Real-time isotope monitoring network at the Biosphere 2 Landscape Evolution Observatory resolves meter-to-catchment scale flow dynamics

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Van Haren, J. L. M.; Kim, M.; Harman, C. J.; Pangle, L.; Meredith, L. K.; Troch, P. A.

2017-12-01

Stable isotope analysis is a powerful tool for tracking flow pathways, residence times, and the partitioning of water resources through catchments. However, the capacity of stable isotopes to characterize catchment hydrological dynamics has not been fully exploited as commonly used methodologies constrain the frequency and extent at which isotopic data is available across hydrologically-relevant compartments (e.g. soil, plants, atmosphere, streams). Here, building upon significant recent developments in laser spectroscopy and sampling techniques, we present a fully automated monitoring network for tracing water isotopes through the three model catchments of the Landscape Evolution Observatory (LEO) at the Biosphere 2, University of Arizona. The network implements state-of-the-art techniques for monitoring in great spatiotemporal detail the stable isotope composition of water in the subsurface soil, the discharge outflow, and the atmosphere above the bare soil surface of each of the 330-m2 catchments. The extensive valving and probing systems facilitate repeated isotope measurements from a total of more than five-hundred locations across the LEO domain, complementing an already dense array of hydrometric and other sensors installed on, within, and above each catchment. The isotope monitoring network is operational and was leveraged during several months of experimentation with deuterium-labelled rain pulse applications. Data obtained during the experiments demonstrate the capacity of the monitoring network to resolve sub-meter to whole-catchment scale flow and transport dynamics in continuous time. Over the years to come, the isotope monitoring network is expected to serve as an essential tool for collaborative interdisciplinary Earth science at LEO, allowing us to disentangle changes in hydrological behavior as the model catchments evolve in time through weathering and colonization by plant communities.

Isotope Geochemistry for Comparative Planetology of Exoplanets

NASA Technical Reports Server (NTRS)

Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

2017-01-01

Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

Integrating isotopic fingerprinting with petrology: how do igneous rocks evolve?

NASA Astrophysics Data System (ADS)

Davidson, J. P.

2002-12-01

In the title of his seminal work, N.L. Bowen recognized the fundamental importance of magmatic evolution in producing the spectrum of igneous rocks. Indeed it is difficult to imagine a hot highly reactive fluid passing through c. 100 km of a chemically distinct medium (lithosphere) without evolving through cooling, crystallization and interaction with the wall rocks. The fact that magmas evolve - almost invariably through open system processes - has been largely marginalized in the past 30 years by the desire to use them as probes of mantle source regions. This perspective has been driven principally by advances offered by isotope geochemistry, through which components and sources can be effectively fingerprinted. Two fundamental observations urge caution in ignoring differentiation effects; 1) the scarcity of truly primary magmas according to geochemical criteria (recognized long ago by petrologists), and 2) the common occurrence of petrographic criteria attesting to open system evolution. Recent advances in multicollector mass spectrometry permit integration of the powerful diagnostic tools of isotope geochemistry with petrographic observations through accurate and precise analysis of small samples. Laser ablation and microdrilling enable sampling within and between mineral phases. The results of our microsampling investigations give widespread support for open system evolution of magmas, and provide insights into the mechanisms and timescales over which this occurs. For example; 1) core-rim decreases in 87Sr/86Sr in zoned plagioclase crystals from 1982 lavas of El Chichon volcano, Mexico, argue that the zoning and isotopic changes are in response to magma recharge mixing with an originally contaminated resident magma; 2) Single grain and intra-grain isotopic analyses of mineral phases from Ngauruhoe andesites (New Zealand) are highly variable, arguing that bulk rock data reflect mechanical aggregations of components which have evolved in discrete domains of the magma storage and delivery system; 3) 87Sr/86Sr variations within feldspars from a single ignimbrite exceed the entire rhyolite bulk rock range of 87Sr/86Sr recorded from the Taupo volcanic zone, New Zealand; arguing that the isotopic heterogeneity encountered during differentiation is greater than that erupted; and 4) Gabbros from the Rum intrusion (NW Scotland) exhibit inter and intra-grain isotopic heterogeneity arguing that accumulation involved mixing of crystal populations which evolved in different domains of an open system magma chamber. These studies suggest that isotopic modification of magmas in the crust (according to P-T estimates of plagiocalse stability) is the rule rather than the exception. Although it is conceivable that isotopic signatures are all inherited from mantle-derived melts which interacted before, during and after crystal growth, it is more likely that the isotopic diversity reflects contamination and mixing which obscures the signature of the mantle contributions. Furthermore, it is perhaps unrealistic to think of the evolution of a particular igneous rock. Rather each rock appears to be an aggregate of components with separate evolutionary histories. Because isotopic composition is leveraged by the mass balance of these components (Sr is typically concentrated in plagioclase, Nd in glass and accessories, Hf in zircon, Pb in feldspar and glass), the isotopic systematics of bulk rocks can become decoupled from each other. Thus the isotope characteristics of the rock components give a more faithful record of evolution processes than the bulk rock itself.

Recharge sources and geochemical evolution of groundwater in the Quaternary aquifer at Atfih area, the northeastern Nile Valley, Egypt

NASA Astrophysics Data System (ADS)

El-Sayed, Salah Abdelwahab; Morsy, Samah M.; Zakaria, Khalid M.

2018-06-01

This study addresses the topic of recharge sources and evolution of groundwater in the Atfih area situated in the northeastern part of the Nile Valley, Egypt. Inventory of water wells and collection of groundwater and surface water samples have been achieved. Water samples are analyzed for major ions according to the American Society for Testing and Materials and for the environmental isotopes analysis (oxygen-18 and deuterium) by using a Triple Liquid Isotopic Water Analyzer (Los Gatos). The groundwater is available from the Quaternary aquifer formed mainly of graded sand and gravel interbedded with clay lenses. The hydrogeologic, hydrogeochemical and isotopic investigations indicate the hydrodynamic nature of the aquifer, where different flow paths, recharge sources and evolution mechanisms are distinguished. The directions of groundwater flow are from E, W and S directions suggesting the contribution from Nile River, the Eocene aquifer and the Nile basin, respectively. The groundwater altitudes range from 13 m (MSL) to 44 m (MSL). The hydraulic gradient varies between 0.025 and 0.0015. The groundwater is alkaline (pH > 7) and has salinity ranging from fresh to brackish water (TDS between 528 mg/l and 6070 mg/l). The observed wide range in the ionic composition and water types reflects the effect of different environmental and geological conditions through which the water has flowed. The isotopic compositions of groundwater samples vary between -14.13‰ and +23.56 for δD and between - 2.91‰ and +3.10 for δ18O. The isotopic data indicates that the Quaternary aquifer receive recharge from different sources including the Recent Nile water, surplus irrigation water, old Nile water before the construction of Aswan High Dam, surface runoff of local rains and Eocene aquifer. Evaporation, water rock interaction and mixing between different types of waters are the main processes in the groundwater evolution. Major suggestions are presented to develop the aquifer productivity and to mitigate the deterioration of groundwater quality.

Simulation of dual carbon-bromine stable isotope fractionation during 1,2-dibromoethane degradation.

PubMed

Jin, Biao; Nijenhuis, Ivonne; Rolle, Massimo

2018-06-01

We performed a model-based investigation to simultaneously predict the evolution of concentration, as well as stable carbon and bromine isotope fractionation during 1,2-dibromoethane (EDB, ethylene dibromide) transformation in a closed system. The modelling approach considers bond-cleavage mechanisms during different reactions and allows evaluating dual carbon-bromine isotopic signals for chemical and biotic reactions, including aerobic and anaerobic biological transformation, dibromoelimination by Zn(0) and alkaline hydrolysis. The proposed model allowed us to accurately simulate the evolution of concentrations and isotope data observed in a previous laboratory study and to successfully identify different reaction pathways. Furthermore, we illustrated the model capabilities in degradation scenarios involving complex reaction systems. Specifically, we examined (i) the case of sequential multistep transformation of EDB and the isotopic evolution of the parent compound, the intermediate and the reaction product and (ii) the case of parallel competing abiotic pathways of EDB transformation in alkaline solution.

Hydrogeochemical processes and isotopes analysis. Study case: "La Línea Tunnel", Colombia

NASA Astrophysics Data System (ADS)

Piña, Adriana; Donado, Leonardo; Cramer, Thomas

2017-04-01

Hydrogeochemical and stable isotopes analyses have been widely used to identify recharge and discharge zones, flowpaths, type, origin and age of water, chemical processes between minerals and groundwater as well as effects caused by anthropogenic or natural pollution. In this paper we analyze the interactions between groundwater and surface water using as laboratory the tunnels located at the La Línea Massif in the Cordillera Central of the Colombian Andes. The massif is formed by two igneous-metamorphic fractured complexes (Cajamarca and Quebradagrande group) plus andesithic porphyry rocks from the tertiary period. There, eight main fault zones related to surface creeks were identified and main inflows inside the tunnels were reported. 60 water samples were collected in surface and inside the tunnel in fault zones in two different years, 2010 and 2015. To classify water samples, a multivariate statistical analysis combining Factor Analysis (FA) with Hierarchical Cluster Analysis (HCA) was performed. Then, analyses of the major chemical elements and water isotopes (18O, 2H and 3H) were used to define the origin of dissolved components and to analyse the evolution in time. Most samples were classified as bicarbonate calcite water or bicarbonate magnesium water type. Isotopic analyses show a characteristic behavior for east and west watershed and each geologic group. According to the FA and HCA, obtained factors and clusters are first related to the location of the samples (surface or tunnel samples) followed by the geology. Surface samples behave according to the Colombian meteoric line as inflows related to permeable faults while less permeable faults show hydrothermal processes. Finally, water evolution in time shows a decrease of pH, conductivity and Mg2+ related to silicate weathering or precipitation/dissolution processes that affect the spacing in fractures and consequently, the hydraulic properties.

Shape evolution with angular momentum in Lu isotopes

NASA Astrophysics Data System (ADS)

Kardan, Azam; Sayyah, Sepideh

2016-06-01

The nuclear potential energies of Lu isotopes with neutron number N = 90 - 98 up to high spins are computed within the framework of the unpaired cranked Nilsson-Strutinsky method. The potential and the macroscopic Lublin-Strasbourg drop (LSD) energy-surface diagrams are analyzed in terms of quadrupole deformation and triaxiality parameter. The shape evolution of these isotopes with respect to angular momentum, as well as the neutron number is studied.

Using environmental isotopes along with major hydro-geochemical compositions to assess deep groundwater formation and evolution in eastern coastal China

NASA Astrophysics Data System (ADS)

Xu, Naizheng; Gong, Jianshi; Yang, Guoqiang

2018-01-01

Hydrochemical analysis and environmental isotopic tracing are successfully applied to study groundwater evolution processes. Located in eastern China, the Jiangsu Coastal Plain is characterized by an extensively exploited deep groundwater system, and groundwater salinization has become the primary water environmental problem. This paper provides a case study on the use of a hydrochemical and environmental isotopic approach to assess possible mixing and evolution processes at Yoco Port, Jiangsu Province, China. Hydrochemical and isotopic patterns of deep groundwater allow one to distinguish different origins in deep water systems. HCO3- is the dominant anion in the freshwater samples, whereas Na+ and Cl- are the dominant major ions in the saline samples. According to δ18O, δ2H and 14C dating, the fresh water is derived from precipitation under a colder climate during the Glacial Maximum (Dali Glacial), while the saline groundwater is influenced by glacial-interglacial cycles during the Holocene Hypsithermal. The δ18O, δ2H and 3H data confirm that deep groundwater in some boreholes is mixed with overlying saline water. The deep groundwater reservoir can be divided into a saline water sector and a fresh water sector, and each show distinct hydrochemical and isotopic compositions. The saline groundwater found in the deep aquifer cannot be associated with present seawater intrusion. Since the Last Glacial Maximum in the Late Pleistocene, the deep groundwater flow system has evolved to its current status with the decrease in ice cover and the rising of sea level. However, the hydraulic connection is strengthened by continuous overexploitation, and deep groundwater is mixed with shallow groundwater at some points.

Using environmental isotopes along with major hydro-geochemical compositions to assess deep groundwater formation and evolution in eastern coastal China.

PubMed

Xu, Naizheng; Gong, Jianshi; Yang, Guoqiang

2018-01-01

Hydrochemical analysis and environmental isotopic tracing are successfully applied to study groundwater evolution processes. Located in eastern China, the Jiangsu Coastal Plain is characterized by an extensively exploited deep groundwater system, and groundwater salinization has become the primary water environmental problem. This paper provides a case study on the use of a hydrochemical and environmental isotopic approach to assess possible mixing and evolution processes at Yoco Port, Jiangsu Province, China. Hydrochemical and isotopic patterns of deep groundwater allow one to distinguish different origins in deep water systems. HCO 3 - is the dominant anion in the freshwater samples, whereas Na + and Cl - are the dominant major ions in the saline samples. According to δ 18 O, δ 2 H and 14 C dating, the fresh water is derived from precipitation under a colder climate during the Glacial Maximum (Dali Glacial), while the saline groundwater is influenced by glacial-interglacial cycles during the Holocene Hypsithermal. The δ 18 O, δ 2 H and 3 H data confirm that deep groundwater in some boreholes is mixed with overlying saline water. The deep groundwater reservoir can be divided into a saline water sector and a fresh water sector, and each show distinct hydrochemical and isotopic compositions. The saline groundwater found in the deep aquifer cannot be associated with present seawater intrusion. Since the Last Glacial Maximum in the Late Pleistocene, the deep groundwater flow system has evolved to its current status with the decrease in ice cover and the rising of sea level. However, the hydraulic connection is strengthened by continuous overexploitation, and deep groundwater is mixed with shallow groundwater at some points. Copyright © 2017 Elsevier B.V. All rights reserved.

The sources and time-integrated evolution of diamond-forming fluids - Trace elements and isotopic evidence

NASA Astrophysics Data System (ADS)

Klein-BenDavid, Ofra; Pearson, D. Graham; Nowell, Geoff M.; Ottley, Chris; McNeill, John C. R.; Logvinova, Alla; Sobolev, Nikolay V.

2014-01-01

Sub-micrometer inclusions in fibrous diamond growth zones 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 major and trace element patterns of diamond-forming fluids vary widely. Such 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. Thus, the combination of elemental and isotope data is a powerful tool in constraining the origin of fluids from which diamonds precipitate. Here we present combined trace element composition (34 diamonds) and Sr isotopic data (23 diamonds) for fluid-rich diamonds from six worldwide locations. The Nd and Pb isotopic composition of two of the diamonds were also obtained. Several of the samples were analyzed in at least 2 locations to investigate variations in the fluid during diamond growth. The data was acquired using an off-line laser sampling technique followed by solution ICPMS and TIMS analysis. The Sr isotopic compositions of diamond fluids from the different suites range between convecting mantle values for Udachnaya (87Sr/86Sr363 = 0.70300 ± 16 to 0.70361 ± 4), to highly enriched values, up to 87Sr/86Sr = 0.72330 ± 3, for a diamond from Congo. No isochronous relationships were observed in any of the suites. The lowest Nd isotopic composition recorded so far in a diamond is from Congo (εNd71 = -40.4), which also contains the most radiogenic Sr isotopic composition. In contrast, a less enriched but still rather unradiogenic Nd isotope composition (εNd540 = -11) was obtained for a diamond from Snap Lake, which has moderately radiogenic Sr isotopic enrichment (87Sr/86Sr540 = 0.70821 ± 1). The Pb isotopic system measured in one diamond indicates a complex evolution for the fluid source, with extreme 207Pb/204Pb ratio (15.810 ± 3) and moderate, kimberlite-like 206Pb/204Pb and 208Pb/204Pb ratios. A multi-stage evolution of the diamond-forming fluids source can be constrained from our new isotopic data, indicating an Achaean enrichment event resulting in elevated U/Pb, Rb/Sr ratios and enrichment in LREEs. This source underwent a more recent fractionation, in the last 500 Myr that may have been related to the diamond-forming event. There is a strong correspondence between fluids with relatively unradiogenic Sr isotopes and relatively low (La, Nd, Sm)/(Nb, Zr) and (Ba, Th)/(Nb) ratios. Sr isotopic enrichment is accompanied by an increase in these ratios. The least trace element enriched and most isotopically depleted fluids are from the high-Mg carbonatitic suite. Thus, HDFs could be derived from asthenospheric mantle as low degree melts that interact to varying degrees with an ancient, metasomatized, rutile- and phlogopite bearing, sub continental lithosphere mantle. The internal heterogeneity in the Sr isotopic ratios within a single diamond suite and even within single diamonds may indicate fluid-mixing processes. Such mixing may occur during migration through preferred mantle veins and may be affected by the small-scale geochemical variability within them.

Open system models of isotopic evolution in Earth's silicate reservoirs: Implications for crustal growth and mantle heterogeneity

NASA Astrophysics Data System (ADS)

Kumari, Seema; Paul, Debajyoti; Stracke, Andreas

2016-12-01

An open system evolutionary model of the Earth, comprising continental crust (CC), upper and lower mantle (UM, LM), and an additional isolated reservoir (IR) has been developed to study the isotopic evolution of the silicate Earth. The model is solved numerically at 1 Myr time steps over 4.55 Gyr of Earth history to reproduce both the present-day concentrations and isotope ratios of key radioactive decay systems (Rb-Sr, Sm-Nd, and U-Th-Pb) in these terrestrial reservoirs. Various crustal growth scenarios - continuous versus episodic and early versus late crustal growth - and their effect on the evolution of Sr-Nd-Pb isotope systematics in the silicate reservoirs have been evaluated. Modeling results where the present-day UM is ∼60% of the total mantle mass and a lower mantle that is non-primitive reproduce the estimated geochemical composition and isotope ratios in Earth's silicate reservoirs. The isotopic evolution of the silicate Earth is strongly affected by the mode of crustal growth; only an exponential crustal growth pattern with crustal growth since the early Archean satisfactorily explains the chemical and isotopic evolution of the crust-mantle system and accounts for the so-called Pb paradoxes. Assuming that the OIB source is located in the deeper mantle, our model could, however, not reproduce its target ɛNd of +4.6 for the UM, which has been estimated from the average isotope ratios of 32 individual ocean island localities. Hence, either mantle plumes sample the LM in a non-representative way, or the simplified model set-up does not capture the full complexity of Earth's lower mantle (Nd isotope) evolution. Compared to the results obtained for a 4.55 Ga Earth, a model assuming a protracted U-Pb evolution of silicate Earth by ca. 100 Myr reproduces a slightly better fit for the Pb isotope ratios in Earth's silicate reservoirs. One notable feature of successful models is the early depletion of incompatible elements (as well as rapid decrease in Th/U) in the UM within the initial 500 Myr, as a result of early formation of CC, which supports other evidence in favor of the presence of Hadean continental crust. Therefore, a chondritic Th/U ratio (4 ± 0.2) in the UM until 2 Gyr appears rather unlikely. We find that the κ conundrum - the observation that measured Th/U ratios and those deduced from 208Pb-206Pb isotope systematics differ - is a natural outcome of an open system evolution in which preferential recycling of U for the past 2 Gyr has played a dominant role. Overall, our simulations strongly favor exponential crustal growth, starting in the early Hadean, the transient preservation of compositionally distinct mantle reservoirs over billion year time periods, and a generally less incompatible element depleted, but non-primitive composition of the lower mantle.

A climate and environmental context for hominid evolution: Preliminary biomarker and compound specific isotope data from Lake Magadi, Kenya

NASA Astrophysics Data System (ADS)

Werne, J. P.; Ferland, T.; Cohen, A. S.; Lowenstein, T. K.; Deocampo, D.; Renaut, R.; Bernhart, O. R.

2016-12-01

The Hominid Sites and Paleolakes Drilling Project (HSPDP) seeks to understand the paleoclimatic and paleoenvironmental context of human evolution and development by analysis of paleolacustrine cores taken near key hominin fossil and artifact localities in Kenya and Ethiopia. Here, we present biomarker and compound specific isotope data from a 200 m drill core from Lake Magadi, Kenya. Located 20 km from the Koora Plain in the southern Kenya Rift, and adjacent to the Olorgesailie basin, Lake Magadi is in one of the richest Early-Late Pleistocene archaeological localities in Africa, a region that has been key in debates about the relationship between climate and evolution. Preliminary biomarker work has shown promising abundances of leaf waxes, whose isotopic compositions of hydrogen and carbon are commonly used as proxies for paleoprecipitation and watershed vegetation composition, respectively. A complementary record of glycerol dialkyl glycerol tetraethers (GDGTs), which can serve as a proxy for temperature, soil input, and/or pH, will be presented alongside the leaf wax data to enhance the paleoenvironmental reconstruction of Lake Magadi. Present-day Lake Magadi is a saline pan, a descendant of a series of paleolakes that have occupied its drainage basin for approximately one million years. Hominid evolution milestones such as the mastering of fire as a tool, rapid encephalization, and the emergence of Homo sapiens all are thought to have occurred in the time frame encompassed by our record.

An Impaired View of Earth's Early History

NASA Astrophysics Data System (ADS)

Vervoort, J. D.; Kemp, A. I.; Bauer, A.; Bowring, S. A.; Fisher, C.

