Isotopes in the Arctic atmospheric water cycle

NASA Astrophysics Data System (ADS)

Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen Larsen, Hans Christian; Masson-Delmotte, Valérie

2016-04-01

The ISO-ARC project aims at documenting the Arctic atmospheric hydrological cycle, by assessing the imprint of the marine boundary conditions (e.g. temperature variations, circulation changes, or meltwater input) to the isotopic composition of the atmospheric water cycle (H218O and HDO) with a focus on North Atlantic and Arctic oceans. For this purpose, two continuous monitoring water vapour stable isotopes cavity ring-down spectrometers have been installed in July 2015: on-board the Polarstern research vessel and in the Siberian Lena delta Samoylov research station (N 72° 22', E 126° 29'). The Polarstern measurements cover the summer 2015 Arctic campaign from July to mid-October, including six weeks in the Fram Strait region in July- August, followed by a campaign reaching the North Pole and a transect from the Norwegian Sea to the North Sea. These vapour observations are completed by water isotopic measurements in samples from the surface ocean water for Polarstern and from precipitation in Samoylov and Tiksi (120 km south-east of the station). A custom-made designed automatic calibration system has been implemented in a comparable manner for both vapour instruments, based on the injection of different liquid water standards, which are completely vaporised in dry air at high temperature. Subsequent humidity level can be adjusted from 2000 to at least 30000 ppm. For a better resilience, an independent calibration system has been added on the Samoylov instrument, allowing measurements of one standard at humidity levels ranging from 2000 to 15000 ppm: dry air is introduced in a tank containing a large amount of liquid water standard, undergoing evaporation under a controlled environment. The measurement protocol includes an automatic calibration every 25 hours. First instrument characterisation experiments depict a significant isotope-humidity effect at low humidity, dependant on the isotopic composition of the standard. For ambient air, our first isotope measurements highlighted significant synoptic variations in summer in both sites. In Samoylov, the premises of a seasonal cycle have been observed during the summer-fall transition, with a fast humidity level and isotopic decrease. The latitudinal gradient is also highly visible on the Polarstern record. Complementing simulations of the water vapour isotopic composition by the ECHAM5-wiso model reproduce the Polarstern synoptic variability and spatial patterns with a good accuracy. In the near future, our records will be combined with simultaneous water isotope measurements in Iceland (by Hans Christian Steen-Larsen, CIC), Svalbard (by Valérie-Masson Delmotte, LSCE) and paired with complementing climate simulations enhanced by water isotope diagnostics. These data sets, covering an approx. 6,000 km transect of Northern Eurasia will allow for a quantitative assessment of the isotopic variations of the Arctic water cycle. The results of these analyses will also be of relevance for the interpretation of isotope signals found in ice cores and on terrestrial Arctic sites in terms of past climate change.

Evolution of the lithospheric mantle beneath Mt. Baekdu (Changbaishan)

NASA Astrophysics Data System (ADS)

Choi, S. H.; Park, K.; Cho, M.; Lee, D. C.

2017-12-01

Major and trace element compositions of minerals as well as Sr-Nd-Hf isotopic compositions of clinopyroxenes from spinel peridotite xenoliths entrained in Late Cenozoic trachybasalt from Mt. Baekdu (Changbaishan) were used to elucidate lithospheric mantle formation and evolution in the eastern North China Craton (NCC). The analyzed peridotites were mainly spinel lherzolites with rare harzburgites. They consisted of olivine, enstatite, diopside and spinel. Plots of the Cr# in spinel against the Mg# in coexisting olivine or spinel suggested an affinity with abyssal peridotites. Comparisons of Cr# and TiO2 in spinel were also compatible with an abyssal peridotite-like composition; however, harzburgites were slightly enriched in TiO2 because of the reaction with MORB-like melt. Temperatures estimated using two-pyroxene thermometry ranged from 750 to 1,010°C, reflecting their lithospheric mantle origin. The REE patterns in clinopyroxenes of the peridotites varied from LREE-depleted to spoon shaped to LREE-enriched, reflecting secondary overprinting effects of metasomatic melts or fluids on the residues from primordial melting. The calculated trace element pattern of metasomatic melt equilibrated with clinopyroxene in Mt. Baekdu peridotite showed strong enrichment in LILEs, Th and U together with slight fractionation in HREEs and considerable depletion in Nb and Ti. The Sr-Nd-Hf isotopic compositions of clinopyroxenes separated from the peridotites varied from more depleted than present-day MORB to bulk Earth values. However, some clinopyroxene showed a decoupling between Nd and Sr isotopes, deviating from the mantle array with a high 87Sr/86Sr ratio. This sample also showed a significant Nd-Hf isotope decoupling lying well above the mantle array. The Lu-Hf and Sm-Nd model ages of residual clinopyroxenes yielded Early Proterozoic to Phanerozoic ages. No signature of Archean cratonic mantle was present. Therefore, Mt. Baekdu peridotite is residual lithospheric mantle that has undergone variable degrees of diachronous melt extraction and infiltration metasomatism involving subduction-related, fluid-bearing silicate melts. The predominance of Phanerozoic Hf model ages indicates that the lherzolites represent lithospheric mantle fragments newly accreted underneath the eastern NCC.

Determining and quantifying specific sources of light alkane

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.

2015-12-01

Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

Tungsten isotopes in bulk meteorites and their inclusions—Implications for processing of presolar components in the solar protoplanetary disk

PubMed Central

Holst, J. C.; Paton, C.; Wielandt, D.; Bizzarro, M.

2016-01-01

We present high precision, low- and high-resolution tungsten isotope measurements of iron meteorites Cape York (IIIAB), Rhine Villa (IIIE), Bendego (IC), and the IVB iron meteorites Tlacotepec, Skookum, and Weaver Mountains, as well as CI chondrite Ivuna, a CV3 chondrite refractory inclusion (CAI BE), and terrestrial standards. Our high precision tungsten isotope data show that the distribution of the rare p-process nuclide 180W is homogeneous among chondrites, iron meteorites, and the refractory inclusion. One exception to this pattern is the IVB iron meteorite group, which displays variable excesses relative to the terrestrial standard, possibly related to decay of rare 184Os. Such anomalies are not the result of analytical artifacts and cannot be caused by sampling of a protoplanetary disk characterized by p-process isotope heterogeneity. In contrast, we find that 183W is variable due to a nucleosynthetic s-process deficit/r-process excess among chondrites and iron meteorites. This variability supports the widespread nucleosynthetic s/r-process heterogeneity in the protoplanetary disk inferred from other isotope systems and we show that W and Ni isotope variability is correlated. Correlated isotope heterogeneity for elements of distinct nucleosynthetic origin (183W and 58Ni) is best explained by thermal processing in the protoplanetary disk during which thermally labile carrier phases are unmixed by vaporization thereby imparting isotope anomalies on the residual processed reservoir. PMID:27445452

Utility of stable isotope analysis in studying foraging ecology of herbivores: Examples from moose and caribou

USGS Publications Warehouse

Ben-David, Merav; Shochat, Einav; Adams, Layne G.

2001-01-01

Recently, researchers emphasized that patterns of stable isotope ratios observed at the individual level are a result of an interaction between ecological, physiological, and biochemical processes. Isotopic models for herbivores provide additional complications because those mammals consume foods that have high variability in nitrogen concentrations. In addition, distribution of amino acids in plants may differ greatly from that required by a herbivore. At northern latitudes, where the growing season of vegetation is short, isotope ratios in herbivore tissues are expected to differ between seasons. Summer ratios likely reflect diet composition, whereas winter ratios would reflect diet and nutrient recycling by the animals. We tested this hypothesis using data collected from blood samples of caribou (Rangifer tarandus) and moose (Alces alces) in Denali National Park and Preserve, Alaska, USA. Stable isotope ratios of moose and caribou were significantly different from each other in late summer-autumn and winter. Also, late summer-autumn and winter ratios differed significantly between seasons in both species. Nonetheless, we were unable to evaluate whether differences in seasonal isotopic ratios were a result of diet selection or a response to nutrient recycling. We believe that additional studies on plant isotopic ratios as related to ecological factors in conjunction with investigations of diet selection by the herbivores will enhance our understanding of those interactions. Also, controlled studies investigating the relation between diet and physiological responses in herbivores will increase the utility of isotopic analysis in studying foraging ecology of herbivores.