2014-12-01

The Hf and Nd isotope records of Earth's early history are sparse, difficult to interpret, and controversial, much like the few remnants of crust older than 4 Ga. New analytical techniques have been brought to bear on this problem but despite this recent work­-or, perhaps, because of it-the record is no clearer than it was 15 years ago. Several studies, based on highly variable calculated initial isotopic compositions, have argued for highly heterogeneous crust and mantle reservoirs in the early Earth1,2 and an ultra-depleted Eoarchean mantle3. These data come mostly from two sources: Hf-Nd isotope analyses of ultramafic rocks and Hf isotope analyses of zircons by solution or laser ablation. An important question for understanding the chemical evolution of the early Earth is: Do these data offer a unique window into the early Earth or are they artefacts not representative of crust/mantle evolution, giving an impaired view of the Earth's early history? In complex samples, measured isotopic compositions can result from open-system behavior in easily altered ultramafic compositions, in multicomponent, polymetamorphic gneisses, or in zircons with multiple generations of growth. Perhaps most importantly, accurate age assignment is often lacking, compromised, or impossible in these rocks, making calculation of initial epsilon Hf and Nd values ambiguous at best. In order to gain insight into crust mantle evolution in the early Earth we need, above all, a robust and unambiguous isotopic record to work with. This can be achieved by integrating zircon U-Pb and Hf and whole-rock Hf and Nd isotope compositions in relatively undisturbed igneous rocks with well-constrained ages. When this approach is used apparent isotopic heterogeneity decreases and a simpler model for crust-mantle evolution in the early Earth emerges. Careful screening of geological relationships, petrology, and geochemistry of samples from the early Earth should be done before interpreting isotopic data. Indiscriminate inclusion of isotope data from disturbed and multicomponent rocks and zircons will do more to obscure our understanding of the Hf-Nd isotope evolution of the Earth than to clarify it. [1] Harrison et al. 2005, Science 310, 1947-1950. [2] Blichert-Toft and Albarède, 2008, EPSL 265, 686-702. [3] Hoffmann et al., 2010, GCA, 74, 7236-7260.

The evolution of 13C and 18O isotope composition of DIC in a calcite depositing film of water with isotope exchange between the DIC and a CO2 containing atmosphere, and simultaneous evaporation of the water. Implication to climate proxies from stalagmites: A theoretical model

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Romanov, Douchko

2016-12-01

The most widely applied climate proxies in speleothems are the isotope compositions of carbon and oxygen expressed by δ13C and δ18O values. However, mechanisms, which are not related to climate changes, overlay the climate signal. One is the temporal increase of both, δ13C and δ18O values by kinetic processes during precipitation of calcite. Isotope exchange between DIC in the water and the CO2 in the surrounding cave atmosphere can also change isotope composition. Here we present a theoretical model of the temporal isotope evolution of DIC in a thin water layer during precipitation of calcite and simultaneous isotope exchange with the cave atmosphere, and simultaneous evaporation of water. The exchange of oxygen isotopes in the DIC with those in the water is also considered.

New Insights Into the Genesis and Compositional Evolution of I-type Granitic magmas in the Lachlan Fold Belt (SE Australia) by in situ Hf Isotopic Analysis of Zircon

NASA Astrophysics Data System (ADS)

Kemp, T. I.; Hawkesworth, C. J.; Hergt, J. M.; Woodhead, J.

2004-05-01

Isotope studies have proved of enormous benefit in fingerprinting the source rocks of silicic magmas and tracing open system petrogenetic processes, such as crustal assimilation or magma mixing. Quantification of these processes, especially the role of mantle-derived magmas, is essential to formulating realistic models for the thermal regime and compositional evolution of the continental crust. However, this remains problematic, since whole-rock isotopic data registers the final state of the magmatic system but gives no information on the pathways by which this state was attained. For example, the eNd - initial 87Sr/86Sr isotopic array defined by the classic I- and S-type granites of the Lachlan Fold Belt has been variously interpreted to reflect (1) mixing between two end-member magmas, one depleted mantle-like, the other evolved and continental crust-like, (2) mixing between a juvenile magma and a magma sourced from mafic lower crust, accompanied by sediment assimilation, (3) derivation of the granites from mixed source rocks and (4) derivation from a sequence of protoliths of various ages and sedimentary maturity. The implications of these possibilities for crustal architecture, and whether granitic magmatism was associated with the recycling or growth of new continental crust are drastically different. One way to now resolve such ambiguities is by unravelling the isotopic information encoded in the fine-scale growth zoning of minerals such as zircon, which potentially tracks the processes operative during crystallisation. To this end we report the first laser-ablation ICP-MS study into the Hf isotope stratigraphy of zircons hosted by LFB I-type granites and their mafic enclaves. This is integrated with a prior U-Pb isotope study and trace element concentrations measured on the same zircons. Two suites were investigated, the Cobargo and Why Worry Suites of the Bega Batholith. Although the bulk rock isotopic variation within these suites is restricted, this study reveals remarkable fluctuations in Hf isotopic ratios recorded within and between melt-precipitated zircons of granitic and enclave samples. This can only be reconciled by open-system behaviour, though contrasting patterns of Hf isotope variation within zoned zircons demonstrate that this differed significantly between the two suites. The Cobargo Suite was generated by mixing between two contrasting magmas, followed by crustal assimilation. Zircons from the Why Worry Suite have more evolved Hf isotope ratios, consistent with recycling of older crust during granitic generation, though increase in eHf towards zircon rims manifests interaction with primitive magmas. Globules of these are represented by mafic enclaves, the mantle heritage of which is preserved by high eHf values of zircon cores, even though whole-rock isotope contrasts with the host have been erased by equilibration. Analysis of inherited zircons contained by the Why Worry Suite establishes that the 450-600 Ma age population have evolved eHf values, and thus meta-igneous rocks of this age are appropriate protoliths for these granites. The primitive eHf values of the Cobargo Suite preclude derivation from similar sources, instead suggesting formation from mantle-derived materials. Incorporating the existing geochemical and isotope datasets, the Hf-in-zircon data will be coupled with recent thermal simulations to erect a general model for granite formation and the evolution of the continental crust during Lachlan orogenesis.

Archean Pb Isotope Evolution: Implications for the Early Earth.

NASA Astrophysics Data System (ADS)

Vervoort, J. D.; Thorpe, R.; Albarede, F.; Blichert-Toft, J.

2008-12-01

The U-Pb isotope system provides us with a powerful tool for understanding the chemical evolution of the Earth. Pb isotopes in Archean rocks, however, have not been widely utilized because U mobility makes initial Pb isotope ratios from old silicate rocks difficult, if not impossible, to determine. Galenas in syngenetic volcanogenic massive sulfide (VMS) deposits, however, provide snapshots of initial Pb ratios because their Pb isotopic composition is time invariant at their formation (U/Pb=0). The Pb isotopic record from galenas from rocks of all age have been utilized for over 70 years to answer a wide range of scientific problems beginning with Al Nier's pioneering work analyzing Pb isotopes in the 1930's but are no longer widely used by the isotopic community because they have been produced by older TIMS techniques. We have begun a re-examination of Archean Pb by an extensive analysis of over 100 galena samples from Archean VMS deposits throughout the Superior and Slave Provinces in Canada as well as from other VMS deposits in Finland, South Africa and Western Australia. The goal of this work is to provide modern, high precision measurements and update an old, but venerable, Pb isotopic data set. We feel these data provide important constraints on not only the Pb isotopic evolution of the Earth, but planetary differentiation and recycling processes operating in the first 2 b.y. of Earth's history. Our analytical techniques include dissolving the Pb sulfide minerals, purifying them with ion chromatography, and analyzing them using MC-ICPMS at both Washington State University (Neptune) and Ecole Normale Superieure in Lyon, France (Nu). All Pb solutions are doped with Tl in order to correct for mass fractionation. In this abstract we report preliminary galena Pb isotope data from 6 VMS deposits in the Abitibi greenstone belt: Chibougamu, Matagami, Noranda, Normetal, Timmins, and Val d"Or. These deposits are all approximately 2.7 Ga in age but in detail vary from 2.728 Ga (Normetal) to 2.70 Ga (Noranda). The Pb isotopic compositions from these galenas, when normalized to a common age of 2.7 Ga, define a highly linear array in 207Pb/204Pb vs. 206Pb/204Pb. This array is nearly coincident with the 2.7 Ga geochron with a slope that corresponds to an age of ~4.4 Ga and with an extraordinary large range of 207Pb/204Pb, about the same magnitude as modern MORB. These data have important implications for the evolution of the Archean mantle. First, the slope of the Abitibi Pb-Pb array and its coincidence with the 2.7 Ga geochron suggests widespread U-Pb differentiation within the first hundred million years of Earth's history. This may have been due to either core formation or silicate/melt differentiation due to widespread melting of the mantle (e.g., formation of a magma ocean). Second, variations in μ in the Abitibi mantle and the subsequent Pb isotopic heterogeneities, whatever their cause, have not been significantly changed from 4.4 until 2.7 Ga. This implies that changes in μ in the Abitibi mantle source between 4.4 and 2.7 Ga, such as would be caused by crust extraction or recycling of older crust into this region of the mantle, were insufficient to destroy the original μ variations created at 4.4 Ga. Therefore, it appears that this portion of the mantle had essentially remained isolated and undisturbed from the early Hadean until the late Archean.

Neodymium isotope evolution of NW Tethyan upper ocean waters throughout the Cretaceous

NASA Astrophysics Data System (ADS)

Pucéat, Emmanuelle; Lécuyer, Christophe; Reisberg, Laurie

2005-08-01

Neodymium isotope compositions of twenty-four fish teeth, nineteen from the NW Tethys and five from different locations within the Tethys, are interpreted to reflect the evolution of Tethyan upper ocean water composition during the Cretaceous and used to track changes in erosional inputs to the NW Tethys and in oceanic circulation throughout the Cretaceous. The rather high ɛNd (up to - 7.6) of the NW Tethyan upper ocean waters recorded from the Late Berriasian to the Early Aptian and the absence of negative excursions during this interval support the presence of a permanent westward flowing Tethys Circumglobal Current (TCC). This implies that temperature variations during this time period, inferred from the oxygen isotope analysis of fish tooth enamel, were not driven by changes in surface oceanic currents, but rather by global climatic changes. The results presented here represent a significant advance over previously published Cretaceous seawater Nd isotope records. Our newly acquired data now allow the identification of two stages of low ɛNd values in the NW Tethys, during the Early Albian-Middle Albian interval (down to - 10) and the Santonian-Early Campanian (down to - 11.4), which alternate with two stages of higher ɛNd values (up to - 9) during the Late Albian-Turonian interval and the Maastrichtian. Used in conjunction with the oxygen isotope record, the fluctuations of ɛNd values can be related to major climatic, oceanographic, and tectonic events that appeared in the western Tethyan domain.

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

PubMed

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

2008-07-01

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

Post-eruptive alteration of silicic ignimbrites and lavas, Gran Canaria, Canary Islands - Strontium, neodymium, lead, and oxygen isotopic evidence

NASA Technical Reports Server (NTRS)

Cousens, Brian L.; Spera, Frank J.; Dobson, Patrick F.

1993-01-01

The isotopic composition of lavas from oceanic islands provides important information about the composition and evolution of the earth's mantle. Isotopic analyses of Miocene comenditic, pantelleritic, and trachyphonolitic ignimbrites and lavas from the Canary islands were performed. Results provide evidence for posteruptive mobility of Rb and Sr during low temperature postemplacement interaction with circulating ground water. Calculated Sr isotope ratios define a magmatic trend in the stratigraph section. 87Sr/86Sr ratios in hydrated vitrophyte and devitrified matrix separates indicate significant posteruptive interaction with meteoric water starting soon after deposition. This process extends patchily through the entire pyroclastic flow and may be ongoing. 87Sr/86Sr ratios determined by whole rock analysis of silicic rocks from oceanic islands are suspect and should not be incorporated into mantle tracer studies. Anorthoclase phenocrysts are resistant to these processes and may produce useful data.

Fully automatic and precise data analysis developed for time-of-flight mass spectrometry.

PubMed

Meyer, Stefan; Riedo, Andreas; Neuland, Maike B; Tulej, Marek; Wurz, Peter

2017-09-01

Scientific objectives of current and future space missions are focused on the investigation of the origin and evolution of the solar system with the particular emphasis on habitability and signatures of past and present life. For in situ measurements of the chemical composition of solid samples on planetary surfaces, the neutral atmospheric gas and the thermal plasma of planetary atmospheres, the application of mass spectrometers making use of time-of-flight mass analysers is a technique widely used. However, such investigations imply measurements with good statistics and, thus, a large amount of data to be analysed. Therefore, faster and especially robust automated data analysis with enhanced accuracy is required. In this contribution, an automatic data analysis software, which allows fast and precise quantitative data analysis of time-of-flight mass spectrometric data, is presented and discussed in detail. A crucial part of this software is a robust and fast peak finding algorithm with a consecutive numerical integration method allowing precise data analysis. We tested our analysis software with data from different time-of-flight mass spectrometers and different measurement campaigns thereof. The quantitative analysis of isotopes, using automatic data analysis, yields results with an accuracy of isotope ratios up to 100 ppm for a signal-to-noise ratio (SNR) of 10 4 . We show that the accuracy of isotope ratios is in fact proportional to SNR -1 . Furthermore, we observe that the accuracy of isotope ratios is inversely proportional to the mass resolution. Additionally, we show that the accuracy of isotope ratios is depending on the sample width T s by T s 0.5 . Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Isotopic and noble gas geochemistry in geothermal research

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

Kennedy, B.M.; DePaolo, D.J.

1997-12-31

The objective of this program is to provide, through isotopic analyses of fluids, fluid inclusions, and rocks and minerals coupled with improved methods for geochemical data analysis, needed information regarding sources of geothermal heat and fluids, the spatial distribution of fluid types, subsurface flow, water-rock reaction paths and rates, and the temporal evolution of geothermal systems. Isotopic studies of geothermal fluids have previously been limited to the light stable isotopes of H, C, and O. However, other isotopic systems such as the noble gases (He, Ne, Ar, Kr and Xe) and reactive elements (e.g. B, N, S, Sr and Pb)more » are complementary and may even be more important in some geothermal systems. The chemistry and isotopic composition of a fluid moving through the crust will change in space and time in response to varying chemical and physical parameters or by mixing with additional fluids. The chemically inert noble gases often see through these variations, making them excellent tracers for heat and fluid sources. Whereas, the isotopic compositions of reactive elements are useful tools in characterizing water-rock interaction and modeling the movement of fluids through a geothermal reservoir.« less

Melt solidification and late-stage evaporation in the evolution of a FUN inclusion from the Vigarano C3V chondrite

NASA Technical Reports Server (NTRS)

Davis, Andrew M.; Clayton, Robert N.; Mayeda, Toshiko K.; Sylvester, Paul J.; Macpherson, Glenn J.

1991-01-01

Results are presented on a detailed petrologic, chemical, and isotopic study of the so-called FUN inclusion (1623-5) from the Vigarano C3V chondrite. It is shown that the precursor material from which the Vigarano 1623-5 has formed contained some nuclear isotopic anomalies; this precursor was composed of melted and crystallized spinel, olivine, fassaite, and melilite. The results on the petrologic and isotopic properties of 1623-5 indicate unambiguously the action of volatilization in the evolution of this inclusion.

What Hf isotopes in zircon tell us about crust-mantle evolution

NASA Astrophysics Data System (ADS)

Iizuka, Tsuyoshi; Yamaguchi, Takao; Itano, Keita; Hibiya, Yuki; Suzuki, Kazue

2017-03-01

The 176Lu-176Hf radioactive decay system has been widely used to study planetary crust-mantle differentiation. Of considerable utility in this regard is zircon, a resistant mineral that can be precisely dated by the U-Pb chronometer and record its initial Hf isotope composition due to having low Lu/Hf. Here we review zircon U-Pb age and Hf isotopic data mainly obtained over the last two decades and discuss their contributions to our current understanding of crust-mantle evolution, with emphasis on the Lu-Hf isotope composition of the bulk silicate Earth (BSE), early differentiation of the silicate Earth, and the evolution of the continental crust over geologic history. Meteorite zircon encapsulates the most primitive Hf isotope composition of our solar system, which was used to identify chondritic meteorites best representative of the BSE (176Hf/177Hf = 0.282793 ± 0.000011; 176Lu/177Hf = 0.0338 ± 0.0001). Hadean-Eoarchean detrital zircons yield highly unradiogenic Hf isotope compositions relative to the BSE, providing evidence for the development of a geochemically enriched silicate reservoir as early as 4.5 Ga. By combining the Hf and O isotope systematics, we propose that the early enriched silicate reservoir has resided at depth within the Earth rather than near the surface and may represent a fractionated residuum of a magma ocean underlying the proto-crust, like urKREEP beneath the anorthositic crust on the Moon. Detrital zircons from world major rivers potentially provide the most robust Hf isotope record of the preserved granitoid crust on a continental scale, whereas mafic rocks with various emplacement ages offer an opportunity to trace the Hf isotope evolution of juvenile continental crust (from εHf[4.5 Ga] = 0 to εHf[present] = + 13). The river zircon data as compared to the juvenile crust composition highlight that the supercontinent cycle has controlled the evolution of the continental crust by regulating the rates of crustal generation and intra-crustal reworking processes and the preservation potential of granitoid crust. We use the data to explore the timing of generation of the preserved continental crust. Taking into account the crustal residence times of continental crust recycled back into the mantle, we further propose a model of net continental growth that stable continental crust was firstly established in the Paleo- and Mesoarchean and significantly grew in the Paleoproterozoic.

Tourmaline as a recorder of ore-forming processes

USGS Publications Warehouse

Slack, John F.; Trumbull, Robert B.

2011-01-01

Tourmaline occurs in diverse types of hydrothermal mineral deposits and can be used to constrain the nature and evolution of ore-forming fl uids. Because of its broad range in composition and retention of chemical and isotopic signatures, tourmaline may be the only robust recorder of original mineralizing processes in some deposits. Microtextures and in situ analysis of compositional and isotopic variations in ore-related tourmaline provide valuable insights into hydrothermal systems in seafl oor, sedimentary, magmatic, and metamorphic environments. Deciphering the hydrothermal record in tourmaline also holds promise for aiding exploration programs in the search for new ore deposits.

Meteorite zircon constraints on the bulk Lu-Hf isotope composition and early differentiation of the Earth.

PubMed

Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

2015-04-28

Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The (176)Lu-(176)Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day (176)Hf/(177)Hf and (176)Lu/(177)Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess (176)Hf due to the accelerated decay of (176)Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu-Hf system. Herein we report the first, to our knowledge, high-precision Lu-Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial (176)Hf/(177)Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess (176)Hf and accurately represent the Lu-Hf system of the bulk Earth ((176)Hf/(177)Hf = 0.282793 ± 0.000011; (176)Lu/(177)Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago.

Meteorite zircon constraints on the bulk Lu−Hf isotope composition and early differentiation of the Earth

PubMed Central

Iizuka, Tsuyoshi; Yamaguchi, Takao; Hibiya, Yuki; Amelin, Yuri

2015-01-01

Knowledge of planetary differentiation is crucial for understanding the chemical and thermal evolution of terrestrial planets. The 176Lu−176Hf radioactive decay system has been widely used to constrain the timescales and mechanisms of silicate differentiation on Earth, but the data interpretation requires accurate estimation of Hf isotope evolution of the bulk Earth. Because both Lu and Hf are refractory lithophile elements, the isotope evolution can be potentially extrapolated from the present-day 176Hf/177Hf and 176Lu/177Hf in undifferentiated chondrite meteorites. However, these ratios in chondrites are highly variable due to the metamorphic redistribution of Lu and Hf, making it difficult to ascertain the correct reference values for the bulk Earth. In addition, it has been proposed that chondrites contain excess 176Hf due to the accelerated decay of 176Lu resulting from photoexcitation to a short-lived isomer. If so, the paradigm of a chondritic Earth would be invalid for the Lu−Hf system. Herein we report the first, to our knowledge, high-precision Lu−Hf isotope analysis of meteorite crystalline zircon, a mineral that is resistant to metamorphism and has low Lu/Hf. We use the meteorite zircon data to define the Solar System initial 176Hf/177Hf (0.279781 ± 0.000018) and further to identify pristine chondrites that contain no excess 176Hf and accurately represent the Lu−Hf system of the bulk Earth (176Hf/177Hf = 0.282793 ± 0.000011; 176Lu/177Hf = 0.0338 ± 0.0001). Our results provide firm evidence that the most primitive Hf in terrestrial zircon reflects the development of a chemically enriched silicate reservoir on Earth as far back as 4.5 billion years ago. PMID:25870298

Isotopic homogeneity of iron in the early solar nebula.

PubMed

Zhu, X K; Guo, Y; O'Nions, R K; Young, E D; Ash, R D

2001-07-19

The chemical and isotopic homogeneity of the early solar nebula, and the processes producing fractionation during its evolution, are central issues of cosmochemistry. Studies of the relative abundance variations of three or more isotopes of an element can in principle determine if the initial reservoir of material was a homogeneous mixture or if it contained several distinct sources of precursor material. For example, widespread anomalies observed in the oxygen isotopes of meteorites have been interpreted as resulting from the mixing of a solid phase that was enriched in 16O with a gas phase in which 16O was depleted, or as an isotopic 'memory' of Galactic evolution. In either case, these anomalies are regarded as strong evidence that the early solar nebula was not initially homogeneous. Here we present measurements of the relative abundances of three iron isotopes in meteoritic and terrestrial samples. We show that significant variations of iron isotopes exist in both terrestrial and extraterrestrial materials. But when plotted in a three-isotope diagram, all of the data for these Solar System materials fall on a single mass-fractionation line, showing that homogenization of iron isotopes occurred in the solar nebula before both planetesimal accretion and chondrule formation.

[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.

Mass transfer and carbon isotope evolution in natural water systems

USGS Publications Warehouse

Wigley, T.M.L.; Plummer, Niel; Pearson, F.J.

1978-01-01

This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1. (1) carbon-14 dating of groundwaters; 2. (2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and 3. (3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of ??C13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation. ?? 1978.

Evolution of ectomycorrhizas as a driver of diversification and biogeographic patterns in the model mycorrhizal mushroom genus Laccaria.

PubMed

Wilson, Andrew W; Hosaka, Kentaro; Mueller, Gregory M

2017-03-01

A systematic and evolutionary ecology study of the model ectomycorrhizal (ECM) genus Laccaria was performed using herbarium material and field collections from over 30 countries covering its known geographic range. A four-gene (nrITS, 28S, RPB2, EF1α) nucleotide sequence dataset consisting of 232 Laccaria specimens was analyzed phylogenetically. The resulting Global Laccaria dataset was used for molecular dating and estimating diversification rates in the genus. Stable isotope analysis of carbon and nitrogen was used to evaluate the origin of Laccaria's ECM ecology. In all, 116 Laccaria molecular species were identified, resulting in a near 50% increase in its known diversity, including the new species described herein: Laccaria ambigua. Molecular dating indicates that the most recent common ancestor to Laccaria existed in the early Paleocene (56-66 million yr ago), probably in Australasia. At this time, Laccaria split into two lineages: one represented by the new species L. ambigua, and the other reflecting a large shift in diversification that resulted in the remainder of Laccaria. L. ambigua shows a different isotopic profile than all other Laccaria species. Isotopes and diversification results suggest that the evolution of the ECM ecology was a key innovation in the evolution of Laccaria. Diversification shifts associated with Laccaria's dispersal to the northern hemisphere are attributed to adaptations to new ecological niches. © 2016 The Authors. New Phytologist © 2016 New Phytologist Trust.

Developing SNMS for Full-Spectrum High-Sensitivity In-Situ Isotopic Analysis of Individual Comet Grains Collected by Stardust?

NASA Technical Reports Server (NTRS)

Chen, Chun-Yen; Shen, Jason Jiun-San; Lee, Typhoon; Calaway, Wallis; Veryovkin, Igor; Moore, Jerry; Pellin, Michael

2005-01-01

In anticipation of the return of comet (and ISM?) dust grains by the Stardust mission [1] in mid-January next year, Academia Sinica (AS) and Argonne National Laboratory (ANL) have entered into a collaboration to develop instrument and method for the isotopic analysis of these samples. We need to achieve the highest possible sensitivity so that we can analyze individual grains one at a time to the smallest possible size. Only by doing so can we hope to reach one of the main science goals of the mission, namely the recognition of those isotopically distinct grains each carrying the characteristic signature of a particular nucleosynthetic stage of its parent star. In order to facilitate the interpretation of these grains the second requirement of our method is that the measurements must be made over the widest possible mass range before samples exhaustion. For instance, the thermonuclear fusion reactions that produced the isotopes of various major elements of a wide mass range required drastically different temperatures. Therefore their abundances could constrain the conditions at greatly varying depth inside the source star hence its structure and evolution.

Evolution of atmospheric xenon and other noble gases inferred from Archean to Paleoproterozoic rocks

NASA Astrophysics Data System (ADS)

Avice, G.; Marty, B.; Burgess, R.; Hofmann, A.; Philippot, P.; Zahnle, K.; Zakharov, D.

2018-07-01

We have analyzed ancient atmospheric gases trapped in fluid inclusions contained in minerals of Archean (3.3 Ga) to Paleozoic (404 Ma) rocks in an attempt to document the evolution of the elemental composition and isotopic signature of the atmosphere with time. Doing so, we aimed at understanding how physical and chemical processes acted over geological time to shape the modern atmosphere. Modern atmospheric xenon is enriched in heavy isotopes by 30-40‰ u-1 relative to Solar or Chondritic xenon. Previous studies demonstrated that, 3.3 Ga ago, atmospheric xenon was isotopically fractionated (enriched in the light isotopes) relative to the modern atmosphere, by 12.9 ± 1.2 (1σ) ‰ u-1, whereas krypton was isotopically identical to modern atmospheric Kr. Details about the specific and progressive isotopic fractionation of Xe during the Archean, originally proposed by Pujol et al. (2011), are now well established by this work. Xe isotope fractionation has evolved from 21‰ u-1 at 3.5 Ga to 12.9‰ u-1 at 3.3 Ga. The current dataset provides some evidence for stabilization of the Xe fractionation between 3.3 and 2.7 Ga. However, further studies will be needed to confirm this observation. After 2.7 Ga, the composition kept evolving and reach the modern-like atmospheric Xe composition at around 2.1 Ga ago. Xenon may be the second atmospheric element, after sulfur, to show a secular isotope evolution during the Archean that ended shortly after the Archean-Proterozoic transition. Fractionation of xenon indicates that xenon escaped from Earth, probably as an ion, and that Xe escape stopped when the atmosphere became oxygen-rich. We speculate that the Xe escape was enabled by a vigorous hydrogen escape on the early anoxic Earth. Organic hazes, scavenging isotopically heavy Xe, could also have played a role in the evolution of atmospheric Xe. For 3.3 Ga-old samples, Ar-N2 correlations are consistent with a partial pressure of nitrogen (pN2) in the Archean atmosphere similar to, or lower than, the modern one, thus requiring other processes than a high pN2 to keep the Earth's surface warm despite a fainter Sun. The nitrogen isotope composition of the atmosphere at 3.3 Ga was already modern-like, attesting to inefficient nitrogen escape to space since that time.

High precision tungsten isotope analysis using MC-ICP-MS and application for terrestrial samples

NASA Astrophysics Data System (ADS)

Suzuki, K.; Takamasa, A.

2017-12-01

Tungsten has five isotopes (M = 180, 182, 183, 184, 186), and 182W isotope is a rediogenic isotope produced by b-decay of 182Hf. Its half life is short (8.9 m.y.), and 182W isotope has been investigated to understand the early Earth geochemical evolution. Both Hf and W are highly refractory elements. As Hf is a lithophile and W is a siderophile elements, 182Hf-182W system could give constraints on metal-silicate (core-mantle) differentiation such as especially early Earth system because of its larege fractionation betwenn core-mantle and short half life. Improvement of analytical techniques of W isotope analyses leads to findings of W isotope anomaly (mostly positive) in old komatiites (2.4 - 3.8 Ga) and young volcanic rocks (12 Ma Ontong Java Plateau and 6 Ma Baffin Bay). In our study, high-precision W isotope ratio measurement with MC-ICP-MS (Thermo co. Ltd., NEPTUNE PLUS). We have measured W standard solution (SRM 3163) and obtained the isotopic compositions with an precision of ± 5ppm. However, the standard solution, which separated by cation or anion exchange resin, has systematical 183W/184W drift to -5ppm. These phenomena was also reported by Willbold et al. (2011). Therefore, we used the standard solution for correction of isotopic fractionation of samples which was processed by the same method as that of the samples. We will present the data of terrestrial samples obtained by the technique dveloped in this study.

Magmatic and Crustal Differentiation History of Granitic Rocks from Hf-O Isotopes in Zircon

NASA Astrophysics Data System (ADS)

Kemp, , A. I. S.; Hawkesworth, , C. J.; Foster, , G. L.; Paterson, , B. A.; Woodhead, , J. D.; Hergt, , J. M.; Gray, , C. M.; Whitehouse, M. J.

2007-02-01

Granitic plutonism is the principal agent of crustal differentiation, but linking granite emplacement to crust formation requires knowledge of the magmatic evolution, which is notoriously difficult to reconstruct from bulk rock compositions. We unlocked the plutonic archive through hafnium (Hf) and oxygen (O) isotope analysis of zoned zircon crystals from the classic hornblende-bearing (I-type) granites of eastern Australia. This granite type forms by the reworking of sedimentary materials by mantle-like magmas instead of by remelting ancient metamorphosed igneous rocks as widely believed. I-type magmatism thus drives the coupled growth and differentiation of continental crust.

Organic Analysis in the Miller Range 090657 CR2 Chondrite: Part 3 C and N Isotopic Imaging

NASA Technical Reports Server (NTRS)

Messenger, S.; Nakamura-Messenger, K.; Elsila, J. E.; Berger, E. L.; Burton, A. S.; Clemett, S. J.; Cao, T.

2016-01-01

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble nanoglobules of macro-molecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Large H, C and N isotopic anomalies suggest some organic components formed in low-T interstellar or outer Solar System environments. The highest isotope anomalies occur in m-scale inclusions in the most primitive materials, such as cometary dust and the least altered carbonaceous chondrites. Often, the hosts of these isotopically anomalous 'hotspots' are discrete organic nanoglobules that probably formed in the outermost reaches of the protosolar disk or cold molecular cloud. Molecular and isotopic studies of meteoritic organic matter are aimed at identifying the chemical properties and formation processes of interstellar organic materials and the subsequent chemical evolutionary pathways in various Solar System environments. The combination of soluble and insoluble analyses with in situ and bulk studies provides powerful constraints on the origin and evolution of organic matter in the Solar System. Using macroscale extraction and analysis techniques as well as microscale in situ observations we have been studying both insoluble and soluble organic material in primitive astromaterial samples. Here, we present results of bulk C and N isotopic measurements and coordinated in situ C and N isotopic imaging and mineralogical and textural studies of carbonaceous materials in a Cr2 carbonaceous chondrite. In accompanying abstracts we discuss the morphology and distribution of carbonaceous components and soluble organic species of this meteorite.

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

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Teske, A.

1996-01-01

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

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.

An evolution strategy for lunar nuclear surface power

NASA Technical Reports Server (NTRS)

Mason, Lee S.

1992-01-01

The production and transmission of electric power for a permanently inhabited lunar base poses a significant challenge which can best be met through an evolution strategy. Nuclear systems offer the best opportunity for evolution in terms of both life and performance. Applicable nuclear power technology options include isotope systems (either radioisotope thermoelectric generators or dynamic isotope power systems) and reactor systems with either static (thermoelectric or thermionic) or dynamic (Brayton, Stirling, Rankine) conversion. A power system integration approach that takes evolution into account would benefit by reduced development and operations cost, progressive flight experience, and simplified logistics, and would permit unrestrained base expansion. For the purposes of defining a nuclear power system evolution strategy, the lunar base development shall consist of four phases: precursor, emplacement, consolidation, and operations.

Common Pb isotope mapping of UHP metamorphic zones in Dabie orogen, Central China: Implication for Pb isotopic structure of subducted continental crust

NASA Astrophysics Data System (ADS)

Shen, Ji; Wang, Ying; Li, Shu-Guang

2014-10-01

We report Pb isotopic compositions for feldspars separated from 57 orthogneisses and 2 paragneisses from three exhumed UHPM slices representing the North Dabie zone, the Central Dabie zone and the South Dabie zone of the Dabie orogen, central-east China. The feldspars from the gneisses were recrystallized during Triassic continental subduction and UHP metamorphism. Precursors of the orthogneisses are products of Neoproterozoic bimodal magmatic events, those in north Dabie zone emplaced into the lower crust and those in central and south Dabie zones into middle or upper crust, respectively. On a 207Pb/204Pb vs. 206Pb/204Pb diagram, almost all orthogneisses data lie to the left of the 0.23 Ga paleogeochron and plot along the model mantle evolution curve with the major portion of the data plotting below it. On a 208Pb/204Pb vs. 206Pb/204Pb diagram the most of data of north Dabie zone extend in elongate arrays along the lower crustal curve and others extend between the lower crustal curve to near the mantle evolution curve for the plumbotectonics model. This pattern demonstrates that the Pb isotopic evolution of the feldspars essentially ended at 0.23 Ga and the orthogneiss protoliths were principally dominated by reworking of ancient lower crust with some addition of juvenile mantle in the Neoproterozoic rifting tectonic zone. According to geological evolution history of the locally Dabie orogen, a four-stage Pb isotope evolution model including a long time evolution between 2.0 and 0.8 Ga with a lower crust type U/Pb ratio (μ = 5-6) suggests that magmatic emplacement levels of the protoliths of the orthogneisses in the Dabie orogen at 0.8 Ga also play an important role in the Pb evolution of the exhumed UHPM slices, corresponding to their respective Pb characters at ca. 0.8-0.23 Ga. For example, north Dabie zone requires low μ values (3.4-9.6), while central and south Dabie zones require high μ values (10.9-17.2). On the other hand, Pb isotopic mixing between north and central or south Dabie zones during retro-grade metamorphism enhanced by the extensive magmatism in the Cretaceous has also been observed in the 207Pb/204Pb vs. 206Pb/204Pb and 208Pb/204Pb vs. 206Pb/204Pb diagrams. A combined study of common Pb isotopic compositions of Dabie orthogneisses and Sulu UHPM rocks from the Chinese Continental Scientific Drilling project demonstrates that a slab marked by extremely unradiogenic Pb observed in the main hole was absent in the Dabie orogen. However, occurrence of some Mesozoic granitoids with such unradiogenic character in the Dabie orogen suggests that their source may be a buried unradiogenic unit underlying below north Dabie zone. This case study clearly shows that whether the position of the Dabie data relative to the orogen curve of the plumbotectonic model is helpful in understanding the Pb isotopic structure and evolution of subducted continental crust.

Modeling crust-mantle evolution using radiogenic Sr, Nd, and Pb isotope systematics

NASA Astrophysics Data System (ADS)

Kumari, Seema; Paul, Debajyoti

2015-04-01

The present-day elemental and isotopic composition of Earth's terrestrial reservoirs can be used as geochemical constraints to study evolution of the crust-mantle system. A flexible open system evolutionary model of the Earth, comprising continental crust (CC), upper depleted mantle (UM) -source of mid-ocean ridge basalts (MORB), and lower mantle (LM) reservoir with a D" layer -source of ocean island basalts (OIB), and incorporating key radioactive isotope systematics (Rb-Sr, Sm-Nd, and U-Th-Pb), is solved numerically at 1 Ma time step for 4.55 Ga, the age of the Earth. The best possible solution is the one that produces the present-day concentrations as well as isotopic ratios in terrestrial reservoirs, compiled from published data. Different crustal growth scenarios (exponential, episodic, early and late growth), proposed in earlier studies, and its effect on the evolution of isotope systematics of terrestrial reservoirs is studied. Model simulations strongly favor a layered mantle structure satisfying majority of the isotopic constraints. In the successful model, which is similar to that proposed by Kellogg et al. (1999), the present-day UM comprises of 60% of mantle mass and extends to a depth 1600 km, whereas the LM becomes non-primitive and more enriched than the bulk silicate Earth, mainly due to addition of recycled crustal material. Modeling suggest that isotopic evolution of reservoirs is affected by the mode of crustal growth. Only two scenarios satisfied majority of the Rb-Sr and Sm-Nd isotopic constraints but failed to reproduce the present-day Pb-isotope systematics; exponential growth of crust (mean age, tc=2.3 Ga) and delayed and episodic growth (no growth for initial 900 Ma, tc=2.05 Ga) proposed by Patchett and Arndt (1986). However, assuming a slightly young Earth (4.45 Ga) better satisfies the Pb-isotope systematics. Although, the delayed crustal growth model satisfied Sr-Nd isotopic constraints, presence of early Hadean crust (4.03 and 4.4 Ga detrital zircon in Acasta gneiss and Yilgarn block, respectively), argues against it. One notable feature of successful models is an early depletion of incompatible elements (as well as Th/U ratio in the UM) by the initial 500 Ma, as a result of early formation of continental crust. Our results strongly favor exponential crustal growth and layered mantle structure. Patchett, P.J., Arndt, N.T. (1986), Earth and Planetary Science Letters, 78, 329-338. Kellogg, L.H., Hager, B.H., van der Hilst, R.D (1999), Science, 283, 1881-1884.

Do Hf isotopes in magmatic zircons represent those of their host rocks?

NASA Astrophysics Data System (ADS)

Wang, Di; Wang, Xiao-Lei; Cai, Yue; Goldstein, Steven L.; Yang, Tao

2018-04-01

Lu-Hf isotopic system in zircon is a powerful and widely used geochemical tracer in studying petrogenesis of magmatic rocks and crustal evolution, assuming that zircon Hf isotopes can represent initial Hf isotopes of their parental whole rock. However, this assumption may not always be valid. Disequilibrium partial melting of continental crust would preferentially melt out non-zircon minerals with high time-integrated Lu/Hf ratios and generate partial melts with Hf isotope compositions that are more radiogenic than those of its magma source. Dissolution experiments (with hotplate, bomb and sintering procedures) of zircon-bearing samples demonstrate this disequilibrium effect where partial dissolution yielded variable and more radiogenic Hf isotope compositions than fully dissolved samples. A case study from the Neoproterozoic Jiuling batholith in southern China shows that about half of the investigated samples show decoupled Hf isotopes between zircons and the bulk rocks. This decoupling could reflect complex and prolonged magmatic processes, such as crustal assimilation, magma mixing, and disequilibrium melting, which are consistent with the wide temperature spectrum from ∼630 °C to ∼900 °C by Ti-in-zircon thermometer. We suggest that magmatic zircons may only record the Hf isotopic composition of their surrounding melt during crystallization and it is uncertain whether their Hf isotopic compositions can represent the primary Hf isotopic compositions of the bulk magmas. In this regard, using zircon Hf isotopic compositions to trace crustal evolution may be biased since most of these could be originally from disequilibrium partial melts.

Light Isotopes and Trace Organics Analysis of Mars Samples with Mass Spectrometry

NASA Technical Reports Server (NTRS)

Mahaffy, P.; Niemann, Hasso (Technical Monitor)

2001-01-01

Precision measurement of light isotopes in Mars surface minerals and comparison of this isotopic composition with atmospheric gas and other, well-mixed reservoirs such as surface dust are necessary to understand the history of atmospheric evolution from a possibly warmer and wetter Martian surface to the present state. Atmospheric sources and sinks that set these ratios are volcanism, solar wind sputtering, photochemical processes, and weathering. Measurement of a range of trace organic species with a particular focus on species such as amino acids that are the building blocks of terrestrial life are likewise important to address the questions of prebiotic and present or past biological activity on Mars. The workshop topics "isotopic mineralogy" and "biology and pre-biotic chemistry" will be addressed from the point of view of the capabilities and limitations of insitu mass spectrometry (MS) techniques such as thermally evolved gas analysis (TEGA) and gas chromatography (GC) surface experiments using MS, in both cases, as a final chemical and isotopic composition detector. Insitu experiments using straightforward adaptations of existing space proven hardware can provide a substantial improvement in the precision and accuracy of our present knowledge of isotopic composition both in molecular and atomic species in the atmosphere and those chemically bound in rocks and soils. Likewise, detection of trace organic species with greatly improved sensitivity from the Viking GCMS experiment is possible using gas enrichment techniques. The limits to precision and accuracy of presently feasible insitu techniques compared to laboratory analysis of returned samples will be explored. The insitu techniques are sufficiently powerful that they can provide a high fidelity method of screening samples obtained from a diverse set of surface locations such as the subsurface or the interior of rocks for selection of those that are the most interesting for return to Earth.

Lunar basalt chronology, mantle differentiation and implications for determining the age of the Moon

NASA Astrophysics Data System (ADS)

Snape, Joshua F.; Nemchin, Alexander A.; Bellucci, Jeremy J.; Whitehouse, Martin J.; Tartèse, Romain; Barnes, Jessica J.; Anand, Mahesh; Crawford, Ian A.; Joy, Katherine H.

2016-10-01

Despite more than 40 years of studying Apollo samples, the age and early evolution of the Moon remain contentious. Following the formation of the Moon in the aftermath of a giant impact, the resulting Lunar Magma Ocean (LMO) is predicted to have generated major geochemically distinct silicate reservoirs, including the sources of lunar basalts. Samples of these basalts, therefore, provide a unique opportunity to characterize these reservoirs. However, the precise timing and extent of geochemical fractionation is poorly constrained, not least due to the difficulty in determining accurate ages and initial Pb isotopic compositions of lunar basalts. Application of an in situ ion microprobe approach to Pb isotope analysis has allowed us to obtain precise crystallization ages from six lunar basalts, typically with an uncertainty of about ± 10 Ma, as well as constrain their initial Pb-isotopic compositions. This has enabled construction of a two-stage model for the Pb-isotopic evolution of lunar silicate reservoirs, which necessitates the prolonged existence of high-μ reservoirs in order to explain the very radiogenic compositions of the samples. Further, once firm constraints on U and Pb partitioning behaviour are established, this model has the potential to help distinguish between conflicting estimates for the age of the Moon. Nonetheless, we are able to constrain the timing of a lunar mantle reservoir differentiation event at 4376 ± 18 Ma, which is consistent with that derived from the Sm-Nd and Lu-Hf isotopic systems, and is interpreted as an average estimate of the time at which the high-μ urKREEP reservoir was established and the Ferroan Anorthosite (FAN) suite was formed.