Climatic signals registered as Carbon isotopic values in Metasequoia leaf tissues: A statistical analysis

NASA Astrophysics Data System (ADS)

Yang, H.; Blais, B.; Perez, G.; Pagani, M.

2006-12-01

To examine climatic signals registered as carbon isotopic values in leaf tissues of C3 plants, we collected mature leaf tissues from sun and shade leaves of Metasequoia trees germinated from the 1947 batch of seeds from China and planted along a latitudinal gradient of the United States. Samples from 40 individual trees, along with fossilized material from the early Tertiary of the Canadian Arctic, were analyzed for C and concentration and isotopic values using EA-IRMS after the removal of free lipids. The generated datasets were then merged with climate data compiled from each tree site recorded as average values over the past thirty years (1971-2002, NOAA database). When the isotope data were cross plotted against each geographic and climatic indicator, Latitude, Mean Annual Temperature (MAT), Average Summer Mean Temperature (ASMT)(June-August), Mean Annual Precipitation (MAP), and Average Summer Mean Precipitation (ASMP) respectively correlation patterns were revealed. The best correlating trend was obtained between temperature parameters and C isotopic values, and this correlation is stronger in the northern leaf samples than the southern samples. We discovered a strong positive correlation between latitude and the offset of C isotopic values between shade and sun leaves. This investigation represents a comprehensive examination on climatic signals registered as C isotopic values on a single species that is marked by single genetic source. The results bear implications on paleoclimatic interpretations of C isotopic signals obtained from fossil plant tissues.

Indian Summer Monsoon dynamics during Termination II and MIS 5e

NASA Astrophysics Data System (ADS)

Magiera, Matthias; Erhardt, Andrea M.; Hartland, Adam; Kwiecien, Ola; Cheng, Hai; Immenhauser, Adrian; Turchyn, Alexandra; Breitenbach, Sebastian F. M.

2017-04-01

The interpretation of speleothem oxygen isotope ratios (δ18O) as proxy for Indian Summer Monsoon (ISM) dynamics is ambiguous, due to multiple influencing factors. Here we combine δ18O and calcium isotope δ44Ca analyses with elemental data to delineate regional shifts in moisture source, local rainfall amount, and changes in ISM intensity and length during Termination II and MIS 5e. Oxygen isotope ratios reflect a mixed signal of moisture source dynamics and rainfall amount; δ44Ca and Mg/Ca ratios are interpreted as proxies for local effective moisture and prior calcite precipitation (PCP) in the epikarst. The age of stalagmite MAW-3 from Mawmluh Cave, NE India, is constraint by six U-series dates. 108 samples, obtained at 0.4 mm resolution from the 70 mm long speleothem sample, have been analysed for δ18O, δ44Ca and Mg/Ca. Oxygen isotope ratios were measured on a ThermoFisher Scientific MAT 253 at Ruhr-University Bochum. Elemental ratios were measured on a quadrupole ICP-MS at Waikato University. Calcium isotope ratios were analyzed on a ThermoFisher Scientific Triton at University of Cambridge. MAW-3 grew from 136 kyrs BP to 96 kyrs BP, covering Termination II and MIS 5e. Oxygen isotope values are high (ca. +0.91 ‰) during Termination II, reach a minimum during MIS 5e (-3.5 ‰), and rise again to -0.2 ‰ at the end of MIS 5e. Calcium isotope ratios range from -0.32 ‰ to -0.70 ‰ and show a positive correlation (R2= 0.7) with δ18O. High δ18O values during Termination II reflect reduced atmospheric circulation and/or a proximal moisture source (Bay of Bengal), implying lowered ISM intensity. A positive correlation of δ18O with δ44Ca suggests concurrent changes of moisture source location and local rainfall amount, with a proximal moisture source and reduced effective rainfall during periods of weak ISM. Elevated Mg/Ca ratios at such intervals corroborate PCP occurrence, which reflects dry conditions. The beginning of MIS 5e (ca. 132 kyrs BP) is marked by a rapid change to lower δ18O and δ44Ca, suggesting increased local infiltration with increasing ISM rainfall, and a concurrent change to a more distal moisture source. The MAW-3 multi-proxy record compares well with reconstructions from China and northern India, the latter being more depleted, due to Rayleigh fractionation. We suggest that multi-proxy analyses of δ18O, δ44Ca and Mg/Ca greatly help to delineate regional circulation pattern and local effective moisture dynamics in monsoonal settings.

Convergence of soil nitrogen isotopes across global climate gradients

USGS Publications Warehouse

Craine, Joseph M.; Elmore, Andrew J.; Wang, Lixin; Augusto, Laurent; Baisden, W. Troy; Brookshire, E. N. J.; Cramer, Michael D.; Hasselquist, Niles J.; Hobbie, Erik A.; Kahmen, Ansgar; Koba, Keisuke; Kranabetter, J. Marty; Mack, Michelle C.; Marin-Spiotta, Erika; Mayor, Jordan R.; McLauchlan, Kendra K.; Michelsen, Anders; Nardoto, Gabriela B.; Oliveira, Rafael S.; Perakis, Steven S.; Peri, Pablo L.; Quesada, Carlos A.; Richter, Andreas; Schipper, Louis A.; Stevenson, Bryan A.; Turner, Benjamin L.; Viani, Ricardo A. G.; Wanek, Wolfgang; Zeller, Bernd

2015-01-01

Quantifying global patterns of terrestrial nitrogen (N) cycling is central to predicting future patterns of primary productivity, carbon sequestration, nutrient fluxes to aquatic systems, and climate forcing. With limited direct measures of soil N cycling at the global scale, syntheses of the 15 N: 14 N ratio of soil organic matter across climate gradients provide key insights into understanding global patterns of N cycling. In synthesizing data from over 6000 soil samples, we show strong global relationships among soil N isotopes, mean annual temperature (MAT), mean annual precipitation (MAP), and the concentrations of organic carbon and clay in soil. In both hot ecosystems and dry ecosystems, soil organic matter was more enriched in 15 N than in corresponding cold ecosystems or wet ecosystems. Below a MAT of 9.8°C, soil δ15N was invariant with MAT. At the global scale, soil organic C concentrations also declined with increasing MAT and decreasing MAP. After standardizing for variation among mineral soils in soil C and clay concentrations, soil δ15N showed no consistent trends across global climate and latitudinal gradients. Our analyses could place new constraints on interpretations of patterns of ecosystem N cycling and global budgets of gaseous N loss.

Convergence of soil nitrogen isotopes across global climate gradients.

PubMed

Craine, Joseph M; Elmore, Andrew J; Wang, Lixin; Augusto, Laurent; Baisden, W Troy; Brookshire, E N J; Cramer, Michael D; Hasselquist, Niles J; Hobbie, Erik A; Kahmen, Ansgar; Koba, Keisuke; Kranabetter, J Marty; Mack, Michelle C; Marin-Spiotta, Erika; Mayor, Jordan R; McLauchlan, Kendra K; Michelsen, Anders; Nardoto, Gabriela B; Oliveira, Rafael S; Perakis, Steven S; Peri, Pablo L; Quesada, Carlos A; Richter, Andreas; Schipper, Louis A; Stevenson, Bryan A; Turner, Benjamin L; Viani, Ricardo A G; Wanek, Wolfgang; Zeller, Bernd

2015-02-06

Quantifying global patterns of terrestrial nitrogen (N) cycling is central to predicting future patterns of primary productivity, carbon sequestration, nutrient fluxes to aquatic systems, and climate forcing. With limited direct measures of soil N cycling at the global scale, syntheses of the (15)N:(14)N ratio of soil organic matter across climate gradients provide key insights into understanding global patterns of N cycling. In synthesizing data from over 6000 soil samples, we show strong global relationships among soil N isotopes, mean annual temperature (MAT), mean annual precipitation (MAP), and the concentrations of organic carbon and clay in soil. In both hot ecosystems and dry ecosystems, soil organic matter was more enriched in (15)N than in corresponding cold ecosystems or wet ecosystems. Below a MAT of 9.8°C, soil δ(15)N was invariant with MAT. At the global scale, soil organic C concentrations also declined with increasing MAT and decreasing MAP. After standardizing for variation among mineral soils in soil C and clay concentrations, soil δ(15)N showed no consistent trends across global climate and latitudinal gradients. Our analyses could place new constraints on interpretations of patterns of ecosystem N cycling and global budgets of gaseous N loss.