Ba isotopic compositions in stardust SiC grains from the Murchison meteorite: Insights into the stellar origins of large SiC grains

NASA Astrophysics Data System (ADS)

Ávila, Janaína N.; Ireland, Trevor R.; Gyngard, Frank; Zinner, Ernst; Mallmann, Guilherme; Lugaro, Maria; Holden, Peter; Amari, Sachiko

2013-11-01

We report barium isotopic measurements in 12 large (7-58 μm) stardust silicon carbide grains recovered from the Murchison carbonaceous chondrite. The C-, N-, and Si-isotopic compositions indicate that all 12 grains belong to the mainstream population and, as such, are interpreted to have condensed in the outflows of low-mass carbon-rich asymptotic giant branch (AGB) stars with close-to-solar metallicity. Barium isotopic analyses were carried out on the Sensitive High Resolution Ion Microprobe - Reverse Geometry (SHRIMP-RG) with combined high mass resolution and energy filtering to eliminate isobaric interferences from molecular ions. Contrary to previous measurements in small (<5 μm) mainstream grains, the analyzed large SiC grains do not show the classical s-process enrichment, having near solar Ba isotopic compositions. While contamination with solar material is a common explanation for the lack of large isotopic anomalies in stardust SiC grains, particularly for these large grains which have low trace element abundances, our results are consistent with previous observations that Ba isotopic ratios are dependent on grain size. We have compared the SiC data with theoretical predictions of the evolution of Ba isotopic ratios in the envelopes of low-mass AGB stars with a range of stellar masses and metallicities. The Ba isotopic measurements obtained for large SiC grains from the LS + LU fractions are consistent with grain condensation in the envelope of very low-mass AGB stars (1.25 M⊙) with close-to-solar metallicity, which suggests that conditions for growth of large SiC might be more favorable in very low-mass AGB stars during the early C-rich stages of AGB evolution or in stable structures around AGB stars whose evolution was cut short due to binary interaction, before the AGB envelope had already been largely enriched with the products of s-process nucleosynthesis.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

C-isotope composition of fossil sedges and grasses

NASA Astrophysics Data System (ADS)

Kurschner, Wolfram M.

2010-05-01

C4 plants differ from C3 plants regarding their anatomy and their C-isotope composition. Both features can be used in the geological record to determine the presence of C4 plants. Yet, the evolution of the C4 pathway in the fossil record is enigmatic as palaeobotanical and geological evidence for C4 plants is sparse. The oldest structural evidence for Kranz anatomy has been found in Late Miocene permineralized grass leaf remains. But studies on the C-isotope composition of sedimentary organic matter indicate that abundant C4 biomass was present in N-America and Asia throughout the Miocene in expanding savannahs and grasslands. The success of C4 plants appears to be related also to an increasing seasonal aridity in the tropical climate belts and the co-evolution of grazers. However, C- isotope composition of palaeosols or vertebrate teeth only allows to estimate the abundance of C4 plant biomass in the vegetation or in the diet without further taxonomical specification which plant groups would have had C4 metabolism. In this contribution the first extensive C-isotope analysis of fossil seeds of sedges and a few grasses are presented. The age of the carpological material ranges from Late Eocene to Pliocene and was collected from several central European brown coal deposits. The 52 different taxa studied include several species of Carex, Cladiocarya, Eriopherum, Eleocharis, Scirpus, Sparganium. Most of them representing herbaceous elements of a (sub)tropical vegetation growing near the edge of a lake. The C-isotope composition of the fossil seeds varies between -30 and -23 o/oo indicating C3 photosynthesis. This first systematic inventory shows that C4 plants were absent in the European (sub)tropical brown coal forming wetland vegetation during the Tertiary. These preliminary data are in agreement with phylogenetic studies which predict the origin of C4 plants outside the European realm.

Nd Isotope and U-Th-Pb Age Mapping of Single Monazite Grains by Laser Ablation Split Stream Analysis

NASA Astrophysics Data System (ADS)

Fisher, C. M.; Hanchar, J. M.; Miller, C. F.; Phillips, S.; Vervoort, J. D.; Martin, W.

2015-12-01

Monazite is a common accessory mineral that occurs in medium to high grade metamorphic and Ca-poor felsic igneous rocks, and often controls the LREE budget (including Sm and Nd) of the host rock in which it crystallizes. Moreover, it contains appreciable U and Th, making it an ideal mineral for determining U-Th-Pb ages and Sm-Nd isotopic compositions, both of which are readily determined using in situ techniques with very high spatial resolution like LA-MC-ICPMS. Here, we present the results of laser ablation split stream analyses (LASS), which allows for simultaneous determination of the age and initial Nd isotopic composition in a single analysis. Analyses were done using a 20mm laser spot that allowed for detailed Nd isotope mapping of monazite grains (~30 analyses per ~250mm sized grain). Combined with LREE ratios (e.g., Sm/Nd, Ce/Gd, and Eu anomalies) these results yield important petrogenetic constraints on the evolution of peraluminous granites from the Old Woman-Piute batholith in southeastern California. Our findings also allow an improved understanding of the causes of isotope heterogeneity in granitic rocks. U-Th-Pb age mapping across the crystals reveals a single Cretaceous age for all grains with precision and accuracy typical of laser ablation analyses (~2%). In contrast, the concurrent Nd isotope mapping yields homogeneous initial Nd isotope compositions for some grains and large initial intra-grain variations of up to 8 epsilon units in others. The grains that yield homogeneous Nd isotope compositions have REE ratios suggesting that they crystallized in a fractionally crystallizing magma. Conversely, other grains, which also record fractional crystallization of both feldspar and LREE rich minerals, demonstrate a change in the Nd isotope composition of the magma during crystallization of monazite. Comparison of inter- and intra-grain Nd isotope compositions reveals further details on the potential mechanisms responsible for isotope heterogeneity present in single rock samples. This method highlights the potential of single grain isotope mapping of LREE phases such as monazite, allanite, and titanite for understanding both igneous and metamorphic petrogenesis.

Crustal growth and episodic reworking over one billion years in the Capricorn Orogen, Western Australia: evidence from Lu-Hf and O isotope data

NASA Astrophysics Data System (ADS)

Jahn, Inalee; Clark, Chris; Reddy, Steve; Taylor, Rich

2017-04-01

Fundamental to understanding the generation and evolution of a crustal block is knowledge of the relationship between additions of new material from the mantle, and the extent of crustal recycling [1]. Hafnium isotope ratios can be used to characterise relative contributions from mantle, crustal and recycled reservoirs within magmas. Oxygen isotopes can be used to constrain the extent of crustal interaction during magma emplacement. When used in conjunction, they can help unravel multiple crystallisation histories of a crustal block, and follow the source composition through magma evolution. The Capricorn Orogen records the Paleoproterozoic collision of the Yilgarn and Pilbara Cratons to form the West Australian Craton, and over one billion years of subsequent intracontinental crustal reworking. U-Pb zircon geochronology records three discrete tectono-magmatic events which resulted in voluminous granitic magmatism: the 2005-1975 Ma Glenburgh Orogeny, the 1820-1770 Ma Capricorn Orogeny, and the 1680-1620 Ma Durlacher Orogeny [2]. We present U-Pb, Lu-Hf and δ18O isotopic data from zircon from 50 samples of granites and granitoids from the Capricorn Orogen to provide constraints on the crustal evolution of the Paleoproterozoic crust. Our results confirm crustal growth by juvenile mantle input was limited to the Glenburgh Orogeny associated with the amalgamation of the West Australian Craton, while all subsequent Paleoproterozoic magmatism was primarily derived from significant reworking of the pre-existing crustal components. Time-sliced maps showing the variation in Hf and O isotopes can be used to image crustal evolution in space and time, and are particularly useful in constraining the spatial and temporal extent of juvenile magmatic additions to the crust. These maps suggest that crustal growth was concentrated along, or in the terranes adjacent to, the Yilgarn Craton margin. Our results are in agreement with previous isotopic studies [3], and provide additional constraints for the evolution of the Paleoproterozoic crust within the Capricorn Orogen. [1] Cawood et al. 2013. Geological Society of America Bulletin, 125(1-2), 14-32 [2] Sheppard et al. 2010. Geological Survey of Western Australia, Perth, Western Australia, 336 [3] Johnson et al. 2017. Lithos, 268, 76-86

Continental fragmentation and the strontium isotopic evolution of seawater.

NASA Astrophysics Data System (ADS)

Eric, H.; Jean Pascal, C.

2008-12-01

The time evolution of the strontium isotopic composition of seawater over the last 600 million years has the form of an asymmetric trough. The values are highest in the Cambrian and recent and lowest in the Jurassic. Superimposed on this trend are a number of smaller oscillations. The mechanisms responsible for these global isotopic fluctuations are subject to much debates. In order to get a quantitative picture of the changing paleogeography, we have characterized land-ocean distributions over Late Proterozoic to Phanerozoic times from measurement of perimeters and areas of continental fragments, based on paleomagnetic reconstructions. These measurements served to calculate geophysically constrainted breakup and scatter indexes of continental land masses from 0 to 1100 Ma (Cogne and Humler, 2008). Both parameters (strontium isotopic ratios of seawater and continental fragmentation indexes) are obviously highly correlated during the last 600 Ma. Low continental dispersion (that is large continental land masses) are associated with low seawater strontium isotopic ratios (that is when the continental inputs to oceans are minimum) and high continental dispersion (that is relatively small and widely distributed continents) with high seawater strontium isotopic ratios (that is when the continental input to ocean is maximum). Importantly, this first order evolution appears to conflict with the common idea of mountains erosion as a source for radiogenic strontium to oceans because high strontium isotopic ratios in seawater correspond to period of maximum dispersion of continents and not with period of general collisions. At first glance, it would seem that continental erosion increases with the degree of continental dispersion. Models showing that continental precipitation increases when continental masses are smaller and more widely dispersed and/or the length of continental margins available for rivers to carry continental material to oceans are thus favoured in order to resolve the paradox.

Measurement of in situ sulfur isotopes by laser ablation multi-collector ICPMS: opening Pandora’s Box

USGS Publications Warehouse

Ridley, William I.; Pribil, Michael; Koenig, Alan E.; Slack, John F.

2015-01-01

Laser ablation multi-collector ICPMS is a modern tool for in situ measurement of S isotopes. Advantages of the technique are speed of analysis and relatively minor matrix effects combined with spatial resolution sufficient for many applications. The main disadvantage is a more destructive sampling mechanism relative to the ion microprobe technique. Recent advances in instrumentation allow precise measurement with spatial resolutions down to 25 microns. We describe specific examples from economic geology where increased spatial resolution has greatly expanded insights into the sources and evolution of fluids that cause mineralization and illuminated genetic relations between individual deposits in single mineral districts.

Examination of Cr(VI) treatment by zero-valent iron using in situ, real-time X-ray absorption spectroscopy and Cr isotope measurements

NASA Astrophysics Data System (ADS)

Jamieson-Hanes, Julia H.; Lentz, Adam M.; Amos, Richard T.; Ptacek, Carol J.; Blowes, David W.

2014-10-01

A series of replicate flow-through cell experiments was conducted to characterize Cr isotope fractionation during Cr(VI) treatment by granular zero-valent iron (ZVI). Synthetic groundwater containing 50 mg L-1 Cr(VI) was pumped upward through a custom-made cell packed with ZVI under anaerobic conditions. The geochemical evolution of the system was monitored using pH and redox measurements, while aqueous effluent samples were retained for analysis of cations and Cr isotopes. Real-time, in situ X-ray absorption near edge structure (XANES) spectroscopy collected via a Kapton® window in the cell provided additional information on the speciation of the reaction products. Increases in δ53Cr values corresponding to decreases in Cr(VI) concentration suggested the occurrence of redox processes. Spectroscopic results correlated well with the isotope data, indicating reduction of Cr(VI) to Cr(III). The isotope data did not appear to follow a single trend. A two-stage system was proposed to explain the complex isotope trend, where the rapid Cr removal was associated with very little fractionation (ε = -0.2‰), whereas slower removal was associated with a greater degree of fractionation (ε = -1.2‰ to -1.5‰). Reactive transport modeling was used to quantify distinct isotope fractionation values (ε), differentiated by a significant change in the Cr removal rate.

Studies of the di-iron(VI) Intermediate in ferrate-dependent oxygen evolution from water.

PubMed

Sarma, Rupam; Angeles-Boza, Alfredo M; Brinkley, David W; Roth, Justine P

2012-09-19

Molecular oxygen is produced from water via the following reaction of potassium ferrate (K(2)FeO(4)) in acidic solution: 4[H(3)Fe(VI)O(4)](+) + 8H(3)O(+) → 4Fe(3+) + 3O(2) + 18H(2)O. This study focuses upon the mechanism by which the O-O bond is formed. Stopped-flow kinetics at variable acidities in H(2)O and D(2)O are used to complement the analysis of competitive oxygen-18 kinetic isotope effects ((18)O KIEs) upon consumption of natural abundance water. The derived (18)O KIEs provide insights concerning the identity of the transition state. Water attack (WA) and oxo-coupling (OC) transition states were evaluated for various reactions of monomeric and dimeric ferrates using a calibrated density functional theory protocol. Vibrational frequencies from optimized isotopic structures are used here to predict (18)O KIEs for comparison to experimental values determined using an established competitive isotope-fractionation method. The high level of agreement between experimental and theoretic isotope effects points to an intramolecular OC mechanism within a di-iron(VI) intermediate, consistent with the analysis of the reaction kinetics. Alternative mechanisms are excluded based on insurmountably high free energy barriers and disagreement with calculated (18)O KIEs.

Marine sulfur cycle constrained from isotope analysis of different forms of sulfur in the 3.2 Ga black shale (DXCL-DP) from Pilbara, Australia

NASA Astrophysics Data System (ADS)

Kobayashi, Y.; Yamaguchi, K. E.; Sakamoto, R.; Naraoka, H.; Kiyokawa, S.; Ikehara, M.; Ito, T.

2012-12-01

Co-evolution of early life and surface environment has been one of the most important events on Earth. Rise of atmospheric oxygen, or as known as GOE (Great Oxidation Event: e.g., Holland, 1994), has been widely believed to have occurred at around 2.4 billion years ago. But geological and geochemical evidence suggest possibility of much earlier (by hundreds of millions of years) existence of oxic atmosphere and oceans. In order to further investigate the mystery of biological and environmental evolution, we conducted continental drilling in northwestern Pilbara, Western. Australia, to obtain 3.2 billion-years-old least-metamorphosed drillcore black shale samples (DXCL-DP:Dixon Island - Cleaverville Drilling Project; Yamaguchi et al., 2009). Preliminary stable isotope analyses using these samples suggested that photosynthetic organisms produced organic matter (Hosoi et al., 2011), nitrogen fixing bacteria were intermittently active (Yamada et al., 2011), and sulfate-reducing bacteria were active in environment with a limited supply of sulfate (Sakamoto et al., 2011) in the 3.2 Ga ocean. Bulk S isotope compositions could only provide limited information on the biogeochemical cycling of sedimentary S, because it is normally present as different facies (acid-volatile sulfur: AVS, pyrite: FeS2, sulfate, organic sulfur: Sorg, and elemental sulfur: S0) that depend on physicochemical and biological conditions. Therefore, abundance and isotope ratios of these species possess very useful information on oceanic and diagenetic conditions such as redox state and microbiological activity. In order to constrain biogeochemical cycling of S in the 3.2 Ga ocean, we conducted sequential extraction analysis using the DXCL-DP black shales to obtain different S-bearing species and S isotopic analysis. Average S contents for each form of S-bearing species were: ΣS = 2.56 wt.%, AVS = 0.02 wt.%, pyrite = 1.61 wt.%, and sulfate = 0.57 wt%. Relationship between amounts of pyrite-S and organic C suggest presence of syngenetic pyrite (formed in water column) as well as diagenetic pyrite. Average S isotope compositions are: pyrite = 12.3±6.3 ‰, sulfate = 17.3 ± 7.1 ‰, and difference between them are up to as high as 16.8 ‰. These results show that depositional environment was probably close to the modern Black Sea, where sulfate-reducing bacteria are active in anaerobic water mass in semi-closed deep basin, with a limited supply of sulfate from the oxic surface ocean.

Mg-Fe Isotope Systems of Mantle Xenoliths: Constrains on the Evolution of Siberian Craton

NASA Astrophysics Data System (ADS)

An, Y.; Kiseeva, E. S.; Sobolev, N. V.; Zhang, Z.

2017-12-01

Mantle xenoliths bring to the surface a variety of lithologies (dunites, lherzolites, harzburgites, wehrlites, eclogites, pyroxenites, and websterites) and represent snapshots of the geochemical processes that occur deep within the Earth. Recent improvements in the precision of the MC-ICP-MS measurements have allowed us to expand the amount of data on Mg and Fe isotopes for mantle-derived samples. For instance, to constrain the isotopic composition of the Earth based on the study of spinel and garnet peridotites (An et al., 2017; Teng et al., 2010), to trace the origin and to investigate the isotopic fractionation mechanism during metamorphic process using cratonic or orogenic eclogites (Li et al., 2011; Wang et al., 2012) and to reveal the metasomatism-induced mantle heterogeneity by pyroxenites (Hu et al., 2016). Numerous multi-stage modification events and mantle layering are detected in the subcontinental lithospheric mantle under the Siberian craton (Ashchepkov et al., 2008a; Sobolev et al., 1975, etc). Combined analyses of Mg and Fe isotopic systems could provide new constraints on the formation and evolution of the ancient cratonic mantle. In order to better constrain the magnitude and mechanism of inter-mineral Mg and Fe isotopic fractionations at high temperatures, systematic studies of mantle xenoliths are needed. For example, theoretical calculations and natural samples measurements have shown that large equilibrium Mg isotope fractionations controlled by the difference in coordination number of Mg among minerals could exist (Huang et al., 2013; Li et al., 2011). Thus, the Mg isotope geothermometer could help us trace the evolution history of ancient cratons. In this study we present Mg and Fe isotopic data for whole rocks and separated minerals (clinopyroxene (cpx) and garnet (grt)) from different types of mantle xenoliths (garnet pyroxenites, eclogites, grospydites and garnet peridotites) from a number of kimberlite pipes in Siberian craton (Udachnaya, Obnazhennaya, Mir, and Zagadochnaya). The large Mg and Fe isotope fractionations between clinopyroxene and garnet for various mantle rocks (Δ26Mg cpx-gnt= 0.360‰ 0.888‰, Δ56Fe cpx-gnt= 0.018‰ 0.348‰) indicate that the Siberian cratonic lithosphetic mantle has undergone multiple complex metasomatic and re-equilibration events.

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.

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.

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

NASA Astrophysics Data System (ADS)

Pope, Emily C.; Bird, Dennis K.; Arnórsson, Stefán; Fridriksson, Thráinn; Elders, Wilfred A.; Fridleifsson, Gudmundur Ó.

2009-08-01

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as -23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δDEPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from -60 to -78‰, and δ18OEPIDOTE in these wells are between -3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ18O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δDFLUID of ˜ -79‰ and -89‰, respectively, show δDEPIDOTE values of -115‰ and -125‰. In contrast, δDEPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is -68‰; comparable to δDEPIDOTE from well RN-10 at Reykjanes. Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ18O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δDFLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ18OFLUID values are within range of the observed fluid isotope composition. We propose that modern δDEPIDOTE and δDFLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δDROCK value is -125‰ and the water to rock mass ratio is 0.25, predicts a δDFLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.

Hydrogen Isotopes Record the History of the Martian Hydrosphere and Atmosphere

NASA Technical Reports Server (NTRS)

Usui, T.; Simon, J. I.; Jones, J. H.; Kurokawa, H.; Sato, M.; Alexander, C. M. O'D; Wang, J.

2015-01-01

The surface geology and geomorphology of Mars indicates that it was once warm enough to maintain a large body of liquid water on its surface, though such a warm environment might have been transient. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. This study presents insights from hydrogen isotopes for the origin and evolution of Martian water reservoirs.

Final Summary of Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

O'D. Alexander, Conel

2003-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe.

Final Summary of Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

O'D.Alexander, Conel

2004-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4. These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si,N,, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, 0 and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system we have developed for the Carnegie 6f ion probe.

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.

Quantifying inter- and intra-population niche variability using hierarchical bayesian stable isotope mixing models.

PubMed

Semmens, Brice X; Ward, Eric J; Moore, Jonathan W; Darimont, Chris T

2009-07-09

Variability in resource use defines the width of a trophic niche occupied by a population. Intra-population variability in resource use may occur across hierarchical levels of population structure from individuals to subpopulations. Understanding how levels of population organization contribute to population niche width is critical to ecology and evolution. Here we describe a hierarchical stable isotope mixing model that can simultaneously estimate both the prey composition of a consumer diet and the diet variability among individuals and across levels of population organization. By explicitly estimating variance components for multiple scales, the model can deconstruct the niche width of a consumer population into relevant levels of population structure. We apply this new approach to stable isotope data from a population of gray wolves from coastal British Columbia, and show support for extensive intra-population niche variability among individuals, social groups, and geographically isolated subpopulations. The analytic method we describe improves mixing models by accounting for diet variability, and improves isotope niche width analysis by quantitatively assessing the contribution of levels of organization to the niche width of a population.

Reappraising Accretion to Vesta and the Angrite Parent Body Through Mineral-Scale Platinum Group Element and Os-Isotope Analyses

NASA Astrophysics Data System (ADS)

Riches, A. J. V.; Burton, K. W.; Nowell, G. M.; Dale, C. W.; Ottley, C. J.

2016-08-01

New methods presented here enable quantitative determination of mineral-scale PGE-abundances and Os-isotope compositions in meteorite materials thereby providing valuable new insight into planetary evolution.

Os isotopes in SNC meteorites and their implications to the early evolution of Mars and Earth

NASA Technical Reports Server (NTRS)

Jagoutz, E.; Luck, J. M.; Othman, D. Ben; Wanke, H.

1993-01-01

A new development on the measurement of the Os isotopic composition by mass spectrometry using negative ions opened a new field of applications. The Re-Os systematic provides time information on the differentiation of the nobel metals. The nobel metals are strongly partitioned into metal and sulphide phases, but also the generation of silicate melts might fractionate the Re-Os system. Compared to the other isotopic systems which are mainly dating the fractionation of the alkalis and alkali-earth elements, the Re-Os system is expected to disclose entirely new information about the geochemistry. Especially the differentiation and early evolution of the planets such as the formation of the core will be elucidated with this method.

Processes and time scales of magmatic evolution as revealed by Fe-Mg chemical and isotopic zoning in natural olivines

NASA Astrophysics Data System (ADS)

Oeser, Martin; Dohmen, Ralf; Horn, Ingo; Schuth, Stephan; Weyer, Stefan

2015-04-01

In this study, we applied high-precision in situ Fe and Mg isotope analyses by femtosecond laser ablation (fs-LA) MC-ICP-MS on chemically zoned olivine xeno- and phenocrysts from intra-plate volcanic regions in order to investigate the magnitude of Fe and Mg isotope fractionation and its suitability to gain information on magma evolution. Our results show that chemical zoning (i.e., Mg#) in magmatic olivines is commonly associated with significant zoning in δ56Fe and δ26Mg (up to 1.7‰ and 0.7‰, respectively). We explored different cases of kinetic fractionation of Fe and Mg isotopes by modeling diffusion in the melt or olivine and simultaneous growth or dissolution. Combining the information of chemical and isotopic zoning in olivine allows to distinguish between various processes that may occur during magma evolution, namely diffusive Fe-Mg exchange between olivine and melt, rapid crystal growth, and Fe-Mg inter-diffusion simultaneous to crystal dissolution or growth. Chemical diffusion in olivine appears to be the dominant process that drives isotope fractionation in magmatic olivine. Simplified modeling of Fe and Mg diffusion is suitable to reproduce both the chemical and the isotopic zoning in most of the investigated olivines and, additionally, provides time information about magmatic processes. For the Massif Central (France), modeling of diffusive re-equilibration of mantle olivines in basanites revealed a short time span (<2 years) between the entrainment of a mantle xenolith in an intra-plate basaltic magma and the eruption of the magma. Furthermore, we determined high cooling rates (on the order of a few tens to hundreds of °C per year) for basanite samples from a single large outcrop in the Massif Central, which probably reflects the cooling of a massive lava flow after eruption. Results from the modeling of Fe and Mg isotope fractionation in olivine point to a systematic difference between βFe and βMg (i.e., βFe/βMg ≈ 2), implying that the diffusivity ratio of 54Fe and 56Fe (i.e., D54Fe/D56Fe) is very similar to that of 24Mg and 26Mg, despite the smaller relative mass difference for the 54Fe-56Fe pair. This study demonstrates that a combined investigation of Fe-Mg chemical and isotopic zoning in olivine provides additional and more reliable information on magma evolution than chemical zoning alone.

In-situ measurement of sulfur isotopic ratios in zoned apatite crystals via SIMS: a new tool for interpreting dynamic sulfur behavior in magmas

NASA Astrophysics Data System (ADS)

Economos, R. C.; Boehnke, P.; Burgisser, A.

2017-12-01

Sulfur is an important element in igneous systems due to its impact on magma redox, its role in the formation of economically valuable ore deposits, and the influence of catastrophic volcanogenic sulfur degassing on global climate. The mobility and geochemical behavior of sulfur in magmas is complex due to its multi-valent (from S2- to S6+) and multi-phase (solid, immiscible liquid, gaseous, dissolved ions) nature. Sulfur behavior is closely linked with the evolution of oxygen fugacity (fO2) in magmas; the record of fO2 evolution is often difficult to extract from rock records, particularly for intrusive systems that undergo cyclical magmatic processes and crystallize to the solidus. We apply a novel method of measuring S isotopic ratios via secondary ion mass spectrometry (SIMS) in zoned apatite crystals that we interpret as a record of open-system magmatic processes. We analyzed the S concentration and isotopic variations preserved in multiple apatite crystals from single hand specimens from the Cadiz Valley Batholith, CA via electron microprobe and ion microprobe at UCLA. A single, isotopically homogeneous crystal of Durango apatite was characterized for absolute isotopic ratio for this study (UCLA-D1). Isotopic variations in single apatite crystals ranged from 0 to 3.8‰ δ34S and total variation within a single hand sample was 6.1‰ δ34S. High S concentration cores yielded high isotopic ratios while low S concentration rims yielded low isotopic ratios. We favor an explanation of a combination of magma mixing and open-system, ascent-driven degassing under moderately reduced conditions: fO2 at or below NNO +1, although the synchronous crystallization of apatite and anhydrite is also a viable scenario. These findings have implications for the coupled S and fO2 evolution of granitic plutons and suggest that in-situ apatite S isotopic measurements could be a powerful new tool for evaluating redox and S systematics in magmatic systems.

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

DOE workshop: Sedimentary systems, aqueous and organic geochemistry

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

Not Available

1993-07-01

A DOE workshop on sedimentary systems, aqueous and organic geochemistry was held July 15-16, 1993 at Lawrence Berkeley Laboratory. Papers were organized into several sections: Fundamental Properties, containing papers on the thermodynamics of brines, minerals and aqueous electrolyte solutions; Geochemical Transport, covering 3-D imaging of drill core samples, hydrothermal geochemistry, chemical interactions in hydrocarbon reservoirs, fluid flow model application, among others; Rock-Water Interactions, with presentations on stable isotope systematics of fluid/rock interaction, fluid flow and petotectonic evolution, grain boundary transport, sulfur incorporation, tracers in geologic reservoirs, geothermal controls on oil-reservoir evolution, and mineral hydrolysis kinetics; Organic Geochemistry covered new methodsmore » for constraining time of hydrocarbon migration, kinetic models of petroleum formation, mudstones in burial diagenesis, compound-specific carbon isotope analysis of petroleums, stability of natural gas, sulfur in sedimentary organic matter, organic geochemistry of deep ocean sediments, direct speciation of metal by optical spectroscopies; and lastly, Sedimentary Systems, covering sequence stratigraphy, seismic reflectors and diagenetic changes in carbonates, geochemistry and origin of regional dolomites, and evidence of large comet or asteroid impacts at extinction boundaries.« less

Crustal forensics in arc magmas

NASA Astrophysics Data System (ADS)

Davidson, Jon P.; Hora, John M.; Garrison, Jennifer M.; Dungan, Michael A.

2005-01-01

The geochemical characteristics of continental crust are present in nearly all arc magmas. These characteristics may reflect a specific source process, such as fluid fluxing, common to both arc magmas and the continental crust, and/or may reflect the incorporation of continental crust into arc magmas either at source via subducted sediment, or via contamination during differentiation. Resolving the relative mass contributions of juvenile, mantle-derived material, versus that derived from pre-existing crust of the upper plate, and providing these estimates on an element-by-element basis, is important because: (1) we want to constrain crustal growth rates; (2) we want to quantitatively track element cycling at convergent margins; and (3) we want to determine the origin of economically important elements and compounds. Traditional geochemical approaches for determining the contributions of various components to arc magmas are particularly successful when applied on a comparative basis. Studies of suites from multiple magmatic systems along arcs, for which differentiation effects can be individually constrained, can be used to extrapolate to potential source compositions. In the Lesser Antilles Arc, for example, differentiation trends from individual volcanoes are consistent with open-system evolution. However, such trends do not project back to a common primitive magma composition, suggesting that differentiation modifies magmas that were derived from distinct mantle sources. We propose that such approaches should now be complemented by petrographically constrained mineral-scale isotope and trace element analysis to unravel the contributing components to arc magmas. This innovative approach can: (1) better constrain true end-member compositions by returning wider ranges in geochemical compositions among constituent minerals than is found in whole rocks; (2) better determine magmatic evolution processes from core-rim isotopic or trace element profiles from the phases contained in magmas; and (3) constrain rates of differentiation by applying diffusion-controlled timescales to element profiles. An example from Nguaruhoe Volcano, New Zealand, underscores the importance of such a microsampling approach, showing that mineral isotopic compositions encompass wide ranges, that whole-rock isotopic compositions are consequently simply element-weighted averages of the heterogeneous crystal cargo, and that open-system evolution is proved by core-rim variations in Sr isotope ratios. Nguaruhoe is just one of many systems examined through microanalytical approaches. The overwhelming conclusion of these studies is that crystal cargoes are not truly phenocrystic, but are inherited from various sources. The implication of this realization is that the interpretation of whole-rock isotopic data, including the currently popular U-series, needs careful evaluation in the context of petrographic observations.

Lead Isotopes in Olivine-Phyric Shergottite Tissint: Implications for the Geochemical Evolution of the Shergottite Source Mantle

NASA Technical Reports Server (NTRS)

Moriwaki, R.; Usui, T.; Simon, J. I.; Jones, J. H.; Yokoyama, T.

2015-01-01

Geochemically-depleted shergottites are basaltic rocks derived from a martian mantle source reservoir. Geochemical evolution of the martian mantle has been investigated mainly based on the Rb-Sr, Sm-Nd, and Lu-Hf isotope systematics of the shergottites [1]. Although potentially informative, U-Th- Pb isotope systematics have been limited because of difficulties in interpreting the analyses of depleted meteorite samples that are more susceptible to the effects of near-surface processes and terrestrial contamination. This study conducts a 5-step sequential acid leaching experiment of the first witnessed fall of the geochemically-depleted olivinephyric shergottite Tissint to minimize the effect of low temperature distrubence. Trace element analyses of the Tissint acid residue (mostly pyroxene) indicate that Pb isotope compositions of the residue do not contain either a martian surface or terrestrial component, but represent the Tissint magma source [2]. The residue has relatively unradiogenic initial Pb isotopic compositions (e.g., 206Pb/204Pb = 10.8136) that fall within the Pb isotope space of other geochemically-depleted shergottites. An initial µ-value (238U/204Pb = 1.5) of Tissint at the time of crystallization (472 Ma [3]) is similar to a time-integrated mu- value (1.72 at 472 Ma) of the Tissint source mantle calculated based on the two-stage mantle evolution model [1]. On the other hand, the other geochemically-depleted shergottites (e.g., QUE 94201 [4]) have initial µ-values of their parental magmas distinctly lower than those of their modeled source mantle. These results suggest that only Tissint potentially reflects the geochemical signature of the shergottite mantle source that originated from cumulates of the martian magma ocean

Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO2 nuclear fuel

NASA Astrophysics Data System (ADS)

Piro, M. H. A.; Banfield, J.; Clarno, K. T.; Simunovic, S.; Besmann, T. M.; Lewis, B. J.; Thompson, W. T.

2013-10-01

Predictive capabilities for simulating irradiated nuclear fuel behavior are enhanced in the current work by coupling thermochemistry, isotopic evolution and heat transfer. Thermodynamic models that are incorporated into this framework not only predict the departure from stoichiometry of UO2, but also consider dissolved fission and activation products in the fluorite oxide phase, noble metal inclusions, secondary oxides including uranates, zirconates, molybdates and the gas phase. Thermochemical computations utilize the spatial and temporal evolution of the fission and activation product inventory in the pellet, which is typically neglected in nuclear fuel performance simulations. Isotopic computations encompass the depletion, decay and transmutation of more than 2000 isotopes that are calculated at every point in space and time. These computations take into consideration neutron flux depression and the increased production of fissile plutonium near the fuel pellet periphery (i.e., the so-called “rim effect”). Thermochemical and isotopic predictions are in very good agreement with reported experimental measurements of highly irradiated UO2 fuel with an average burnup of 102 GW d t(U)-1. Simulation results demonstrate that predictions are considerably enhanced when coupling thermochemical and isotopic computations in comparison to empirical correlations. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

Collectivity of light Ge and As isotopes

NASA Astrophysics Data System (ADS)

Corsi, A.; Delaroche, J.-P.; Obertelli, A.; Baugher, T.; Bazin, D.; Boissinot, S.; Flavigny, F.; Gade, A.; Girod, M.; Glasmacher, T.; Grinyer, G. F.; Korten, W.; Libert, J.; Ljungvall, J.; McDaniel, S.; Ratkiewicz, A.; Signoracci, A.; Stroberg, R.; Sulignano, B.; Weisshaar, D.

2013-10-01

Background: The self-conjugate nuclei of the A˜70 mass region display rapid shape evolution over isotopic or isotonic chains. Shape coexistence has been observed in Se and Kr isotopes reflecting the existence of deformed subshell gaps corresponding to different shell configurations. As and Ge isotopes are located halfway between such deformed nuclei and the Z=28 shell closure.Purpose: The present work aims at clarifying the low-lying spectroscopy of 66Ge and 67As, and providing a better insight into the evolution of collectivity in light even-even Ge and even-odd As isotopes.Methods: We investigate the low-lying levels and collectivity of the neutron deficient 67As and 66Ge through intermediate-energy Coulomb excitation, inelastic scattering, and proton knockout measurements. The experiment was performed using a cocktail beam of 68Se, 67As, and 66Ge nuclei at an energy of 70-80 MeV/nucleon. Spectroscopic properties of the low-lying states are compared to those calculated via shell model with the JUN45 interaction and beyond-mean-field calculations with the five-dimensional collective Hamiltonian method implemented using the Gogny D1S interaction. The structure evolution of the lower-mass Ge and As isotopes is discussed.Results: Reduced electric quadrupole transition probabilities B(E2) have been extracted from the Coulomb-excitation cross sections measured in 66Ge and 67As. The value obtained for the B(E2;01+→21+) in 66Ge is in agreement with a recent measurement, ruling out the existence of a minimum at N=34 in the B(E2) systematics as previously observed. New transitions have been found in 67As and were assigned to the decay of low-lying negative-parity states.

Triple Oxygen Isotope Constraints on Seawater δ18O and Temperature

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Lead isotope evolution across the Neoproterozoic boundary between craton and juvenile crust, Bayuda Desert, Sudan

NASA Astrophysics Data System (ADS)

Evuk, David; Lucassen, Friedrich; Franz, Gerhard

2017-11-01

Metaigneous mafic and ultramafic rocks from the juvenile Neoproterozoic Arabian Nubian Shield (ANS) and the Proterozoic, reworked Saharan Metacraton (SMC) have been analysed for major- and trace elements and Sr, Nd, and Pb isotopes. Most of the rocks are amphibolites metamorphosed at amphibolite facies conditions, some with relicts of a granulite facies stage. The other rocks are metapyroxenites, metagabbros, and some ultramafic rocks. Trace element compositions of the metabasaltic (dominantly tholeiitic) rocks resemble the patterns of island arcs and primitive lavas from continental arcs. Variable Sr and Nd isotope ratios indicate depleted mantle dominance for most of the samples. 207Pb/204Pb signatures distinguish between the influence of high 207Pb/204Pb old SMC crust and depleted mantle signatures of the juvenile ANS crust. The Pb isotope signatures for most metabasaltic rocks, metapyroxenites and metagabbros from SMC indicate an autochthonous formation. The interpretation of the new data together with published evidence from mafic xenoliths on SMC and ophiolite from ANS allows an extrapolation of mantle evolution in time. There are two lines of evolution in the regional mantle, one, which incorporates potential upper crust material during Neoproterozoic, and a second one with a depleted mantle signature since pre-Neoproterozoic that still is present in the Red Sea and Gulf of Aden spreading centres.

Chemical evolution via beta decay: a case study in strontium-90

NASA Astrophysics Data System (ADS)

Marks, N. A.; Carter, D. J.; Sassi, M.; Rohl, A. L.; Sickafus, K. E.; Uberuaga, B. P.; Stanek, C. R.

2013-02-01

Using 90Sr as a representative isotope, we present a framework for understanding beta decay within the solid state. We quantify three key physical and chemical principles, namely momentum-induced recoil during the decay event, defect creation due to physical displacement, and chemical evolution over time. A fourth effect, that of electronic excitation, is also discussed, but this is difficult to quantify and is strongly material dependent. The analysis is presented for the specific cases of SrTiO3 and SrH2. By comparing the recoil energy with available threshold displacement data we show that in many beta-decay situations defects such as Frenkel pairs will not be created during decay as the energy transfer is too low. This observation leads to the concept of chemical evolution over time, which we quantify using density functional theory. Using a combination of Bader analysis, phonon calculations and cohesive energy calculations, we show that beta decay leads to counter-intuitive behavior that has implications for nuclear waste storage and novel materials design.

Chemical evolution via beta decay: a case study in strontium-90.

PubMed

Marks, N A; Carter, D J; Sassi, M; Rohl, A L; Sickafus, K E; Uberuaga, B P; Stanek, C R

2013-02-13

Using (90)Sr as a representative isotope, we present a framework for understanding beta decay within the solid state. We quantify three key physical and chemical principles, namely momentum-induced recoil during the decay event, defect creation due to physical displacement, and chemical evolution over time. A fourth effect, that of electronic excitation, is also discussed, but this is difficult to quantify and is strongly material dependent. The analysis is presented for the specific cases of SrTiO(3) and SrH(2). By comparing the recoil energy with available threshold displacement data we show that in many beta-decay situations defects such as Frenkel pairs will not be created during decay as the energy transfer is too low. This observation leads to the concept of chemical evolution over time, which we quantify using density functional theory. Using a combination of Bader analysis, phonon calculations and cohesive energy calculations, we show that beta decay leads to counter-intuitive behavior that has implications for nuclear waste storage and novel materials design.

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

NASA Astrophysics Data System (ADS)

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

New isotopic and trace element measurements on lavas from the submarine southwest rift zone (SWR) of Mauna Loa continue the temporal trends of subaerial Mauna Loa flows, extending the known compositional range for this volcano, and suggesting that many of the SWR lavas are older than any exposed on land. He and Nd isotopic compositions are similar to those in the oldest subaerial Mauna Loa lavas (Kahuku and Ninole Basalts), while 87Sr/86Sr ratios are slightly lower (as low as .7036) and Pb isotopes are higher (206Pb'204Pb up to 18.30). The coherence of all the isotopes suggests that helium behaves as an incompatible element, and that helium isotopic variations in the Hawaiian lavas are produced by melting and mantle processes, rather than magma chamber or metasomatic processes unique to the gaseous elements. The variations of He, Sr, and Nd are most pronounced in lavas of approximately 10 ka age range [Kurz and Kammer, 1991], but the largest Pb isotopic variation occurs earlier. These variations are interpreted as resulting from the diminishing contribution from the upwelling mantle plume material as the shield building ends at Mauna Loa. The order of reduction in the plume isotopic signature is inferred to be Pb (at >100 ka), He (at ˜14 ka), Sr (at ˜9 ka), and Nd (at ˜8 ka); the different timing may relate to silicate/melt partition coefficients, with most incompatible elements removed first, and also to concentration variations within the plume. Zr/Nb, Sr/Nb, and fractionation-corrected Nb concentrations, correlate with the isotopes and are significantly higher in some of the submarine SWR lavas, suggesting temporal variability on time scales similar to the Pb isotopes (i.e. ˜ 100 ka). Historical lavas define trace element and isotopic trends that are distinct from the longer term (10 to 100 ka) variations, suggesting that different processes cause the short term variability. The temporal evolution of Mauna Loa, and particularly the new data from the submarine SWR, suggest that the isotopic composition of the upwelling plume mantle is best represented by data from Loihi seamount tholeiites. The temporal evolution suggests that the mantle source of the latest stage of Mauna Loa, which is characterized by radiogenic 87Sr/86Sr (up to .70395), unradiogenic 206Pb/204Pb (˜18.0), 3He/4He ratios similar to MORB, and low Nb concentrations, is a small-volume contribution related to non-plume components (such as normal asthenosphere, or entrained mantle).