Kinetic and metabolic isotope effects in coral skeletal carbon isotopes: A re-evaluation using experimental coral bleaching as a case study

NASA Astrophysics Data System (ADS)

Schoepf, Verena; Levas, Stephen J.; Rodrigues, Lisa J.; McBride, Michael O.; Aschaffenburg, Matthew D.; Matsui, Yohei; Warner, Mark E.; Hughes, Adam D.; Grottoli, Andréa G.

2014-12-01

Coral skeletal δ13C can be a paleo-climate proxy for light levels (i.e., cloud cover and seasonality) and for photosynthesis to respiration (P/R) ratios. The usefulness of coral δ13C as a proxy depends on metabolic isotope effects (related to changes in photosynthesis) being the dominant influence on skeletal δ13C. However, it is also influenced by kinetic isotope effects (related to calcification rate) which can overpower metabolic isotope effects and thus compromise the use of coral skeletal δ13C as a proxy. Heikoop et al. (2000) proposed a simple data correction to remove kinetic isotope effects from coral skeletal δ13C, as well as an equation to calculate P/R ratios from coral isotopes. However, despite having been used by other researchers, the data correction has never been directly tested, and isotope-based P/R ratios have never been compared to P/R ratios measured using respirometry. Experimental coral bleaching represents a unique environmental scenario to test this because bleaching produces large physiological responses that influence both metabolic and kinetic isotope effects in corals. Here, we tested the δ13C correction and the P/R calculation using three Pacific and three Caribbean coral species from controlled temperature-induced bleaching experiments where both the stable isotopes and the physiological variables that cause isotopic fractionation (i.e., photosynthesis, respiration, and calcification) were simultaneously measured. We show for the first time that the data correction proposed by Heikoop et al. (2000) does not effectively remove kinetic effects in the coral species studied here, and did not improve the metabolic signal of bleached and non-bleached corals. In addition, isotope-based P/R ratios were in poor agreement with measured P/R ratios, even when the data correction was applied. This suggests that additional factors influence δ13C and δ18O, which are not accounted for by the data correction. We therefore recommend that the data correction not be routinely applied for paleo-climate reconstruction, and that P/R ratios should only be obtained by direct measurement by respirometry.

Oxygen isotope fractionation effects in soil water via interaction with cations (Mg, Ca, K, Na) adsorbed to phyllosilicate clay minerals

NASA Astrophysics Data System (ADS)

Oerter, Erik; Finstad, Kari; Schaefer, Justin; Goldsmith, Gregory R.; Dawson, Todd; Amundson, Ronald

2014-07-01

In isotope-enabled hydrology, soil and vadose zone sediments have been generally considered to be isotopically inert with respect to the water they host. This is inconsistent with knowledge that clay particles possessing an electronegative surface charge and resulting cation exchange capacity (CEC) interact with a wide range of solutes which, in the absence of clays, have been shown to exhibit δ18O isotope effects that vary in relation to the ionic strength of the solutions. To investigate the isotope effects caused by high CEC clays in mineral-water systems, we created a series of monominerallic-water mixtures at gravimetric water contents ranging from 5% to 32%, consisting of pure deionized water of known isotopic composition with homoionic (Mg, Ca, Na, K) montmorillonite. Similar mixtures were also created with quartz to determine the isotope effect of non-, or very minimally-, charged mineral surfaces. The δ18O value of the water in these monominerallic soil analogs was then measured by isotope ratio mass spectrometry (IRMS) after direct headspace CO2 equilibration. Mg- and Ca-exchanged homoionic montmorillonite depleted measured δ18O values up to 1.55‰ relative to pure water at 5% water content, declining to 0.49‰ depletion at 30% water content. K-montmorillonite enriched measured δ18O values up to 0.86‰ at 5% water content, declining to 0.11‰ enrichment at 30% water. Na-montmorillonite produces no measureable isotope effect. The isotope effects observed in these experiments may be present in natural, high-clay soils and sediments. These findings have relevance to the interpretation of results of direct CO2-water equilibration approaches to the measurement of the δ18O value of soil water. The adsorbed cation isotope effect may bear consideration in studies of pedogenic carbonate, plant-soil water use and soil-atmosphere interaction. Finally, the observed isotope effects may prove useful as molecular scale probes of the nature of mineral-water interactions.

Isotopic modeling of the sub-cloud evaporation effect in precipitation.

PubMed

Salamalikis, V; Argiriou, A A; Dotsika, E

2016-02-15

In dry and warm environments sub-cloud evaporation influences the falling raindrops modifying their final stable isotopic content. During their descent from the cloud base towards the ground surface, through the unsaturated atmosphere, hydrometeors are subjected to evaporation whereas the kinetic fractionation results to less depleted or enriched isotopic signatures compared to the initial isotopic composition of the raindrops at cloud base. Nowadays the development of Generalized Climate Models (GCMs) that include isotopic content calculation modules are of great interest for the isotopic tracing of the global hydrological cycle. Therefore the accurate description of the underlying processes affecting stable isotopic content can improve the performance of iso-GCMs. The aim of this study is to model the sub-cloud evaporation effect using a) mixing and b) numerical isotope evaporation models. The isotope-mixing evaporation model simulates the isotopic enrichment (difference between the ground and the cloud base isotopic composition of raindrops) in terms of raindrop size, ambient temperature and relative humidity (RH) at ground level. The isotopic enrichment (Δδ) varies linearly with the evaporated raindrops mass fraction of the raindrop resulting to higher values at drier atmospheres and for smaller raindrops. The relationship between Δδ and RH is described by a 'heat capacity' model providing high correlation coefficients for both isotopes (R(2)>80%) indicating that RH is an ideal indicator of the sub-cloud evaporation effect. Vertical distribution of stable isotopes in falling raindrops is also investigated using a numerical isotope-evaporation model. Temperature and humidity dependence of the vertical isotopic variation is clearly described by the numerical isotopic model showing an increase in the isotopic values with increasing temperature and decreasing RH. At an almost saturated atmosphere (RH=95%) sub-cloud evaporation is negligible and the isotopic composition hardly changes even at high temperatures while at drier and warm conditions the enrichment of (18)Ο reaches up to 20‰, depending on the raindrop size and the initial meteorological conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

Mass-independent isotope fractionation of Mo, Ru, Cd, and Te

NASA Astrophysics Data System (ADS)

Fujii, T.; Moynier, F.; Albarède, F.

2006-12-01

The variation of the mean charge distribution in the nucleus with the neutron number of different isotopes induces a tenuous shift of the nuclear field. The mass fractionation induced during phase changes is irregular, notably with 'staggering' between odd and even masses, and becomes increasingly non-linear for neutron-rich isotopes. A strong correlation is observed between the deviation of the isotopic effects from the linear dependence with mass and the corresponding nuclear charge radii. We first demonstrated on a number of elements the existence of such mass-independent isotope fractionation in laboratory experiments of solvent extraction with a macrocyclic compound. The isotope ratios were analyzed by multiple-collector inductively coupled plasma mass spectrometry with a typical precision of <100 ppm. The isotopes of odd and even atomic masses are enriched in the solvent to an extent that closely follows the variation of their nuclear charge radii. The present results fit Bigeleisen's (1996) model, which is the standard mass-dependent theory modified to include a correction term named the nuclear field shift effect. For heavy elements like uranium, the mass-independent effect is important enough to dominate the mass-dependent effect. We subsequently set out to compare the predictions of Bigeleisen's theory with the isotopic anomalies found in meteorites. Some of these anomalies are clearly inconsistent with nucleosynthetic effects (either s- or r-processes). Isotopic variations of Mo and Ru in meteorites, especially in Allende (CV3), show a clear indication of nucleosynthetic components. However, the mass-independent anomaly of Ru observed in Murchison (CM2) is a remarkable exception which cannot be explained by the nucleosynthetic model, but fits the nuclear field shift theory extremely well. The abundances of the even atomic mass Te isotopes in the leachates of carbonaceous chondrites, Allende, Murchison, and Orgueil, fit a mass-dependent law well, but the odd atomic mass isotope ^{125}Te clearly deviates from this correlation. The nuclear field shift theory shows that there is no effect on ^{130}Te but that the ^{125}Te anomaly is real. Carbonaceous chondrites do not reveal significant isotope fractionation of Cd isotopes, but a nuclear field shift effect is clearly present in type-3 (unequilibrated) ordinary chondrites. The nuclear field shift effect is temperature dependent and is probably more frequent in nature than commonly thought. It remains, together with nucleosynthetric anomalies, perfectly visible through the normalization of isotopic ratios to a reference value. In meteorites, this effect may originate both during condensation/evaporation processes in the nebular gas and during the metamorphism of the meteorite parent bodies.