Chondrites and the Protoplanetary Disk, Part 3

NASA Technical Reports Server (NTRS)

2004-01-01

Contents include the following: Ca-, Al-Rich Inclusions and Ameoboid Olivine Aggregates: What We Know and Don t Know About Their Origin. Aluminium-26 and Oxygen Isotopic Distributions of Ca-Al-rich Inclusions from Acfer 214 CH Chondrite. The Trapping Efficiency of Helium in Fullerene and Its Implicatiion to the Planetary Science. Constraints on the Origin of Chondritic Components from Oxygen Isotopic Compositions. Role of Planetary Impacts in Thermal Processing of Chondrite Materials. Formation of the Melilite Mantle of the Type B1 CAIs: Flash Heating or Transport? The Iodine-Xenon System in Outer and Inner Portions of Chondrules from the Unnamed Antarctic LL3 Chondrite. Nucleosynthesis of Short-lived Radioactivities in Massive Stars. The Two-Fluid Analysis of the Kelvin-Helmholtz Instability in the Dust Layer of a Protoplanetary Disk: A Possible Path to the Planetesimal Formation Through the Gravitational Instability. Shock-Wave Heating Model for Chonodrule Formation: Heating Rate and Cooling Rate Constraints. Glycine Amide Hydrolysis with Water and OH Radical: A Comparative DFT Study. Micron-sized Sample Preparation for AFM and SEM. AFM, FE-SEM and Optical Imaging of a Shocked L/LL Chondrite: Implications for Martensite Formation and Wave Propagation. Infrared Spectroscopy of Chondrites and Their Components: A Link Between Meteoritics and Astronomy? Mid-Infrared Spectroscopy of CAI and Their Mineral Components. The Origin of Iron Isotope Fractionation in Chondrules, CAIs and Matrix from Allende (CV3) and Chainpur (LL3) Chondrites. Protoplanetary Disk Evolution: Early Results from Spitzer. Kinetics of Evaporation-Condensation in a Melt-Solid System and Its Role on the Chemical Composition and Evolution of Chondrules. Oxygen Isotope Exchange Recorded Within Anorthite Single Crystal in Vigarano CAI: Evidence for Remelting by High Temperature Process in the Solar Nebula. Chondrule Forming Shock Waves in Solar Nebula by X-Ray Flares. Organic Globules with Anormalous Nitrogen Isotopic Compositions in the Tagish Lake Meteorite: Products of Primitive Organic Reactions. Yet Another Chondrule Formation Scenario. CAIs are Not Supernova Condensates. Microcrystals and Amorphous Material in Comets and Primitive Meteorites: Keys to Understanding Processes in the Early Solar System. A Nearby Supernova Injected Short-lived Radionuclides into Our Protoplanetary Disk. REE+Y Systematics in CC and UOC Chondrules. Meteoritic Constraints on Temperatures, Pressures, Cooling Rates, Chemical Compositions, and Modes of Condensation in the Solar Nebula. The I-Xe Record of Long Equilibration in Chondrules from the Unnamed Antarctic Meteorite L3/LL3. Early Stellar Evolution.

Fossil black smoker yields oxygen isotopic composition of Neoproterozoic seawater.

PubMed

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

2018-04-13

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

Unexpectedly large charge radii of neutron-rich calcium isotopes

DOE PAGES

Garcia Ruiz, R. F.; Bissell, M. L.; Blaum, K.; ...

2016-02-08

Here, despite being a complex many-body system, the atomic nucleus exhibits simple structures for certain ‘magic’ numbers of protons and neutrons. The calcium chain in particular is both unique and puzzling: evidence of doubly magic features are known in 40,48Ca, and recently suggested in two radioactive isotopes, 52,54Ca. Although many properties of experimentally known calcium isotopes have been successfully described by nuclear theory, it is still a challenge to predict the evolution of their charge radii. Here we present the first measurements of the charge radii of 49,51,52Ca, obtained from laser spectroscopy experiments at ISOLDE, CERN. The experimental results aremore » complemented by state-of-the-art theoretical calculations. The large and unexpected increase of the size of the neutron-rich calcium isotopes beyond N = 28 challenges the doubly magic nature of 52Ca and opens new intriguing questions on the evolution of nuclear sizes away from stability, which are of importance for our understanding of neutron-rich atomic nuclei.« less

Isotopic composition of Pb and Th in interplinian volcanics from Somma-Vesuvius volcano, Italy

USGS Publications Warehouse

Cortini, M.; Ayuso, R.A.; de Vivo, B.; Holden, P.; Somma, R.

2004-01-01

We present a detailed isotopic study of volcanic rocks emitted from Somma-Vesuvius volcano during three periods of interplinian activity: "Protohistoric" (3550 y B.P. to 79 A.D.), "Ancient Historic" (79 to 472 A.D.) and "Medieval" (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. 232Th/238U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. 232Th/238U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source. The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions of Sr and Nd. We suggest that reactions between magmas and fluids transported Pb and U, but not Sr. These data show that isotope mixing in the mantle is active at different times and scales. ?? Springer-Verlag 2004.

Near-surface clay authigenesis in exhumed fault rock of the Alpine Fault Zone (New Zealand); O-H-Ar isotopic, XRD and chemical analysis of illite and chlorite

NASA Astrophysics Data System (ADS)

Boles, Austin; Mulch, Andreas; van der Pluijm, Ben

2018-06-01

Exhumed fault rock of the central Alpine Fault Zone (South Island, New Zealand) shows extensive clay mineralization, and it has been the focus of recent research that aims to describe the evolution and frictional behavior of the fault. Using Quantitative X-ray powder diffraction, 40Ar/39Ar geochronology, hydrogen isotope (δD) geochemistry, and electron microbeam analysis, we constrain the thermal and fluid conditions of deformation that produced two predominant clay phases ubiquitous to the exposed fault damage zone, illite and chlorite. Illite polytype analysis indicates that most end-member illite and chlorite material formed in equilibrium with meteoric fluid (δD = -55 to -75‰), but two locations preserve a metamorphic origin of chlorite (δD = -36 to -45‰). Chlorite chemical geothermometry constrains crystal growth to T = 210-296 °C. Isotopic analysis also constrains illite growth to T < 100 °C, consistent with the mineralogy, with Ar ages <0.5 Ma. High geothermal gradients in the study area promoted widespread, near-surface mineralization, and limited the window of clay authigenesis in the Alpine Fault Zone to <5 km for chlorite and <2 km for illite. This implies a significant contrast between fault rock exposed at the surface and that at depth, and informs discussions about fault strength, clays and frictional behavior.

Trophic specialization and morphological divergence between two sympatric species in Lake Catemaco, Mexico.

PubMed

Ornelas-García, Claudia Patricia; Córdova-Tapia, Fernando; Zambrano, Luis; Bermúdez-González, María Pamela; Mercado-Silva, Norman; Mendoza-Garfias, Berenit; Bautista, Amando

2018-05-01

The association of morphological divergence with ecological segregation among closely related species could be considered as a signal of divergent selection in ecological speciation processes. Environmental signals such as diet can trigger phenotypic evolution, making polymorphic species valuable systems for studying the evolution of trophic-related traits. The main goal of this study was to analyze the association between morphological differences in trophic-related traits and ecological divergence in two sympatric species, Astyanax aeneus and A. caballeroi, inhabiting Lake Catemaco, Mexico. The trophic differences of a total of 70 individuals (35 A. aeneus and 35 A. caballeroi ) were examined using stable isotopes and gut content analysis; a subset of the sample was used to characterize six trophic and six ecomorphological variables. In our results, we recovered significant differences between both species in the values of stable isotopes, with higher values of δ 15 N for A. caballeroi than for A. aeneus . Gut content results were consistent with the stable isotope data, with a higher proportion of invertebrates in A. caballeroi (a consumption of invertebrates ten times higher than that of A. aeneus , which in turn consumed three times more vegetal material than A. caballeroi ). Finally, we found significant relationship between ecomorphology and stable isotopes ( r  = .24, p  < .01), hence, head length, preorbital length, eye diameter, and δ 15 N were all positively correlated; these characteristics correspond to A. caballeroi . While longer gut and gill rakers, deeper bodies, and vegetal material consumption were positively correlated and corresponded to A. aeneus . Our results are consistent with the hypothesis that morphological divergence in trophic-related traits could be associated with niche partitioning, allowing the coexistence of closely related species and reducing interspecific competition.

Research Report to the National Aeronautics and Space Administration Cosmochemistry Program

NASA Technical Reports Server (NTRS)

Alexander, Conel O'D.

2004-01-01

The discovery of presolar grains in meteorites is one of the most exciting recent developments in meteoritics. Six types of presolar grain have been discovered: diamond, Sic, graphite, Si3N4, Al2O3 and MgAl2O4 (NIITLER, 2003). These grains have been identified as presolar because their isotopic compositions are very different from those of Solar System materials. Comparison of their isotopic compositions with astronomical observations and theoretical models indicates that most of the grains formed in the envelopes of highly evolved stars. They are, therefore, a new source of information with which to test astrophysical models of the evolution of these stars. In fact, because several elements can often be measured in the same grain, including elements that are not measurable spectroscopically in stars, the grain data provide some very stringent constraints for these models. Our primary goal is to create large, unbiased, multi-isotope databases of single presolar Sic, Si3N4, oxide and graphite grains in meteorites, as well as any new presolar grain types that are identified in the future. These will be used to: (i) test stellar and nucleosynthetic models, (ii) constrain the galactic chemical evolution (GCE) paths of the isotopes of Si, Ti, O and Mg, (iii) establish how many stellar sources contributed to the Solar System, (iv) constrain relative dust production rates of various stellar types and (v) assess how representative of galactic dust production the record in meteorites is. The primary tool for this project is a highly automated grain analysis system on the Carnegie 6f ion probe. This proposal was part of a long-standing research effort that is still ongoing.

Odd-even parity splittings and octupole correlations in neutron-rich Ba isotopes

NASA Astrophysics Data System (ADS)

Fu, Y.; Wang, H.; Wang, L.-J.; Yao, J. M.

2018-02-01

The odd-even parity splittings in low-lying parity-doublet states of atomic nuclei with octupole correlations have usually been interpreted as rotational excitations on top of octupole vibration in the language of collective models. In this paper, we report a deep analysis of the odd-even parity splittings in the parity-doublet states of neutron-rich Ba isotopes around neutron number N =88 within a full microscopic framework of beyond-mean-field multireference covariant energy density functional theory. The dynamical correlations related to symmetry restoration and quadrupole-octupole shape fluctuation are taken into account with a generator coordinate method combined with parity, particle-number, and angular-momentum projections. We show that the behavior of odd-even parity splittings is governed by the interplay of rotation, quantum tunneling, and shape evolution. Similar to 224Ra, a picture of rotation-induced octupole shape stabilization in the positive-parity states is exhibited in the neutron-rich Ba isotopes.

Multiple Nebular Gas Reservoirs Recorded by Oxygen Isotope Variation in a Spinel-rich CAI in CO3 MIL 090019

NASA Technical Reports Server (NTRS)

Simon, J. I.; Simon, S. B.; Nguyen, A. N.; Ross, D. K.; Messenger, S.

2017-01-01

We conducted NanoSIMS O-isotopic imaging of a primitive spinel-rich CAI spherule (27-2) from the MIL 090019 CO3 chondrite. Inclusions such as 27-2 are proposed to record inner nebula processes during an epoch of rapid solar nebula evolution. Mineralogical and textural analyses suggest that this CAI formed by high temperature reactions, partial melting, and condensation. This CAI exhibits radial O-isotopic heterogeneity among multiple occurrences of the same mineral, reflecting interactions with distinct nebular O-isotopic reservoirs.

In Situ Missions For Investigation of the Climate, Geology and Evolution of Venus

NASA Astrophysics Data System (ADS)

Grinspoon, David

2017-10-01

In situ Exploration of Venus has been recommended by the Decadal Study of the National Research Council. Many high priority measurements, addressing outstanding first-order, fundamental questions about current processes and evolution of Venus can only be made from in situ platforms such as entry probes, balloons or landers. These include: measuring noble gases and their isotopes to constrain origin and evolution; measuring stable isotopes to constrain the history of water and other volatiles; measuring trace gas profiles and sulfur compounds for chemical cycles and surface-atmosphere interactions, constraining the coupling of radiation, dynamics and chemistry, making visible and infrared descent images, and measuring surface and sub-surface composition. Such measurements will allow us deepen our understanding of the origin and evolution of Venus in the context of the terrestrial planets and extrasolar planets, to determine the level and style of current geological activity and to characterize the divergent climate evolution of Venus and Earth and extend our knowledge of the limits of habitability on hot terrestrial planets.

Paloma: In-Situ Measurement of the Isotopic Composition of Mars Atmosphere

NASA Astrophysics Data System (ADS)

Jambon, A.; Quemerais, E.; Chassiefiere, E.; Berthelier, J. J.; Agrinier, P.; Cartigny, P.; Javoy, M.; Moreira, M.; Sabroux, J. -C.; Sarda, P.; Pineau, J. -F.

2000-07-01

Scientific objectives for an atmospheric analysis of Mars are presented in the DREAM project. Among the information presently available most are fragmentary or limited in their precision for both major element (H, C, O, N) and noble gas isotopes. These data are necessary for the understanding and modelling of Mars atmospheric formation and evolution, and consequently for other planets, particularly the Earth. To fulfill the above requirements, two approaches can be envisonned: 1) analysis of a returned sample (DREAM project) or 2) in situ analysis, e.g. PALOMA project presented here. Among the advantages of in situ analysis, we notice: the minimal terrestrial contamination, the unlimited availability of gas to be analyzed and the possibility of multiple analyses (replicates, daynight... ). Difficulties specific to in situ analyses are of a very different kind to those of returned samples. In situ analysis could also be viewed as a preparation to future analysis of returned samples. Finally, some of the measurements will not be possible on Earth: for instance, radon and its short lived decay products, will provide complementary information to 4-He analysis and can only be obtained in situ, independently of analytical capabilities.

Geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) constraints on Quaternary bimodal volcanism of the Nigde Volcanic Complex (Central Anatolia, Turkey)

NASA Astrophysics Data System (ADS)

Aydin, F.; Siebel, W.; Uysal, I.; Ersoy, E. Y.; Schmitt, A. K.; Sönmez, M.; Duncan, R.

2012-04-01

The Nigde Volcanic Complex (NVC) is a major Late Neogene-Quaternary volcanic centre within the Cappadocian Volcanic Province of Central Anatolia. The Late Neogene evolution of the NVC generally initiated with the eruption of extensive andesitic-dacitic lavas and pyroclastic flow deposits, and minor basaltic lavas. This stage was followed by a Quaternary bimodal magma suite which forms Na-alkaline/transitional basaltic and high-K calc-alkaline to alkaline silicic volcanic rocks. In this study, we present new geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) data for the bimodal volcanic suite within the NVC. Recent data suggest that the eruption of this suite took place ranges between ~650 and ~220 ka (Middle-Late Pleistocene). Silicic rocks consisting of rhyolite and associated pumice-rich pyroclastic fall out and surge deposits define a narrow range of 143Nd/144Nd isotope ratios (0.5126-0.5127), and show virtually no difference in Pb isotope composition (206Pb/204Pb = 18.84-18.87, 207Pb/204Pb = 15.64-15.67 and 208Pb/204Pb = 38.93-38.99). 87Sr/86Sr isotopic compositions of the silicic (0.704-0.705) and basaltic rocks (0.703-0.705) are rather similar reflecting a common source. The most mafic sample from basaltic rocks related to monogenetic cones is characterized by 87Sr/86Sr = 0.704, 143Nd/144Nd = 0.5127, 206Pb/204Pb = 18.80, 207Pb/204Pb = 15.60 and 208Pb/204Pb = 38.68. These values suggest a moderately depleted signature of the mantle source. The geochronological and geochemical data suggest that NVC silicic and basaltic rocks are genetically closely related to each other. Mantle derived differentiated basaltic melts which experienced low degree of crustal assimilation are suggested to be the parent melt of the rhyolites. Further investigations will focus on the spatial and temporal evolution of Quaternary bimodal magma suite in the NVC and the genetic relation between silicic and basaltic rocks through detailed oxygen isotope analysis and (U-Th)/He zircon geochronology.

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.

Generation and Evolution of Quaternary Magmas Beneath Tengchong: Sr-Nd-Pb-Hf Isotope and Zircon U-series Age Constraints

NASA Astrophysics Data System (ADS)

Zou, H.; Ma, M.; Fan, Q.; Xu, B.; Li, S. Q.; Zhao, Y.; King, D. T., Jr.

2017-12-01

The Tengchong volcanic field on the southeastern margin of the Tibetan Plateau represents rare Quaternary volcanic eruptions on the plateau. The Quaternary Tengchong volcanic field formed high-potassium calc-alkaline volcanic rocks that include trachybasalts, basaltic trachyandesites, trachyandesites, and dacites. Herein, we present comprehensive Nd-Sr-Pb-Hf isotopic and elemental data for trachybasalts, basaltic trachyandesites, and trachyandesites from four young Tengchong volcanoes at Maanshan, Dayingshan, Heikongshan, and Laoguipo, in order to understand their magma genesis and evolution. Nd-Sr-Pb-Hf isotopes for the primitive Tengchong magma (trachybasalts with SiO2 <52.5 wt. % and MgO >5.5% wt. %) reflect a heterogeneous enriched mantle source. High Th/U, Th/Ta, and Rb/Nb ratios and Nd-Sr-Pb-Hf isotope characteristics of the primitive magmas suggest that the enriched mantle beneath Tengchong formed as a result of subduction of clay-rich sediments, which probably came from the Indian continental plate. Partial melting of the enriched mantle was generated by deep continental subduction coupled with recent regional extension in the Tengchong area. With regard to the evolved magmas (basaltic trachyandesites and trachyandesites), good correlations between SiO2 content and the ratios 87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb, and 177Hf/176Hf strongly suggest that the combined assimilation and fractional crystallization (AFC) was an important process during magma evolution to form these basaltic trachyandesites and trachyandesites. Uranium-series zircon dating on these evolved lavas from Tengchong is used to constrain their magma evolution and residence timescales.

Evolution of deformation in neutron-rich Ba isotopes up to A =150

NASA Astrophysics Data System (ADS)

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

2018-02-01

The occurrence of octupolar shapes in the Ba isotopic chain was recently established experimentally up to N =90 . To further extend the systematics, the evolution of shapes in the most neutron-rich members of the Z =56 isotopic chain accessible at present, Ba,150148, has been studied via β decay at the ISOLDE Decay Station. This paper reports on the first measurement of the positive- and negative-parity low-spin excited states of 150Ba and presents an extension of the β -decay scheme of 148Cs. Employing the fast timing technique, half-lives for the 21+ level in both nuclei have been determined, resulting in T1 /2=1.51 (1 ) ns for 148Ba and T1 /2=3.4 (2 ) ns for 150Ba. The systematics of low-spin states, together with the experimental determination of the B (E 2 :2+→0+) transition probabilities, indicate an increasing collectivity in Ba-150148, towards prolate deformed shapes. The experimental data are compared to symmetry conserving configuration mixing (SCCM) calculations, confirming an evolution of increasingly quadrupole deformed shapes with a definite octupolar character.

Stabile Chlorine Isotope Study of Martian Shergottites and Nakhlites; Whole Rock and Acid Leachates and Residues

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C-Y; Fujitani, T.; Okano, O.

2011-01-01

We have established a precise analytical technique for stable chlorine isotope measurements of tiny planetary materials by TIMS (Thermal Ionization Mass Spectrometry) [1], for which the results are basically consistent with the IRMS tech-nique (gas source mass spectrometry) [2,3,4]. We present here results for Martian shergottites and nakhlites; whole rocks, HNO3-leachates and residues, and discuss the chlorine isotope evolution of planetary Mars.

Ion microprobe analysis of {sup 18}O/{sup 16}O in authigenic and detrital quartz in the St. Peter Sandstone, Michigan Basin and Wisconsin Arch, USA: Contrasting diagenetic histories

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

Graham, C.M.; Valley, J.W.; Winter, B.L.