Steric effects on the primary isotope dependence of secondary kinetic isotope effects in hydride transfer reactions in solution: caused by the isotopically different tunneling ready state conformations?

PubMed

Maharjan, Binita; Raghibi Boroujeni, Mahdi; Lefton, Jonathan; White, Ormacinda R; Razzaghi, Mortezaali; Hammann, Blake A; Derakhshani-Molayousefi, Mortaza; Eilers, James E; Lu, Yun

2015-05-27

The observed 1° isotope effect on 2° KIEs in H-transfer reactions has recently been explained on the basis of a H-tunneling mechanism that uses the concept that the tunneling of a heavier isotope requires a shorter donor-acceptor distance (DAD) than that of a lighter isotope. The shorter DAD in D-tunneling, as compared to H-tunneling, could bring about significant spatial crowding effect that stiffens the 2° H/D vibrations, thus decreasing the 2° KIE. This leads to a new physical organic research direction that examines how structure affects the 1° isotope dependence of 2° KIEs and how this dependence provides information about the structure of the tunneling ready states (TRSs). The hypothesis is that H- and D-tunneling have TRS structures which have different DADs, and pronounced 1° isotope effect on 2° KIEs should be observed in tunneling systems that are sterically hindered. This paper investigates the hypothesis by determining the 1° isotope effect on α- and β-2° KIEs for hydride transfer reactions from various hydride donors to different carbocationic hydride acceptors in solution. The systems were designed to include the interactions of the steric groups and the targeted 2° H/D's in the TRSs. The results substantiate our hypothesis, and they are not consistent with the traditional model of H-tunneling and 1°/2° H coupled motions that has been widely used to explain the 1° isotope dependence of 2° KIEs in the enzyme-catalyzed H-transfer reactions. The behaviors of the 1° isotope dependence of 2° KIEs in solution are compared to those with alcohol dehydrogenases, and sources of the observed "puzzling" 2° KIE behaviors in these enzymes are discussed using the concept of the isotopically different TRS conformations.

Development of an enantiomer-specific stable carbon isotope analysis (ESIA) method for assessing the fate of α-hexachlorocyclo-hexane in the environment.

PubMed

Badea, Silviu-Laurentiu; Vogt, Carsten; Gehre, Matthias; Fischer, Anko; Danet, Andrei-Florin; Richnow, Hans-Hermann

2011-05-30

α-Hexachlorocyclohexane (α-HCH) is the only chiral isomer of the eight 1,2,3,4,5,6-HCHs and we have developed an enantiomer-specific stable carbon isotope analysis (ESIA) method for the evaluation of its fate in the environment. The carbon isotope ratios of the α-HCH enantiomers were determined for a commercially available α-HCH sample using a gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) system equipped with a chiral column. The GC-C-IRMS measurements revealed δ-values of -32.5 ± 0.8‰ and -32.3 ± 0.5‰ for (-) α-HCH and (+) α-HCH, respectively. The isotope ratio of bulk α-HCH was estimated to be -32.4 ± 0.6‰ which was in accordance with the δ-values obtained by GC-C-IRMS (-32.7 ± 0.2‰) and elemental analyzer-isotope ratio mass spectrometry (EA-IRMS) of the bulk α-HCH (-32.1 ± 0.1‰). The similarity of the isotope ratio measurements of bulk α-HCH by EA-IRMS and GC-C-IRMS indicates the accuracy of the chiral GC-C-IRMS method. The linearity of the α-HCH ESIA method shows that carbon isotope ratios can be obtained for a signal size above 100 mV. The ESIA measurements exhibited standard deviations (2σ) that were mostly < ± 0.5‰. In order to test the chiral GC-C-IRMS method, the isotope compositions of individual enantiomers in biodegradation experiments of α-HCH with Clostridium pasteurianum and samples from a contaminated field site were determined. The isotopic compositions of the α-HCH enantiomers show a range of enantiomeric and isotope patterns, suggesting that enantiomeric and isotope fractionation can serve as an indicator for biodegradation and source characterization of α-HCH in the environment. Copyright © 2011 John Wiley & Sons, Ltd.

In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory

DOE PAGES

Conrad, P. G.; Malespin, C. A.; Franz, H. B.; ...

2016-11-01

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. But, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stablemore » isotopes, unmeasured by Viking. Our new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, but, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.« less

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI—two types of X grains

DOE PAGES

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.; ...

2017-05-10

Here, we used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grainsmore » was fortuitous, because only ~1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. And while one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.« less

In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory

NASA Astrophysics Data System (ADS)

Conrad, P. G.; Malespin, C. A.; Franz, H. B.; Pepin, R. O.; Trainer, M. G.; Schwenzer, S. P.; Atreya, S. K.; Freissinet, C.; Jones, J. H.; Manning, H.; Owen, T.; Pavlov, A. A.; Wiens, R. C.; Wong, M. H.; Mahaffy, P. R.

2016-11-01

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. However, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stable isotopes, unmeasured by Viking. The new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, however, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.

Strontium and barium isotopes in presolar silicon carbide grains measured with CHILI—two types of X grains

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

Stephan, Thomas; Trappitsch, Reto; Davis, Andrew M.

Here, we used CHILI, the Chicago Instrument for Laser Ionization, a new resonance ionization mass spectrometer developed for isotopic analysis of small samples, to analyze strontium, zirconium, and barium isotopes in 22 presolar silicon carbide grains. Twenty of the grains showed detectable strontium and barium, but none of the grains had enough zirconium to be detected with CHILI. Nine grains were excluded from further consideration since they showed very little signals (<1000 counts) for strontium as well as for barium. Among the 11 remaining grains, we found three X grains. The discovery of three supernova grains among only 22 grainsmore » was fortuitous, because only ~1% of presolar silicon carbide grains are type X, but was confirmed by silicon isotopic measurements of grain residues with NanoSIMS. And while one of the X grains showed strontium and barium isotope patterns expected for supernova grains, the two other supernova grains have 87Sr/86Sr < 0.5, values never observed in any natural sample before. From their silicon isotope ratios, the latter two grains can be classified as X2 grains, while the former grain belongs to the more common X1 group. The differences of these grains in strontium and barium isotopic composition constrain their individual formation conditions in Type II supernovae.« less

Chemical changes and carbon isotope variations in a cross-section of a large Miocene gymnospermous log

USGS Publications Warehouse

Bates, A.L.; Spiker, E. C.

1992-01-01

The cross-sectional radius of a 3-m (diam.) brown coal gymnospermous log of Miocene age, previously analyzed for carbohydrate and lignin methoxyl content by solid-state 13C nuclear magnetic resonance spectroscopy, was examined using stable carbon isotopic ratios in order to determine if the isotopic composition could be related to chemical changes or to radial position. This study found a possible relationship between ??13C-values and radial position; however, these changes cannot be linked to carbohydrate content and are probably attributable to changing growth conditions during the lifetime of the tree. An apparent linear relationship between the changes in carbohydrate content after sodium para-periodate treatment and corresponding changes in the ??13C-values indicates constant isotopic fractionation between lignin and carbohydrates along the cross-sectional radius. This result indicates that diagenesis has not produced any significant change in the lignin-carbohydrate carbon isotopic fractionation or, alternatively, that diagenesis has erased any fractionation pattern that once existed. A sample of fresh wood from another gymnospermous species was analyzed by the same methods and found to have lignin-carbohydrate carbon isotopic fractionation significantly different from that of the Miocene log section samples, suggesting that differences may be species-related or that the complex mixture of carbohydrates in the fresh wood was isotopically different from that of the degraded wood, and the whole Miocene log was uniformly altered. ?? 1992.

In Situ Measurement of Atmospheric Krypton and Xenon on Mars with Mars Science Laboratory

NASA Technical Reports Server (NTRS)

Conrad, P. G.; Malespin, C. A.; Franz, H. B.; Pepin, R. O.; Trainer, M. G.; Schwenzer, S. P.; Atreya, S. K.; Freissinet, C.; Jones, J. H.; Manning, H.;

In situ measurement of atmospheric krypton and xenon on Mars with Mars Science Laboratory

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

Conrad, P. G.; Malespin, C. A.; Franz, H. B.