1996-12-01

The oxygen isotopic compositions of authigenic quartz cements in sandstones provide a monitor of the temperatures, compositions, and origins of pore-occluding fluids during diagenesis, but quartz overgrowths are too fine-grained to be amenable to conventional isotopic analysis. We have used a Cameca ims-4f ion microprobe to determine oxygen isotopic variations in authigenic and detrital quartz in four samples of the Ordovician St. Peter Sandstone from the Michigan Basin and Wisconsin Arch, midwestern USA. Ion microprobe isotopic analyses have been successfully accomplished with an internal precision of {+-}1{per_thousand} (1{sigma}) and a spatial resolution of 20-30 {mu}m at low mass resolution usingmore » a high voltage offset technique. Repeated analyses of the quartz standard demonstrate a reproducibility of close to {+-}1{per_thousand} (1 sd) in good agreement with that expected from counting statistics. Conventional and ion microprobe analyses are mutually consistent, supporting the accuracy of the ion microprobe analyses. Within-sample isotopic variations of up to 13{per_thousand} and micro-scale isotopic variations of at least 4{per_thousand} over a distance of 100 {mu}m have been measured within quartz overgrowths in a sandstone from the Wisconsin Arch. Overgrowths are uniformly higher in {delta}{sup 18}O than detrital grains, and gradients of up to 25% exist across a few microns. {sup 18}O-enriched quartz overgrowths in sandstones from the Wisconsin Arch show complex CL zonation and reflect one of two possible processes: (1) low-temperature quartz precipitation during mixing of meteoric waters with upwelling basinal fluids; (2) higher temperature quartz precipitation during episodic gravity-driven upwelling of warm basinal fluids (of comparable isotopic composition to Michigan Basin fluids) from the Illinois Basin, related to evolution of Mississippi Valley type Pb-Zn ore-forming fluids. 59 refs., 7 figs., 4 tabs.« less

Mo isotope fractionation during hydrothermal evolution of porphyry Cu systems

NASA Astrophysics Data System (ADS)

Shafiei, Behnam; Shamanian, GholamHossein; Mathur, Ryan; Mirnejad, Hassan

2015-03-01

We present Mo isotope compositions of molybdenite types from three successive stages of ore deposition in several porphyry copper deposits of the Kerman region, Iran. The data provide new insights into controlling processes on Mo isotope fractionation during the hydrothermal evolution of porphyry systems. The Mo isotope compositions of 27 molybdenite samples show wide variations in δ97Mo ranging from -0.37 to +0.92 ‰. The data reveal that molybdenites in the early and transitional stages of mineralization (preferentially 2H polytypes; δ97Mo mean = 0.35 ‰) have higher δ97Mo values than late stage (mainly 3R polytypes; δ97Mo mean = 0.02 ‰) molybdenites. This trend suggests that fractionation of Mo isotopes occurred in high-temperature stages of mineralization and that hydrothermal systems generally evolve towards precipitation of molybdenite with lower δ97Mo values. Taking into account the genetic models proposed for porphyry Cu deposits along with the temperature-dependent fractionation of Mo isotope ratios, it is proposed that large variations of Mo isotopes in the early and the transitional stages of ore deposition could be controlled by the separation of the immiscible ore-forming fluid phases with different density, pH, and ƒO2 properties (i.e., brine and vapor). The fractionation of Mo isotopes during fluid boiling and Rayleigh distillation processes likely dominates the Mo isotope budget of the remaining ore-forming fluids for the late stage of mineralization. The lower δ97Mo values in the late stage of mineralization can be explained by depletion of the late ore-forming hydrothermal solutions in 97Mo, as these fluids have moved to considerable distance from the source. Finally, the relationship observed between MoS2 polytypes (2H and 3R) and their Mo isotopic compositions can be explained by the molecular vibration theory, in which heavier isotopes are preferentially partitioned into denser primary 2H MoS2 crystals.

Tracing fluid transfer across subduction zones using iron and zinc stable isotopes

NASA Astrophysics Data System (ADS)

Williams, H. M.; Debret, B.; Pons, M. L.; Bouilhol, P.

2016-12-01

In subduction zones, serpentinite devolatilization within the downgoing slab and the fluids released play a fundamental role in volatile transfer as well as the redox evolution of the sub-arc mantle. Constraining subduction-related serpentinite devolatilisation is essential in order to better understand of the nature and composition of slab-derived fluids and fluid/rock interactions. Fe and Zn stable isotopes can trace fluid composition and speciation as isotope partitioning is driven by changes in oxidation state, coordination, and bonding environment. In the case of serpentinite devolatilisation, Fe isotope fractionation should reflect changes in Fe redox state and the formation of Fe-Cl- and SO42- complexes (Hill et al., GCA 2010); Zn isotope fractionation should be sensitive to complexation with CO32-, HS- and SO42- anions (Fujii et al., GCA 2011). We targeted samples from Western Alps ophiolite complexes, interpreted as remnants of serpentinized oceanic lithosphere metamorphosed and devolatilized during subduction (Hattori and Guillot, G3 2007; Debret et al., Chem. Geol. 2013). A striking negative correlation is present between bulk serpentinite Fe isotope composition and Fe3+/Fetot, with the highest grade samples displaying the heaviest Fe isotope compositions and lowest Fe3+/Fetot (Debret et al., Geology, 2016). The same samples also display a corresponding variation in Zn isotopes, with the highest grade samples displaying isotopically light compositions (Pons et al., in revision). The negative correlation between Fe and Zn isotopes and decrease in Fe3+/Fetot can explained by serpentinite sulfide breakdown and the release of fluids enriched in isotopically light Fe and heavy Zn sulphate complexes. The migration of these SOX-bearing fluids from the slab to the slab-mantle interface or mantle wedge has important implications for the redox evolution of the sub-arc mantle and the transport of metals from the subducting slab.

Long-term evolution of the heliospheric magnetic field inferred from cosmogenic 44Ti activity in meteorites

NASA Astrophysics Data System (ADS)

Mancuso, S.; Taricco, C.; Colombetti, P.; Rubinetti, S.; Sinha, N.; Bhandari, N.

2018-02-01

Typical reconstructions of historic heliospheric magnetic field (HMF) BHMF are based on the analysis of the sunspot activity, geomagnetic data or on measurement of cosmogenic isotopes stored in terrestrial reservoirs like trees (14C) and ice cores (10Be). The various reconstructions of BHMF are however discordant both in strength and trend. Cosmogenic isotopes, which are produced by galactic cosmic rays impacting on meteoroids and whose production rate is modulated by the varying HMF convected outward by the solar wind, may offer an alternative tool for the investigation of the HMF in the past centuries. In this work, we aim to evaluate the long-term evolution of BHMF over a period covering the past twenty-two solar cycles by using measurements of the cosmogenic 44Ti activity (τ1/2 = 59.2 ± 0.6 yr) measured in 20 meteorites which fell between 1766 and 2001. Within the given uncertainties, our result is compatible with a HMF increase from 4.87-0.30+0.24 nT in 1766 to 6.83-0.11+0.13 nT in 2001, thus implying an overall average increment of 1.96-0.35+0.43 nT over 235 years since 1766 reflecting the modern Grand maximum. The BHMF trend thus obtained is then compared with the most recent reconstructions of the near-Earth HMF strength based on geomagnetic, sunspot number, and cosmogenic isotope data.

Evolution of the depleted mantle and growth of the continental crust: improving on the imperfect detrital zircon record

NASA Astrophysics Data System (ADS)

Vervoort, J. D.; Kemp, A. I. S.; Patchett, P. J.

2012-04-01

One of the basic tenets of terrestrial geochemistry is that the continental crust has been extracted from the mantle leaving the latter depleted in incompatible elements. Nd and Hf isotopes have long shown that this process has been an essential feature of the Earth throughout its history. There is wide agreement on the general nature of this process, but the details of the isotopic record—and their implications for the depletion of the mantle and the extraction of continental crust—remain debated. Recently, much attention has been given to detrital zircons in both modern and ancient sediments. An advantage of this approach is the integration of the crystallization history of the zircon from the U-Pb chronometer with its Hf isotopic composition, which can provide important information on whether the zircons have been derived from juvenile or reworked crust. One essential requirement in this approach, however, is to unambiguously determine the crystallization ages of the zircons. We suggest that this represents an important—but generally ignored—source of uncertainty in the Hf isotopic record from detrital zircons. The quality filter most often used to assess the integrity of zircon U-Pb systematics is concordance; if a zircon is concordant, it is assumed that the U-Pb age is accurate. A concordance filter is less effective in old zircons, however, because ancient Pb loss, viewed today, parallels concordia. Without the benefit from the geological context of the host rock to the zircons, it is impossible to unambiguously determine it true crystallization age. Ancient Pb loss in zircons produces an apparent age less than the true magmatic age. The initial Hf isotopic composition of these zircons, as a result, will be calculated at the wrong age and will be anomalously low (by ~2.2 epsilon Hf units per 0.1 Ga). Hf model ages, calculated from these parameters, will be artificially old and spurious. The combination of unradiogenic Hf and Hf model ages > U-Pb ages in the zircon record are often given as prima facie evidence of crustal reworking and recycling during Earth's early history, and underpin models for large volumes of ancient continental crust. For many of these old zircons it may have nothing to do with crustal reworking, but simply reflect unrecognized ancient Pb loss. A more robust picture of the isotopic evolution of the Earth can be gained from an integrated approach of Hf and Nd isotopes in well age-constrained magmatic samples: careful U-Pb zircon geochronology to determine the crystallization age of the rock; Hf isotopic composition of the zircons; and Hf and Nd isotopic measurements of the whole-rocks. We demonstrate this with respect to evolution of the depleted mantle, and discuss the implications for the timing of crust formation. An important part of this approach is the realization that not all rock samples (or zircons!) yield useful, unambiguous results. Inclusion of all Hf isotope data from large zircon databases, unscrutinized for quality and lacking in context, will do more to obscure our understanding of the isotopic evolution of the Earth than to clarify it.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Isotopic evolution of the idaho batholith and Challis intrusive province, Northern US Cordillera

USGS Publications Warehouse

Gaschnig, Richard M.; Vervoort, J.D.; Lewis, R.S.; Tikoff, B.

2011-01-01

The Idaho batholith and spatially overlapping Challis intrusive province in the North American Cordillera have a history of magmatism spanning some 55 Myr. New isotopic data from the ???98 Ma to 54 Ma Idaho batholith and ???51 Ma to 43 Ma Challis intrusions, coupled with recent geochronological work, provide insights into the evolution of magmatism in the Idaho segment of the Cordillera. Nd and Hf isotopes show clear shifts towards more evolved compositions through the batholith's history and Pb isotopes define distinct fields correlative with the different age and compositionally defined suites of the batholith, whereas the Sr isotopic compositions of the various suites largely overlap. The subsequent Challis magmatism shows the full range of isotopic compositions seen in the batholith. These data suggest that the early suites of metaluminous magmatism (98-87 Ma) represent crust-mantle hybrids. Subsequent voluminous Atlanta peraluminous suite magmatism (83-67 Ma) results primarily from melting of different crustal components. This can be attributed to crustal thickening, resulting from either subduction processes or an outboard terrane collision. A later, smaller crustal melting episode, in the northern Idaho batholith, resulted in the Bitterroot peraluminous suite (66-54 Ma) and tapped different crustal sources. Subsequent Challis magmatism was derived from both crust and mantle sources and corresponds to extensional collapse of the over-thickened crust. ?? The Author 2011. Published by Oxford University Press. All rights reserved.

Petrology of lunar rocks and implication to lunar evolution

NASA Technical Reports Server (NTRS)

Ridley, W. I.

1976-01-01

Recent advances in lunar petrology, based on studies of lunar rock samples available through the Apollo program, are reviewed. Samples of bedrock from both maria and terra have been collected where micrometeorite impact penetrated the regolith and brought bedrock to the surface, but no in situ cores have been taken. Lunar petrogenesis and lunar thermal history supported by studies of the rock sample are discussed and a tentative evolutionary scenario is constructed. Mare basalts, terra assemblages of breccias, soils, rocks, and regolith are subjected to elemental analysis, mineralogical analysis, trace content analysis, with studies of texture, ages and isotopic composition. Probable sources of mare basalts are indicated.

Chemical evolution with rotating massive star yields - I. The solar neighbourhood and the s-process elements

NASA Astrophysics Data System (ADS)

Prantzos, N.; Abia, C.; Limongi, M.; Chieffi, A.; Cristallo, S.

2018-05-01

We present a comprehensive study of the abundance evolution of the elements from H to U in the Milky Way halo and local disc. We use a consistent chemical evolution model, metallicity-dependent isotopic yields from low and intermediate mass stars and yields from massive stars which include, for the first time, the combined effect of metallicity, mass loss, and rotation for a large grid of stellar masses and for all stages of stellar evolution. The yields of massive stars are weighted by a metallicity-dependent function of the rotational velocities, constrained by observations as to obtain a primary-like 14N behaviour at low metallicity and to avoid overproduction of s-elements at intermediate metallicities. We show that the Solar system isotopic composition can be reproduced to better than a factor of 2 for isotopes up to the Fe-peak, and at the 10 per cent level for most pure s-isotopes, both light ones (resulting from the weak s-process in rotating massive stars) and the heavy ones (resulting from the main s-process in low and intermediate mass stars). We conclude that the light element primary process (LEPP), invoked to explain the apparent abundance deficiency of the s-elements with A < 100, is not necessary. We also reproduce the evolution of the heavy to light s-elements abundance ratio ([hs/ls]) - recently observed in unevolved thin disc stars - as a result of the contribution of rotating massive stars at sub-solar metallicities. We find that those stars produce primary F and dominate its solar abundance and we confirm their role in the observed primary behaviour of N. In contrast, we show that their action is insufficient to explain the small observed values of ^{12}C/^{13}C in halo red giants, which is rather due to internal processes in those stars.

The Azores plume influence on the SASC-Great Meteor and MAR: the importance for the Portuguese Extension of the Continental Shelf Project (PECSP)

NASA Astrophysics Data System (ADS)

Ribeiro, Luisa P.; Madureira, Pedro; Hildenbrand, Anthony; Martins, Sofia; Mata, João

2017-04-01

The Southern Azores Seamount Chain (SASC) is a group of large seamounts located south of the Azores Plateau and east of the Mid-Atlantic Ridge (MAR) and part of the natural prolongation of the Azores land mass. The SASC, including the Great Meteor Seamount (aprox. 1000km south of São Miguel), is rooted on a flat, gently SE dipping Terrace, surrounded by steep scarps with almost 2000 m high. Only a few studies from the 70-80's discuss the geologic and/or geodynamic evolution of this region based on scarce bathymetry and geophysical data. Wendt et al. (1976) presented geochemical data and K-Ar ages on three basalt from the Great Meteor Seamount (<16Ma old), later analyzed for Sr-Nd-Pb isotopes by Geldmacher et al. (2006). Given the rarity of geochemical data, the origin of the seamounts and the regional evolution of this large area of the Atlantic, remains largely unknown. During the preparatory work of the PECSP, the EMEPC promoted three oceanographic campaigns to the SASC (2007, 2008 and 2009) with multidisciplinary teams. Within these cruises, more than 120 samples were dredged or collected with the Luso ROV (rated to 6000m depth) although less than 50 were suitable for major and trace elements analysis, for Sr-Nd-Pb-Hf isotopes and for K-Ar radiometric dating. Early studies relating the SASC with the New England Seamounts can be refuted by geophysical data and kinematic models presented by Gente et al. (2003) and, also by our new isotopic data, which shows that isotope ratios are clearly distinct from New England (Ribeiro et al., in prep). However, the analyzed SASC basalts display isotope ratios that overlap the Azores isotopic signature. Two new K-Ar ages (unspiked Cassignol-Gillot technique on fresh separated groundmass and/or plagioclase microlites) on the seamounts show coeval volcanism at Plato Seamount SE flank (33.4±0.5 Ma) an at Small Hyeres Seamount (31.7±0.5Ma). The SASC basalts erupted on the Terrace through an oceanic crust with 26Ma and 43Ma, respectively, at the time of eruption. Contemporaneous with this activity, the basalts erupted on-axis at the MAR between the Hayes FZ and the Azores, correspond to E-MORB with an radiogenic isotopic signature trending towards the Azores (Dupré and Bougault, 1985; Jenner et al., 1985). The similarity between the SASC and the Azores mantle source can be explained by the impingement of the long-lived (aprox. 85Ma) Azores plume beneath the Nubian Plate, as argued by Gente et al. (2003), which also influenced the MAR evolution. Our study endorses the genetic link between the Azores Archipelago and the SASC to the Azores plume, contributing to better constrain the temporal-spatial evolution of this region of the north Atlantic, which is enclosed by the Azores Platform. Moreover, the new data gathered within the PECSP contributed to constrain the boundary of the Azores Platform submarine elevation according to the provisions of article 76 of UNCLOS. Wendt et al. (1976) Deep-Sea-Research 23; Geldmacher et al. (2006) Lithos 90; Dupré and Bougault, (1985) DSDP82; Jenner et al., (1985) DSDP82; Gente et al. (2003) G3, 4

Ages and Growth of the Continental Crust from Radiogenic Isotopes

NASA Astrophysics Data System (ADS)

Patchett, P. J.; Samson, S. D.

2003-12-01

The development and application of radiogenic isotopes to dating of geologic events, and to questions of growth, evolution, and recycling processes in the continental crust are mature areas of scientific inquiry. By this we understand that many of the approaches used to date rocks and constrain the evolution of the continents are well established, even routine, and that the scope of data available on age and evolution of continents is very large. This is not to say that new approaches have not been developed in recent years, or that new approaches and/or insights cannot be developed in the future. However, the science of continental crustal evolution is definitely a domain where many of the problems are well defined, the power of the techniques used to solve them are well known, and the limitations of field and laboratory databases, as well as the preserved geologic record, are understood.From the very early days of crustal evolution studies, it was innovations and improvements in laboratory techniques that drove the pace of discovery (e.g., Holmes, 1911; Nier, 1939). This remained true through all the increments in capability reviewed in this chapter, up to the present day. Thus, continental crustal evolution is an area of Earth science where a species of very laboratory-oriented investigator, the "radiogenic isotope geologist" or "geochronologist," has made major advances, even breakthroughs, in understanding. This is true in spite of the fact that many of the individuals of the species may have lacked field expertise, or even more than a primitive level of geologic background. Because design and building of instruments like radiation detectors or mass spectrometers requires a knowledge of physics, many of the early practitioners of rock dating were physicists, like Alfred Nier (cited above). Since the 1970s, essentially all mass spectrometers have been constructed by specialized commercial firms, and the level of physics expertise among isotope geologists has been lower. These firms, based mainly (but not exclusively) in and around Manchester, England, and Bremen, Germany, have spearheaded technical innovations in mass spectrometry. Isotope geology researchers are one group of consumers for this technology, along with chemists, nuclear-weapon laboratories and nuclear-power generating facilities. Today, the vast majority of isotope geology researchers are derived from geological backgrounds.This chapter will briefly review historical aspects of the development of radiogenic isotope geology as applied to continents. Some details, references and cross-references to other chapters in this volume will be provided for most major radiogenic isotopic methods, and for applications of these. However, this chapter will ultimately concentrate on two major approaches that dominate the research field today: (i) crustal tectonic and magmatic ages from U-Pb dating of accessory minerals like zircon; and (ii) crustal differentiation and growth from neodymium isotopic determinations on total rocks.The sheer amount of data available from continental areas, and the pace of data acquisition today, places any geographically constrained compilation in the impossible category for a chapter like this one. In this chapter, the state of the art in both geochronology and crustal origins will be illustrated by selected examples, not by global compilations or comprehensive discussions of each region that has been studied. Nevertheless, some remarks about the availability of data from different parts of the world need to be made. As with other areas of geology, biology, and botany, the parts of the world that have been longest settled by western civilization have the best data coverage for both ages of continental rocks, and their origins and evolution. Thus, Western Europe, Canada, the USA and Australia have generally somewhat thorough coverage. More limited data have become available from Eastern Europe, Greenland, Central and South America, Africa, Asia, and Antarctica. Some of these data have been produced by groups based in those regions, but much of the data published between 1970 and today have been driven by studies based in, and funded from, western countries. Availability of state-of-the-art results for ages of crust and its evolution are low in Antarctica and Greenland, where climate and ice cover limit work, and in South America, Africa, and parts of Asia, where studies have been sporadic, and are certainly limited in some cases by political instability. This general situation is now changing, however. Two parts of the world where results for ages of orogenic belts and for crustal evolution in general are accumulating more rapidly since about 1990 are China and Russia; this is connected with growth of modern isotope geology facilities in those countries. Understanding of global continent growth and evolution is limited in critical respects by the large regions of the world that are poorly dated. Therefore, gradual improvement of the state of knowledge of less accessible parts of the continents will bring significant benefits, even though the conceptual issues may be understood to a large extent.

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Mechanistic investigation of the formation of H2 from HCOOH with a dinuclear Ru model complex for formate hydrogen lyase.

PubMed

Tokunaga, Taisuke; Yatabe, Takeshi; Matsumoto, Takahiro; Ando, Tatsuya; Yoon, Ki-Seok; Ogo, Seiji

2017-01-01

We report the mechanistic investigation of catalytic H 2 evolution from formic acid in water using a formate-bridged dinuclear Ru complex as a formate hydrogen lyase model. The mechanistic study is based on isotope-labeling experiments involving hydrogen isotope exchange reaction.

Osmium Isotopic Evolution of the Mantle Sources of Precambrian Ultramafic Rocks

NASA Astrophysics Data System (ADS)

Gangopadhyay, A.; Walker, R. J.