Mars Science Laboratory's Sample Analysis at Mars (SAM) investigation has measured all of the stable isotopes of the heavy noble gases krypton and xenon in the martian atmosphere, in situ, from the Curiosity Rover at Gale Crater, Mars. Previous knowledge of martian atmospheric krypton and xenon isotope ratios has been based upon a combination of the Viking mission's krypton and xenon detections and measurements of noble gas isotope ratios in martian meteorites. But, the meteorite measurements reveal an impure mixture of atmospheric, mantle, and spallation contributions. The xenon and krypton isotopic measurements reported here include the complete set of stablemore » isotopes, unmeasured by Viking. Our new results generally agree with Mars meteorite measurements but also provide a unique opportunity to identify various non-atmospheric heavy noble gas components in the meteorites. Kr isotopic measurements define a solar-like atmospheric composition, but deviating from the solar wind pattern at 80Kr and 82Kr in a manner consistent with contributions originating from neutron capture in Br. The Xe measurements suggest an intriguing possibility that isotopes lighter than 132Xe have been enriched to varying degrees by spallation and neutron capture products degassed to the atmosphere from the regolith, and a model is constructed to explore this possibility. Such a spallation component, but, is not apparent in atmospheric Xe trapped in the glassy phases of martian meteorites.« less

A lab in the field: high-frequency analysis of water quality and stable isotopes in stream water and precipitation

NASA Astrophysics Data System (ADS)

von Freyberg, Jana; Studer, Bjørn; Kirchner, James W.

2017-03-01

High-frequency measurements of solutes and isotopes (18O and 2H) in rainfall and streamflow can shed important light on catchment flow pathways and travel times, but the workload and sample storage artifacts involved in collecting, transporting, and analyzing thousands of bottled samples severely constrain catchment studies in which conventional sampling methods are employed. However, recent developments towards more compact and robust analyzers have now made it possible to measure chemistry and water isotopes in the field at sub-hourly frequencies over extended periods. Here, we present laboratory and field tests of a membrane-vaporization continuous water sampler coupled to a cavity ring-down spectrometer for real-time measurements of δ18O and δ2H combined with a dual-channel ion chromatograph (IC) for the synchronous analysis of major cations and anions. The precision of the isotope analyzer was typically better than 0.03 ‰ for δ18O and 0.17 ‰ for δ2H in 10 min average readings taken at intervals of 30 min. Carryover effects were less than 1.2 % between isotopically contrasting water samples for 30 min sampling intervals, and instrument drift could be corrected through periodic analysis of secondary reference standards. The precision of the ion chromatograph was typically ˜ 0.1-1 ppm or better, with relative standard deviations of ˜ 1 % or better for most major ions in stream water, which is sufficient to detect subtle biogeochemical signals in catchment runoff. We installed the coupled isotope analyzer/IC system in an uninsulated hut next to a stream of a small catchment and analyzed stream water and precipitation samples every 30 min over 28 days. These high-frequency measurements facilitated a detailed comparison of event-water fractions via endmember mixing analysis with both chemical and isotope tracers. For two events with relatively dry antecedent moisture conditions, the event-water fractions were < 21 % based on isotope tracers but were significantly overestimated (40 to 82 %) by the chemical tracers. These observations, coupled with the storm-to-storm patterns in precipitation isotope inputs and the associated stream water isotope response, led to a conceptual hypothesis for runoff generation in the catchment. Under this hypothesis, the pre-event water that is mobilized by precipitation events may, depending on antecedent moisture conditions, be significantly shallower, younger, and less mineralized than the deeper, older water that feeds baseflow and thus defines the pre-event endmember used in hydrograph separation. This proof-of-concept study illustrates the potential advantages of capturing isotopic and hydrochemical behavior at a high frequency over extended periods that span multiple hydrologic events.

On-target labeling of intracellular metabolites combined with chemical mapping of individual hyphae revealing cytoplasmic relocation of isotopologues.

PubMed

Hu, Jie-Bi; Chen, Yu-Chie; Urban, Pawel L

2012-06-05

A microscale analytical platform integrating microbial cell culture, isotopic labeling, along with visual and mass spectrometric imaging with single-cell resolution has been developed and applied in the monitoring of cellular metabolism in fungal mycelium. The method implements open chips with a two-dimensional surface pattern composed of hydrophobic and hydrophilic zones. Two hydrophilic islands are used as medium reservoirs, while the hydrophobic area constitutes the support for the growing aerial hyphae, which do not have direct contact with the medium. The first island, containing (12)C(6)-glucose medium, was initially inoculated with the mycelium (Neurospora crassa), and following the initial incubation period, the hyphae progressed toward the second medium island, containing an isotopically labeled substrate ((13)C(6)-glucose). The (13)C atoms were gradually incorporated into cellular metabolites, which was revealed by MALDI-MS. The fate of the chitin-biosynthesis precursor, uridine diphosphate N-acetylglucosamine (UDP-GlcNAc), was monitored by recording mass spectra with characteristic isotopic patterns, which indicated the presence of various (12)C/(13)C isotopologues. The method enabled mapping the (13)C-labeled UDP-GlcNAc in fungal mycelium and recording its redistribution in hyphae, directly on the chip.

Stable isotope, site-specific mass tagging for protein identification

DOEpatents

Chen, Xian

2006-10-24

Proteolytic peptide mass mapping as measured by mass spectrometry provides an important method for the identification of proteins, which are usually identified by matching the measured and calculated m/z values of the proteolytic peptides. A unique identification is, however, heavily dependent upon the mass accuracy and sequence coverage of the fragment ions generated by peptide ionization. The present invention describes a method for increasing the specificity, accuracy and efficiency of the assignments of particular proteolytic peptides and consequent protein identification, by the incorporation of selected amino acid residue(s) enriched with stable isotope(s) into the protein sequence without the need for ultrahigh instrumental accuracy. Selected amino acid(s) are labeled with .sup.13C/.sup.15N/.sup.2H and incorporated into proteins in a sequence-specific manner during cell culturing. Each of these labeled amino acids carries a defined mass change encoded in its monoisotopic distribution pattern. Through their characteristic patterns, the peptides with mass tag(s) can then be readily distinguished from other peptides in mass spectra. The present method of identifying unique proteins can also be extended to protein complexes and will significantly increase data search specificity, efficiency and accuracy for protein identifications.

Back arc basalts from Patagonia: sediment input in a distal subduction domain

NASA Astrophysics Data System (ADS)

Hesse, A.; Mandeville, C.; Varekamp, J. C.

2007-12-01

Cinder cones and lava flows from the Loncopue graben in N Patagonia (37 S) were sampled over a 180 km N-S transect. These mainly basaltic and trachybasaltic lava flows carry olivine with Cr-Al-rich spinel inclusions, while some more evolved flows carry clinopyroxene and plagioclase. Most of these rocks have between 5-8 percent MgO, and show highly variable K and LIL trace element concentrations. The rocks have up to 180 ppm Ni and 250 ppm Cr. Relative trace element abundance diagrams show negative Ta-Nb anomalies in most rocks, although their depths vary strongly. The REE patterns show LREE enrichment and most rocks have no Eu anomalies, indicating the absence of significant plagioclase fractionation. The basalts have constant U/Th values (~0.25) that are similar to those found in the nearby Copahue-Caviahue arc volcanics. Microprobe analyses of the main phases show olivine with Mg # of 80-87 and up to 2600 ppm Ni. Simulations with the Melts-pMelts programs and application of mineral-melt geothermometers suggest that most olivine phenocrysts crystallized at ~8-10 kbar pressure at temperatures of 1170-1220 oC and with 1-3 percent H2O in the melt. The Sr isotope compositions of 9 samples show a range from 0.7033 - 0.7043, which are negatively correlated with Nd isotope ratios (0.51273- 0.51292). Surprisingly, the most MgO-rich basalt has the most radiogenic Sr isotope ratio. The Pb isotope ratios, well outside the DMM range, correlate very poorly with either Sr isotope ratios or in Pb-Pb isotope graphs. The lack of correlation between degree of evolution and Sr isotope ratios as well as the primitive nature of the rocks and crystals suggest that crustal assimilation was not a major process impacting the composition of these small magma volumes. Incompatible trace element patterns of several samples resemble those of detrital sediment samples from the Pacific, which together with the isotopic data suggest that these magmas may carry a subducted sediment component. Trace element concentrations and ratios do not correlate with radiogenic isotope ratios, suggesting that more than one contaminant source impacted the mantle domain, e.g., fluids as well as sediment melts. Isotope and trace element ratios vary considerably between cinder cones that are only 10-15 km apart, suggesting that the underlying mantle is highly heterogeneous, enriched in subducted components in thin veins and patches. The Loncopue basalts seem to be transitional in composition between the very voluminous S-Patagonia back-arc basalts and the Copahue-Caviahue arc rocks to the north.

Iron uptake and magnetite biomineralization in the magnetotactic bacterium Magnetospirillum magneticum strain AMB-1: An iron isotope study

NASA Astrophysics Data System (ADS)

Amor, Matthieu; Busigny, Vincent; Louvat, Pascale; Tharaud, Mickaël; Gélabert, Alexandre; Cartigny, Pierre; Carlut, Julie; Isambert, Aude; Durand-Dubief, Mickaël; Ona-Nguema, Georges; Alphandéry, Edouard; Chebbi, Imène; Guyot, François

2018-07-01

Magnetotactic bacteria (MTB) produce intracellular, membrane-bounded magnetite [Fe(II)Fe(III)2O4] crystals in a genetically controlled way. They are ubiquitous in aquatic environments, and have been proposed to represent some of the most ancient biomineralizing organisms on Earth. Although tremendous advances have been made in constraining the mechanisms of magnetite formation in MTB, the precise biomineralization pathways are still a matter of debate. To further constrain the processes of Fe uptake and magnetite precipitation in MTB, Fe stable isotope measurements were carried out with the magnetotactic strain AMB-1 cultivated with Fe(III), Fe(II) or mixed Fe(III)/Fe(II) species in the growth media. The Fe isotope compositions of growth media before and after AMB-1 cultures, bacterial lysates (i.e. cells devoid of magnetite) and magnetite samples were measured. Single valence Fe(III) or Fe(II) growth media after AMB-1 cultures showed depletion in heavy Fe isotopes by 0.2 to 1.5‰ (δ56Fe), relative to the initial Fe source. Contrastingly, heavy Fe isotopes accumulated in the growth media supplemented with mixed Fe(III)/Fe(II) sources, with enrichment up to 0.25‰. These results support a preferential bacterial uptake of Fe(II) when both Fe(III) and Fe(II) are bioavailable. Bacterial lysates contained at least 50% of the total cellular Fe; thus, magnetite was not the main Fe reservoir in AMB-1 under the experimental conditions investigated in this study. In all cultures, bacterial lysates δ56Fe were 0.4 to 0.8‰ higher than the initial Fe sources, while magnetite δ56Fe were 1.2 to 2.5‰ lower. This depletion in heavy Fe isotopes of magnetite can be explained by partial reduction of Fe(III) to Fe(II) within the cell and subsequent magnetite precipitation. The data also show mass-independent fractionations (MIF) in odd (57Fe) but not in even (54Fe, 56Fe, 58Fe) isotopes, expressed mainly in magnetite crystals, and supporting a magnetic isotope effect on 57Fe. Bacterial Fe uptake and MIF patterns suggest that Fe(II) species can freely exchange between the intracellular and external media. Based on these observations, an integrative biogeochemical model for Fe uptake, cellular trafficking, and magnetite precipitation in AMB-1 is presented.

Using stable isotopes of carbon to investigate the seasonal variation of carbon transfer in a northwestern Arkansas cave

USGS Publications Warehouse

Knierim, Katherine J.; Pollock, Erik; Hays, Phillip D.; Khojasteh, Jam

2015-01-01

Stable-isotope analyses are valuable in karst settings, where characterizing biogeochemical cycling of carbon along groundwater flow paths is critical for understanding and protecting sensitive cave and karst water resources. This study quantified the seasonal changes in concentration and isotopic composition (δ13C) of aqueous and gaseous carbon species—dissolved inorganic carbon (DIC) and gaseous carbon dioxide (CO2)—to characterize sources and transfer of these species along a karst flow path, with emphasis on a cave environment. Gas and water samples were collected from the soil and a cave in northwestern Arkansas approximately once a month for one year to characterize carbon cycling along a conceptual groundwater flow path. In the soil, as the DIC concentration increased, the isotopic composition of the DIC became relatively lighter, indicating an organic carbon source for a component of the DIC and corroborating soil DIC as a proxy for soil respiration. In the cave, a positive correlation between DIC and surface temperature was due to increased soil respiration as the organic carbon signal from the soil was transferred to the cave environment via the aqueous phase. CO2 concentration was lowest in the cave during colder months and increased exponentially with increasing surface temperature, presumably due to higher rates of soil respiration during warmer periods and changing ventilation patterns between the surface and cave atmosphere. Isotopic disequilibrium between CO2 and DIC in the cave was greatest when CO2 concentration was changing during November/ December and March/April, presumably due to the rapid addition or removal of gaseous CO2. The isotopic disequilibrium between DIC and CO2 provided evidence that cave CO2 was a mixture of carbon from several sources, which was mostly constrained by mixture between atmospheric CO2 and soil CO2. The concentration and isotopic composition of gaseous and aqueous carbon species were controlled by month-to-month variations in temperature and precipitation and provided insight into the sources of carbon in the cave. Stable carbon isotope ratios provided an effective tool to explore carbon transfer from the soil zone and into the cave, identify carbon sources in the cave, and investigate how seasonality affected the transfer of carbon in a shallow karst system.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Molybdenum Isotopic Composition of Iron Meteorites, Chondrites and Refractory Inclusions

NASA Technical Reports Server (NTRS)

Becker, H.; Walker, R. J.

2003-01-01

Recent Mo isotopic studies of meteorites reported evidence for differences in isotopic compositions for whole rocks of some primitive and differentiated meteorites relative to terrestrial materials. Enrichments of r- and p-process isotopes of up to 3-4 units (e unit = parts in 10(exp 4) over s-process dominated isotopes are the most prominent features. Certain types of presolar grains show large enrichments in s-process isotopes, however, it was concluded on grounds of mass balance that incomplete digestion of such grains cannot explain the enrichments of r- and p-process isotopes in whole rocks of primitive chondrites. If the reported variability in r- and p-process isotope enrichments reflects the true isotopic characteristics of the whole rocks, the implications are quite profound. It would suggest the presence of large scale Mo isotopic heterogeneity within the solar accretion disk with likely collateral effects for other elements. However, such effects were not found for Ru isotopes, nor for Zr isotopes. Another recent Mo isotopic study by multi collector ICP-MS could not confirm the reported deviations in Allende, Murchison or iron meteorites. Here, we present new results for the Mo isotopic composition of iron meteorites, chondrites and CAIs obtained by negative thermal ionization mass spectrometry (NTIMS). We discuss analytical aspects and the homogeneity of Mo isotopic compositions in solar system materials.

Lake carbonate-δ18 records from the Yukon Territory, Canada: Little Ice Age moisture variability and patterns

USGS Publications Warehouse

Anderson, Lesleigh; Finney, Bruce P.; Shapley, Mark D.

2011-01-01

A 1000-yr history of climate change in the central Yukon Territory, Canada, is inferred from sediment composition and isotope geochemistry from small, groundwater fed, Seven Mile Lake. Recent observations of lake-water δ18O, lake level, river discharge, and climate variations, suggest that changes in regional effective moisture (precipitation minus evaporation) are reflected by the lake’s hydrologic balance. The observations indicate that the lake is currently 18O-enriched by summer evaporation and that during years of increased precipitation, when groundwater inflow rates to the lake increase, lake-water δ18O values decrease. Past lake-water δ18O values are inferred from oxygen isotope ratios of fine-grained sedimentary endogenic carbonate. Variations in carbonate δ18O, supplemented by those in carbonate and organic δ13C, C/N ratios, and organic carbon, carbonate and biogenic silica accumulation rates, document changes in effective moisture at decadal time scales during the early Little Ice Age period to present. Results indicate that between ∼AD 1000 and 1600, effective moisture was higher than today. A shift to more arid climate conditions occurred after ∼AD 1650. The 19th and 20th centuries have been the driest of the past millennium. Temporal variations correspond with inferred shifts in summer evaporation from Marcella Lake δ18O, a similarly small, stratified, alkaline lake located ∼250 km to the southwest, suggesting that the combined reconstructions accurately document the regional paleoclimate of the east-central interior. Comparison with regional glacial activity suggests differing regional moisture patterns during early and late Little Ice Age advances.

Lake carbonate-δ 18O records from the Yukon Territory, Canada: Little Ice Age moisture variability and patterns

NASA Astrophysics Data System (ADS)

Anderson, Lesleigh; Finney, Bruce P.; Shapley, Mark D.

2011-04-01

A 1000-yr history of climate change in the central Yukon Territory, Canada, is inferred from sediment composition and isotope geochemistry from small, groundwater fed, Seven Mile Lake. Recent observations of lake-water δ 18O, lake level, river discharge, and climate variations, suggest that changes in regional effective moisture (precipitation minus evaporation) are reflected by the lake's hydrologic balance. The observations indicate that the lake is currently 18O-enriched by summer evaporation and that during years of increased precipitation, when groundwater inflow rates to the lake increase, lake-water δ 18O values decrease. Past lake-water δ 18O values are inferred from oxygen isotope ratios of fine-grained sedimentary endogenic carbonate. Variations in carbonate δ 18O, supplemented by those in carbonate and organic δ 13C, C/N ratios, and organic carbon, carbonate and biogenic silica accumulation rates, document changes in effective moisture at decadal time scales during the early Little Ice Age period to present. Results indicate that between ˜AD 1000 and 1600, effective moisture was higher than today. A shift to more arid climate conditions occurred after ˜AD 1650. The 19th and 20th centuries have been the driest of the past millennium. Temporal variations correspond with inferred shifts in summer evaporation from Marcella Lake δ 18O, a similarly small, stratified, alkaline lake located ˜250 km to the southwest, suggesting that the combined reconstructions accurately document the regional paleoclimate of the east-central interior. Comparison with regional glacial activity suggests differing regional moisture patterns during early and late Little Ice Age advances.

Carbon isotopic composition of forest soil respiration in the decade following bark beetle and stem girdling disturbances in the Rocky Mountains: Carbon isotopes of soil respiration following disturbance

DOE PAGES

Maurer, Gregory E.; Chan, Allison M.; Trahan, Nicole A.; ...

2016-04-26

Bark beetle outbreaks are widespread in western North American forests, reducing primary productivity and transpiration, leading to forest mortality across large areas and altering ecosystem carbon cycling. Here the carbon isotope composition (δ13C) of soil respiration (δJ) was monitored in the decade after disturbance for forests affected naturally by mountain pine beetle infestation and artificially by stem girdling. The seasonal mean δJ changed along both chronosequences. We found (a) enrichment of δJ relative to controls (<1 ‰) in near-surface soils in the first 2 years after disturbance; (b) depletion (1‰ or no change) during years 3–7; and (c) a secondmore » period of enrichment (1–2‰) in years 8–10. Results were consistent with isotopic patterns associated with the gradual death and decomposition of rhizosphere organisms, fine roots, conifer needles and woody roots and debris over the course of a decade after mortality. Finally, δJ was progressively more 13C-depleted deeper in the soil than near the surface, while the bulk soil followed the well-established pattern of 13C-enrichment at depth. Overall, differences in δJ between mortality classes (<1‰) and soil depths (<3‰) were smaller than variability within a class or depth over a season (up to 6‰).« less

Migration of sharks into freshwater systems during the Miocene and implications for Alpine paleoelevation

NASA Astrophysics Data System (ADS)

Kocsis, László; Vennemann, Torsten W.; Fontignie, Denis

2007-05-01

Trace-element and isotopic compositions of fossilized shark teeth sampled from Miocene marine sediments of the north Alpine Molasse Basin, the Vienna Basin, and the Pannonian Basin generally show evidence of formation in a marine environment under conditions geochemically equivalent to the open ocean. In contrast, two of eight shark teeth from the Swiss Upper Marine Molasse locality of La Molière have extremely low δ18O values (10.3‰ and 11.3‰) and low 87Sr/86Sr ratios (0.707840 and 0.707812) compared to other teeth from this locality (21.1‰ 22.4‰ and 0.708421 0.708630). The rare earth element (REE) abundances and patterns from La Molière not only differ between dentine and enameloid of the same tooth, but also between different teeth, supporting variable conditions of diagenesis at this site. However, the REE patterns of enameloid from the “exotic” teeth analyzed for O and Sr isotopic compositions are similar to those of teeth that have O and Sr isotopic compositions typical of a marine setting at this site. Collectively, this suggests that the two “exotic” teeth were formed while the sharks frequented a freshwater environment with very low 18O-content and Sr isotopic composition controlled by Mesozoic calcareous rocks. This is consistent with a paleogeography of high-elevation (˜2300 m) Miocene Alps adjacent to a marginal sea.

Development of a QuEChERS-Based Stable-Isotope Dilution LC-MS/MS Method To Quantitate Ferulic Acid and Its Main Microbial and Hepatic Metabolites in Milk.

PubMed

Waterstraat, Martin; Hildebrand, Andreas; Rosler, Margit; Bunzel, Mirko

2016-11-16

Forage plants of the Poaceae family are grown as pasturage or used for the production of hay, straw, corn stover, etc. Although ferulic acid contents of grasses are generally high, the amount of ingested ferulic acid differs depending on the type of forage, resulting in varying contents of ferulic acid and its microbial and hepatic metabolites in milk. Concentrations and patterns of these metabolites may be used as markers to track different forages in livestock feeding. Therefore, we developed a stable isotope dilution assay to quantitate ferulic acid, 12 ferulic acid-based metabolites, p-coumaric acid, and cinnamic acid in milk. Because most analytes were not commercially available as stable isotope labeled standard compounds, they were synthesized as 13 C- or deuterium-labeled standard compounds. A modification of the QuEChERS method, a Quick, Easy, Cheap, Effective, Rugged, and Safe approach usually applied to analyze pesticides in plant-based products, was used to extract the phenolic acids from milk. Determination was carried out by LC-ESI-MS/MS in scheduled multiple reaction monitoring modus. By using three different milk samples, the applicability of the validated approach was demonstrated.

Seasonal and event variations in δ34S values of stream sulfate in a Vermont forested catchment: Implications for sulfur sources and cycling

USGS Publications Warehouse

Shanley, James B.; Mayer, Bernhard; Mitchell, Myron J.; Bailey, Scott W.

2008-01-01

Stable sulfur (S) isotope ratios can be used to identify the sources of sulfate contributing to streamwater. We collected weekly and high-flow stream samples for S isotopic analysis of sulfate through the entire water year 2003 plus the snowmelt period of 2004. The study area was the 41-ha forested W-9 catchment at Sleepers River Research Watershed, Vermont, a site known to produce sulfate from weathering of sulfide minerals in the bedrock. The δ34S values of streamwater sulfate followed an annual sinusoidal pattern ranging from about 6.5‰ in early spring to about 10‰ in early fall. During high-flow events, δ34S values typically decreased by 1 to 3‰ from the prevailing seasonal value. The isotopic evidence suggests that stream sulfate concentrations are controlled by: (1) an overall dominance of bedrock-derived sulfate (δ34S ~ 6–14‰); (2) contributions of pedogenic sulfate (δ34S ~ 5–6‰) during snowmelt and storms with progressively diminishing contributions during base flow recession; and (3) minor effects of dissimilatory bacterial sulfate reduction and subsequent reoxidation of sulfides. Bedrock should not be overlooked as a source of S in catchment sulfate budgets.

Discovering complex groundwater dynamics of a multiple aquifer system on the base of stable and radio-isotope patterns

NASA Astrophysics Data System (ADS)

Wilske, Cornelia; Rödiger, Tino; Suckow, Axel; Geyer, Stefan; Weise, Stephan; Merchel, Silke; Rugel, Georg; Pavetich, Stefan; Merkel, Broder; Siebert, Christian

2017-04-01

The water supply in semi-arid Israel and Palestine, predominantly relies on groundwater as freshwater resource, stressed by increasing demand and low recharge rates. Sustainable management of such resources requires a sound understanding of its groundwater migration through space and time, particularly in structurally complex multi-aquifer systems as the Eastern Mountain Aquifer, affected by salting. To differentiate between the flow paths of the different water bodies and their respective residence times, a multi-tracer approach, combining age dating isotopes (36Cl/Cl; 3H) with rock specific isotopes like 87Sr/86Sr and δ34S-SO4 was applied. As a result, the investigated groundwaters from the two Cretaceous aquifers and their respective flow paths are differentiable by e.g. their 87Sr/86Sr signatures, resembling the intensity of the rock-water interaction and hence indirectly residence times. In the discharge areas within the Jordan Valley and along the Dead Sea shore, δ34S-SO4 ratios reveal the different sources of salinity (ascending brines, interstitial brines and dissolved salts). Based on 36Cl and 3H and the atmospheric input functions, very heterogeneous infiltration times and effective flow velocities, respectively, indicate an at least dual porosity system, resulting in distinctly different regimes of matrix and pipe flow.

First-principles theory of anharmonicity and the inverse isotope effect in superconducting palladium-hydride compounds.

PubMed

Errea, Ion; Calandra, Matteo; Mauri, Francesco

2013-10-25

Palladium hydrides display the largest isotope effect anomaly known in the literature. Replacement of hydrogen with the heavier isotopes leads to higher superconducting temperatures, a behavior inconsistent with harmonic theory. Solving the self-consistent harmonic approximation by a stochastic approach, we obtain the anharmonic free energy, the thermal expansion, and the superconducting properties fully ab initio. We find that the phonon spectra are strongly renormalized by anharmonicity far beyond the perturbative regime. Superconductivity is phonon mediated, but the harmonic approximation largely overestimates the superconducting critical temperatures. We explain the inverse isotope effect, obtaining a -0.38 value for the isotope coefficient in good agreement with experiments, hydrogen anharmonicity being mainly responsible for the isotope anomaly.

Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

NASA Technical Reports Server (NTRS)

Morgan, Leah E.; Lloyd, Nicholas S.; Ellam, Robert M.; Simon, Justin I.

2012-01-01

Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample-standard bracketing. As cold plasma conditions can amplify matrix effects, experiments were conducted to test the matrix tolerance of measurements; the use of clean, matrix-matched samples and standards is critical. Limitations of the cold-plasma high-resolution MC-ICP-MS methodology with respect to matrix tolerance are discussed and compared with the limitations of TIMS methodologies.

The Alaska Water Isotope Network (AKWIN): Precipitation, lake, river and stream dynamics

NASA Astrophysics Data System (ADS)

Rogers, M.; Welker, J. M.; Toohey, R.

2011-12-01

The hydrologic cycle is central to the structure and function of northern landscapes. The movement of water creates interactions between terrestrial, aquatic, marine and atmospheric processes. Understanding the processes and the spatial patterns that govern the isotopic (δ18O & δD) characteristics of the hydrologic cycle is especially important today as: a) modern climate/weather-isotope relations allow for more accurate interpretation of climate proxies and the calibration of atmospheric models, b) water isotopes facilitate understanding the role of storm tracks in regulating precipitation isotopic variability, c) water isotopes allow for estimates of glacial melt water inputs into aquatic systems, d) water isotopes allow for quantification of surface and groundwater interactions, e) water isotopes allow for quantification of permafrost meltwater use by plant communities, f) water isotopes aid in migratory bird forensics, g) water isotopes are critical to estimating field metabolic rates, h) water isotopes allow for crop and diet forensics and i) water isotopes can provide insight into evaporation and transpiration processes. As part of a new NSF MRI project at the Environment and Natural Resources Institute (ENRI) at the University of Alaska Anchorage and as an extension of the US Network for Isotopes in Precipitation (USNIP); we are forming AKWIN. The network will utilize long-term weekly sampling at Denali National Park and Caribou Poker Creek Watershed (USNIP sites-1989 to present), regular sampling across Alaska involving land management agencies (USGS, NPS, USFWS, EPA), educators, volunteers and citizen scientists, UA extended campuses, individual research projects, opportunistic sampling and published data to construct isoscapes and time series databases and information packages. We will be using a suite of spatial and temporal analysis methods to characterize water isotopes across Alaska and will provide web portals for data products. Our network is designed to interface with the existing USNIP and will provide a research and data platform that will assist with answering the core questions of NEON addressing climate and land use change in Alaska, in the north and across the US.

Clumped isotope composition of cold-water corals: A role for vital effects?

NASA Astrophysics Data System (ADS)

Spooner, Peter T.; Guo, Weifu; Robinson, Laura F.; Thiagarajan, Nivedita; Hendry, Katharine R.; Rosenheim, Brad E.; Leng, Melanie J.

2016-04-01

The carbonate clumped isotope thermometer is a promising tool for determining past ocean temperatures. It is based on the temperature dependence of rare isotopes 'clumping' into the same carbonate ion group in the carbonate mineral lattice. The extent of this clumping effect is independent of the isotope composition of the water from which carbonate precipitates, providing unique advantages over many other paleotemperature proxies. Existing calibrations of this thermometer in cold-water and warm-water corals suggest clumped isotope 'vital effects' are negligible in cold-water corals but may be significant in warm-water corals. Here, we test the calibration of the carbonate clumped isotope thermometer in cold-water corals with a recently collected and well characterised sample set spanning a range of coral genera (Balanophyllia, Caryophyllia, Dasmosmilia, Desmophyllum, Enallopsammia and Javania). The clumped isotope compositions (Δ47) of these corals exhibit systematic dependences on their growth temperatures, confirming the basis of the carbonate clumped isotope thermometer. However, some cold-water coral genera show Δ47 values that are higher than the expected equilibrium values by up to 0.05‰ (equivalent to underestimating temperature by ∼9 °C) similar to previous findings for some warm-water corals. This finding suggests that the vital effects affecting corals Δ47 are common to both warm- and cold-water corals. By comparison with models of the coral calcification process we suggest that the clumped isotope offsets in these genera are related to the kinetic isotope effects associated with CO2 hydration/hydroxylation reactions in the corals' calcifying fluid. Our findings complicate the use of the carbonate clumped isotope thermometer in corals, but suggest that species- or genus-specific calibrations could be useful for the future application of this paleotemperature proxy.

Multiple sulfur isotope constraints on sulfate-driven anaerobic oxidation of methane: Evidence from authigenic pyrite in seepage areas of the South China Sea

NASA Astrophysics Data System (ADS)

Lin, Zhiyong; Sun, Xiaoming; Strauss, Harald; Lu, Yang; Gong, Junli; Xu, Li; Lu, Hongfeng; Teichert, Barbara M. A.; Peckmann, Jörn

2017-08-01

Multiple sulfur isotope signatures and secondary ion mass spectroscopy (SIMS) sulfur isotope compositions of pyrite from two seafloor sites (DH-CL11 and HD109) in seepage areas of the South China Sea were measured in order to study isotope effects of sulfate-driven anaerobic oxidation of methane (SO4-AOM). The multiple sulfur isotopes of pyrite reveal variable ranges for both sites (δ34S: between -44.1‰ and -2.9‰ for DH-CL11 and between -43.8‰ and -1.6‰ for HD109; Δ33S: between 0.02‰ and 0.17‰ for DH-CL11 and between -0.03‰ and 0.14‰ for HD109). SIMS analysis reveals an extreme variability of δ34S values (between -50.3‰ and -2.7‰ in DH-CL11; between -50.1 and 52.4‰ in HD109) for three types of pyrite: (1) framboids, (2) zoned aggregates with radial overgrowth surrounding a framboidal core, and (3) euhedral pyrite crystals. The synchronous changes of geochemical proxies (sulfate and methane concentrations, δ34Ssulfate and δ18Osulfate, δ34Spyrite, and pyrite content) at the sulfate-methane transition zone (SMTZ) at site DH-CL11 are interpreted to be induced by SO4-AOM under steady state conditions. In contrast, pyrite content and δ34S value fluctuations throughout core HD109 suggest that the sediment at this site was affected by multiple pyritization events during diagenesis. Multiple sulfur isotope signatures of early diagenetic pyrite (i.e., with low and high δ34S values, the latter above 315 cmbsf in DH-CL11; above 70 cmbsf in HD109) in the upper sediment column suggest that organoclastic sulfate reduction (OSR) and sulfur disproportionation generated the observed isotopic signatures. In contrast to the early diagenetic 34S depleted framboids, the higher SIMS δ34S values of overgrowth and euhedral crystals suggest a late diagenetic 34S enriched pool of dissolved sulfide derived from SO4-AOM at the current and paleo-SMTZs. Interestingly, pyrite resulting from SO4-AOM in the SMTZ at site DH-CL11 reveals a distinct pattern with higher Δ33S values, different from pyrite resulting from OSR and sulfur disproportionation. Therefore, paired δ34S and Δ33S values may allow to differentiate OSR and SO4-AOM, although a full understanding of the isotope effects associated with SO4-AOM is hampered by uncertainties on the actual electron transfer mechanism in the syntrophic SO4-AOM consortium.