2006-12-01

The Os isotopic composition of the modern mantle, as recorded collectively by ocean island basalts, mid- oceanic ridge basalts (MORB) and abyssal peridotites, is evidently highly heterogeneous (γ Os(I) ranging from <-10 to >+25). One important question, therefore, is how and when the Earth's mantle developed such large-scale Os isotopic heterogeneities. Previous Os isotopic studies of ancient ultramafic systems, including komatiites and picrites, have shown that the Os isotopic heterogeneity of the terrestrial mantle can be traced as far back as the late-Archean (~ 2.7-2.8 Ga). This observation is based on the initial Os isotopic ratios obtained for the mantle sources of some of the ancient ultramafic rocks determined through analyses of numerous Os-rich whole-rock and/or mineral samples. In some cases, the closed-system behavior of these ancient ultramafic rocks was demonstrated via the generation of isochrons of precise ages, consistent with those obtained from other radiogenic isotopic systems. Thus, a compilation of the published initial ^{187}Os/^{188}Os ratios reported for the mantle sources of komatiitic and picritic rocks is now possible that covers a large range of geologic time spanning from the Mesozoic (ca. 89 Ma Gorgona komatiites) to the Mid-Archean (e.g., ca. 3.3 Ga Commondale komatiites), which provides a comprehensive picture of the Os isotopic evolution of their mantle sources through geologic time. Several Precambrian komatiite/picrite systems are characterized by suprachondritic initial ^{187}Os/^{188}Os ratios (e.g., Belingwe, Kostomuksha, Pechenga). Such long-term enrichments in ^{187}Os of the mantle sources for these rocks may be explained via recycling of old mafic oceanic crust or incorporation of putative suprachondritic outer core materials entrained into their mantle sources. The relative importance of the two processes for some modern mantle-derived systems (e.g., Hawaiian picrites) is an issue of substantial debate. Importantly, however, the high-precision initial Os isotopic compositions of the majority of ultramafic systems show strikingly uniform initial ^{187}Os/^{188}Os ratios, consistent with their derivation from sources that had Os isotopic evolution trajectory very similar to that of carbonaceous chondrites. In addition, the Os isotopic evolution trajectories of the mantle sources for most komatiites show resolvably lower average Re/Os than that estimated for the Primitive Upper Mantle (PUM), yet significantly higher than that obtained in some estimates for the modern convecting upper mantle, as determined via analyses of abyssal peridotites. One possibility is that most of the komatiites sample mantle sources that are unique relative to the sources of abyssal peridotites and MORB. Previous arguments that komatiites originate via large extents of partial melting of relatively deep upper mantle, or even lower mantle materials could, therefore, implicate a source that is different from the convecting upper mantle. If so, this source is remarkably uniform in its long-term Re/Os, and it shows moderate depletion in Re relative to the PUM. Alternatively, if the komatiites are generated within the convective upper mantle through relatively large extents of partial melting, they may provide a better estimate of the Os isotopic composition of the convective upper mantle than that obtained via analyses of MORB, abyssal peridotites and ophiolites.

Proterozoic crustal evolution of the Eucla basement, Australia: Implications for destruction of oceanic crust during emergence of Nuna

NASA Astrophysics Data System (ADS)

Kirkland, C. L.; Smithies, R. H.; Spaggiari, C. V.; Wingate, M. T. D.; Quentin de Gromard, R.; Clark, C.; Gardiner, N. J.; Belousova, E. A.

2017-05-01

The crystalline basement beneath the Cretaceous to Cenozoic Bight and Eucla Basins, in Western Australia has received comparatively little attention even though it lies on the eastern margin of one of the most mineral resource endowed regions on the planet. This basement is characterized by a complex geological evolution spanning c. 2 billion years, but paucity of outcrop and younger basin cover present a daunting challenge to understand the basement geology. In this work the composition of the unexposed Proterozoic crystalline basement to the Bight and Eucla Basins is investigated through zircon Hf isotopes and whole rock geochemistry from new drillcore samples. This region includes two geophysically defined basement entities: The Madura Province, containing: 1) c. 1478 Ma Sleeper Camp Formation, which has variable isotopic signatures including evolved values interpreted to reflect reworking of rare slivers of hyperextended Archean crust, 2) 1415-1389 Ma Haig Cave Supersuite, with mantle-like isotope values interpreted as melting of subduction-modified N-MORB source, and 3) 1181-1125 Ma Moodini Supersuite, with juvenile isotopic signatures interpreted to reflect mixed mafic lower-crustal and asthenospheric melts produced at the base of thinned crust. The Coompana Province, to the east of the Madura Province, has three major magmatic components: 1) c. 1610 Ma Toolgana Supersuite, with chemical and isotopic characteristics of primitive arc rock, 2) c. 1490 Ma Undawidgi Supersuite, with juvenile isotope values consistent with extensional processes involving asthenospheric input and 3) 1192-1140 Ma Moodini Supersuite, with strong isotopic similarity to Moodini Supersuite rocks in the Madura Province. This new isotopic and geochemical data shows that the Madura and Coompana regions together represent a huge tract of predominantly juvenile material. Magma sources recognised, include; 1) depleted mantle, producing MORB-like crust at c. 1950 Ma, but also contributing to younger magmatism; 2) recycled c. 1950 Ma crust reworked in primitive arcs and in intra-plate settings and; 3) minor evolved material representing fragments of hyperextended continent. The observed isotopic evolution pattern is comparable to that of other central Australian Proterozoic provinces, including the Musgrave Province, the northern margin of the Gawler Craton, and components within the Rudall Province. Linking these isotopic signatures defines the Mirning Ocean, and its subducted and underplated equivalents. In a global context we suggest c. 1950 Ma crust production reflects the onset of ordered oceanic spreading centres, which swept juvenile crustal fragments into Nuna.

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.

Boron Isotopic Composition of Metasomatized Mantle Xenoliths from the Western Rift, East Africa

NASA Astrophysics Data System (ADS)

Hudgins, T.; Nelson, W. R.

2017-12-01

The Western Branch of the East African Rift System is known to have a thick lithosphere and sparse, alkaline volcanism associated with a metasomatized mantle source. Recent work investigating the relationship between Western Branch metasomatized mantle xenoliths and associated lavas has suggested that these metasomes are a significant factor in the evolution of the rift. Hydrous/carbonated fluids or silicate melts are potent metasomatic agents, however gaining insight into the source of a metasomatic agent proves challenging. Here we investigate the potential metasomatic fluid sources using B isotope analysis of mineral separates from Western Branch xenoliths. Preliminary SIMS analyses of phlogopite from Katwe Kikorongo and Bufumbira have and average B isotopic composition of -28.2‰ ± 5.1 and -16.4‰ ± 3.6, respectively. These values are are dissimilar to MORB (-7.5‰ ± 0.7; Marschall and Monteleone, 2015), primitive mantle (-10‰ ± 2; Chaussidon and Marty, 1995), and bulk continental crust (-9.1‰ ± 2.4; Marschall et al., 2017) and display significant heterogeneity across a relatively short ( 150km) portion of the Western Branch. Though displaying large variability, these B isotopic compositions are indicative of a metasomatic agent with a more negative B isotopic composition than MORB, PM, or BCC. These results are consistent with fluids that released from a subducting slab and may be related to 700 Ma Pan-African subduction.

Mladotice Lake, Czechia: The unique genesis and evolution of the lake basin

NASA Astrophysics Data System (ADS)

Janský, Bohumír; Šobr, Miroslav; Kliment, Zdeněk; Chalupová, Dagmar

2016-04-01

The Mladotice Lake is a lake of unique genetic type in Czechia. In May 1872 a landslide as a result an extreme rainfall event occurred in western Czechia, blocking the Mladoticky stream valley and creating the Mladotice Lake. The 1952 and 1975 air images document that collective farming had a great impact on the lake basin evolution when balks and field terraces were removed and fields were made much larger. Because of this change in land use we expected higher soil erosion and a related increase in the sedimentation rate. First bathymetric measurements of the newly created lake were carried out in 1972 and were repeated in 1999, in 2003 and in 2014. Our analysis of the sedimentary record aims to identify the sediment stratigraphy, its basic physical and chemical properties, isotope content and thin sections yield a detailed temporal resolution of the sedimentation chronology. In some areas a sediment thickness of 4 m was detected. Hence, the average sedimentation rate is from 2.2 to 2.7 cm per year. KEY WORDS: Mladotice Lake - extreme rainfall event - landslide - land use changes - flood events - bathymetric measurements - sedimentation dynamics - stratigraphy and geochemistry of lake sediments - analyses of isotopes - sedimentation rates.

Geochemical and Isotopic (Sr, U) Tracing of Weathering Processes Controlling the Recent Geochemical Evolution of Soil Solutions in the Strengbach Catchment (Vosges, France)

NASA Astrophysics Data System (ADS)

Chabaux, F. J.; Prunier, J.; Pierret, M.; Stille, P.

2012-12-01

The characterization of the present-day weathering processes controlling the chemical composition of waters and soils in natural ecosystems is an important issue to predict and to model the response of ecosystems to recent environmental changes. It is proposed here to highlight the interest of a multi-tracer geochemical approach combining measurement of major and trace element concentrations along with U and Sr isotopic ratios to progress in this topic. This approach has been applied to the small granitic Strengbah Catchment, located in the Vosges Mountain (France), used and equipped as a hydro-geochemical observatory since 1986 (Observatoire Hydro-Géochimique de l'Environnement; http://ohge.u-strasbg.fr). This study includes the analysis of major and trace element concentrations and (U-Sr) isotope ratios in soil solutions collected within two soil profiles located on two experimental plots of this watershed, as well as the analysis of soil samples and vegetation samples from these two plots The depth variation of elemental concentration of soil solutions confirms the important influence of the vegetation cycling on the budget of Ca, K, Rb and Sr, whereas Mg and Si budget in soil solutions are quasi exclusively controlled by weathering processes. Variation of Sr, and U isotopic ratios with depth also demonstrates that the sources and biogeochemical processes controlling the Sr budget of soil solutions is different in the uppermost soil horizons and in the deeper ones, and clearly influence by the vegetation cycling.

influx_s: increasing numerical stability and precision for metabolic flux analysis in isotope labelling experiments.

PubMed

Sokol, Serguei; Millard, Pierre; Portais, Jean-Charles

2012-03-01

The problem of stationary metabolic flux analysis based on isotope labelling experiments first appeared in the early 1950s and was basically solved in early 2000s. Several algorithms and software packages are available for this problem. However, the generic stochastic algorithms (simulated annealing or evolution algorithms) currently used in these software require a lot of time to achieve acceptable precision. For deterministic algorithms, a common drawback is the lack of convergence stability for ill-conditioned systems or when started from a random point. In this article, we present a new deterministic algorithm with significantly increased numerical stability and accuracy of flux estimation compared with commonly used algorithms. It requires relatively short CPU time (from several seconds to several minutes with a standard PC architecture) to estimate fluxes in the central carbon metabolism network of Escherichia coli. The software package influx_s implementing this algorithm is distributed under an OpenSource licence at http://metasys.insa-toulouse.fr/software/influx/. Supplementary data are available at Bioinformatics online.

Conceptualisation of Snowpack Isotope Dynamics in Spatially Distributed Tracer-Aided Runoff Models in Snow Influenced Northern Cathments

NASA Astrophysics Data System (ADS)

Ala-aho, P. O. A.; Tetzlaff, D.; Laudon, H.; McNamara, J. P.; Soulsby, C.

2016-12-01

We use the Spatially distributed Tracer-Aided Rainfall-Runoff (STARR) modelling framework to explore non-stationary flow and isotope response in three northern headwater catchments. The model simulates dynamic, spatially variable tracer concentration in different water stores and fluxes within a catchment, which can constrain internal catchment mixing processes, flow paths and associated water ages. To date, a major limitation in using such models in snow-dominated catchments has been the difficulties in paramaterising the isotopic transformations in snowpack accumulation and melt. We use high quality long term datasets for hydrometrics and stable water isotopes collected in three northern study catchments for model calibration and testing. The three catchments exhibit different hydroclimatic conditions, soil and vegetation types, and topographic relief, which brings about variable degree of snow dominance across the catchments. To account for the snow influence we develop novel formulations to estimate the isotope evolution in the snowpack and melt. Algorithms for the isotopic evolution parameterize an isotopic offset between snow evaporation and melt fluxes and the remaining snow storage. The model for each catchment is calibrated to match both streamflow and tracer concentration at the stream outlet to ensure internal consistency of the system behaviour. The model is able to reproduce the streamflow along with the spatio-temporal differences in tracer concentrations across the three studies catchments reasonably well. Incorporating the spatially distributed snowmelt processes and associated isotope transformations proved essential in capturing the stream tracer reponse for strongly snow-influenced cathments. This provides a transferrable tool which can be used to understand spatio-temporal variability of mixing and water ages for different storages and flow paths in other snow influenced, environments.

Small Volume Isotopic Analysis of Zircon Using LA-MC-ICP-MS U-Pb and Lu-Hf and Sub-ng Amounts of Hf in Solution

NASA Astrophysics Data System (ADS)

Bauer, A.; Horstwood, M. S.

2016-12-01

Crust-mantle evolution studies are greatly informed by zircon U-Pb and Lu-Hf isotopic datasets and the ease with which these data can now be acquired has seen their application become commonplace. In order to deconvolute geochemical change and interpret geologic variation in complexly zoned zircons, this information is most ideally obtained on the smallest volume of zircon by successive SIMS U-Pb and LA-MC-ICP-MS Lu-Hf isotopic analyses. However, due to variations in zircon growth zone geometry at depth, the Lu-Hf analysis may not relate to the lower volume U-Pb analysis, potentially causing inaccuracy of the resultant age-corrected Hf isotope signature. Laser ablation split-stream methods are applied to be certain that U-Pb and Lu-Hf data represent the same volume of zircon, however, the sampling volume remains relatively large at 40x30µm1. Coupled ID-TIMS U-Pb and solution MC-ICP-MS Lu-Hf work traditionally utilize whole-zircon dissolution ( 10-50ng Hf), which has the potential to homogenize different zones of geologic significance within an analysis. Conversely, modern ID-TIMS U-Pb methods utilize microsampling of zircon grains, often providing < 5ng Hf, thereby challenging conventional Lu-Hf acquisition protocols to achieve the required precision. In order to obtain usable precision on minimal zircon volumes, we developed laser ablation methods using successive 25um spot U-Pb and Lu-Hf ablation pits with a combined depth of 18um, and low-volume solution introduction methods without Hf-REE separation utilizing Hf amounts as low as 0.4ng, while retaining an uncertainty level of ca. 1 ɛHf for both methods. We investigated methods of Yb interference correction and the potential for matrix effects, with a particular focus on the accurate quantification of 176Lu/177Hf. These improvements reduce the minimum amount of material required for U-Pb and Hf isotopic analysis of zircon by about an order of magnitude. 1Ibanez-Mejia et al (2015). PreRes, 267, 285-310.

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.

Application of {sup 87}Sr/{sup 86}Sr, {delta}{sup 18}O and {delta}{sup 13}C Isotopes to diagenesis, correlation and connectivity of a fractured chalk reservoir, the Sidi El Kilani Field Tunisia

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

Mearns, E.W.; Mcbride, J.J.; Bramwell, M.

1995-08-01

Strontium Stratigraphy Analysis of the primary matrix chalk of the Abiod Formation reservoir in the Sidi El Kilani Field indicate a Campanian to Maastrichtian age (Upper Cretaceous). A resolution of {+-}1Ma has been achieved and results suggest that there are no major stratigraphic breaks in the studied sequences. Sr-O-C isotope data from early fracture-filling calcite cements suggest they may have formed by the redistribution of CaCO{sub 3} from underlying carbonate sequences and may have precipitated at temperatures in the region of 35-55{degrees}C. The {sup 87}Sr/{sup 86}Sr isotope ratios of formation waters determined by residual salt analysis (SrRSA) suggest that themore » chemical evolution of waters during reservoir filling was controlled by the influx of basinal waters as opposed to in situ water-rock interaction. Late, fracture-filling dolomite and barite cements have Sr-O-C isotope characteristics consistent with precipitation from these migrating basinal fluids at temperatures similar to current reservoir conditions (70-75{degrees}C). Sr RSA results suggest that the reservoir section in two of the wells may have been in direct lateral communication at the time of oil emplacement. These wells however are separated by a strike-slip fault. The SrRSA results therefore suggest that the fault is a partial barrier which has restricted pressure equilibration in the relatively short timescale of oil production, but which may have allowed homogenization of Sr isotope ratios in formation water.« less

Plume-related mantle source of super-large rare metal deposits from the Lovozero and Khibina massifs on the Kola Peninsula, Eastern part of Baltic Shield: Sr, Nd and Hf isotope systematics

NASA Astrophysics Data System (ADS)

Kogarko, L. N.; Lahaye, Y.; Brey, G. P.

2010-03-01

The two world’s largest complexes of highly alkaline nepheline syenites and related rare metal loparite and eudialyte deposits, the Khibina and Lovozero massifs, occur in the central part of the Kola Peninsula. We measured for the first time in situ the trace element concentrations and the Sr, Nd and Hf isotope ratios by LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometer) in loparite, eudialyte an in some other pegmatitic minerals. The results are in aggreement with the whole rock Sr and Nd isotope which suggests the formation of these superlarge rare metal deposits in a magmatic closed system. The initial Hf, Sr, Nd isotope ratios are similar to the isotopic signatures of OIB indicating depleted mantle as a source. This leads to the suggestion that the origin of these gigantic alkaline intrusions is connected to a deep seated mantle source—possibly to a lower mantle plume. The required combination of a depleted mantle and high rare metal enrichment in the source can be explained by the input of incompatible elements by metasomatising melts/fluids into the zones of alkaline magma generation shortly before the partial melting event (to avoid ingrowth of radiogenic isotopes). The minerals belovite and pyrochlore from the pegmatites are abnormally high in 87Sr /86Sr ratios. This may be explained by closed system isotope evolution as a result of a significant increase in Rb/Sr during the evolution of the peralkaline magma.

Argon isotopic composition of Archaean atmosphere probes early Earth geodynamics.

PubMed

Pujol, Magali; Marty, Bernard; Burgess, Ray; Turner, Grenville; Philippot, Pascal

2013-06-06

Understanding the growth rate of the continental crust through time is a fundamental issue in Earth sciences. The isotopic signatures of noble gases in the silicate Earth (mantle, crust) and in the atmosphere afford exceptional insight into the evolution through time of these geochemical reservoirs. However, no data for the compositions of these reservoirs exists for the distant past, and temporal exchange rates between Earth's interior and its surface are severely under-constrained owing to a lack of samples preserving the original signature of the atmosphere at the time of their formation. Here, we report the analysis of argon in Archaean (3.5-billion-year-old) hydrothermal quartz. Noble gases are hosted in primary fluid inclusions containing a mixture of Archaean freshwater and hydrothermal fluid. Our analysis reveals Archaean atmospheric argon with a (40)Ar/(36)Ar value of 143 ± 24, lower than the present-day value of 298.6 (for which (40)Ar has been produced by the radioactive decay of the potassium isotope (40)K, with a half-life of 1.25 billion years; (36)Ar is primordial in origin). This ratio is consistent with an early development of the felsic crust, which might have had an important role in climate variability during the first half of Earth's history.

Position-specific isotope modeling of organic micropollutants transformations through different reaction pathways

NASA Astrophysics Data System (ADS)

Jin, Biao; Rolle, Massimo

2016-04-01

Organic compounds are produced in vast quantities for industrial and agricultural use, as well as for human and animal healthcare [1]. These chemicals and their metabolites are frequently detected at trace levels in fresh water environments where they undergo degradation via different reaction pathways. Compound specific stable isotope analysis (CSIA) is a valuable tool to identify such degradation pathways in different environmental systems. Recent advances in analytical techniques have promoted the fast development and implementation of multi-element CSIA. However, quantitative frameworks to evaluate multi-element stable isotope data and incorporating mechanistic information on the degradation processes [2,3] are still lacking. In this study we propose a mechanism-based modeling approach to simultaneously evaluate concentration as well as bulk and position-specific multi-element isotope evolution during the transformation of organic micropollutants. The model explicitly simulates position-specific isotopologues for those atoms that experience isotope effects and, thereby, provides a mechanistic description of isotope fractionation occurring at different molecular positions. We validate the proposed approach with the concentration and multi-element isotope data of three selected organic micropollutants: dichlorobenzamide (BAM), isoproturon (IPU) and diclofenac (DCF). The model precisely captures the dual element isotope trends characteristic of different reaction pathways and their range of variation consistent with observed multi-element (C, N) bulk isotope fractionation. The proposed approach can also be used as a tool to explore transformation pathways in scenarios for which position-specific isotope data are not yet available. [1] Schwarzenbach, R.P., Egli, T., Hofstetter, T.B., von Gunten, U., Wehrli, B., 2010. Global Water Pollution and Human Health. Annu. Rev. Environ. Resour. doi:10.1146/annurev-environ-100809-125342. [2] Jin, B., Haderlein, S.B., Rolle, M., 2013. Integrated carbon and chlorine isotope modeling: Applications to chlorinated aliphatic hydrocarbons dechlorination. Environ. Sci. Technol. 47, 1443-1451. doi:10.1021/es304053h. [3] Jin, B., Rolle, M., 2014. Mechanistic approach to multi-element isotope modeling of organic contaminant degradation. Chemosphere 95, 131-139. doi:10.1016/j.chemosphere.2013.08.050.

Hydrogen Isotopic Constraints on the Evolution of Surface and Subsurface Water on Mars

NASA Technical Reports Server (NTRS)

Usui, T.; Kurokawa, H.; Wang, J.; Alexander, C. M. O’D.; Simon, J. I.; Jones, J. H.

2017-01-01

The geology and geomorphology of Mars provide clear evidence for the presence of liquid water on its surface during the Noachian and Hesperien eras (i.e., >3 Ga). In contrast to the ancient watery environment, today the surface of Mars is relatively dry. The current desert-like surface conditions, however, do not necessarily indicate a lack of surface or near-surface water/ice. In fact, massive deposits of ground ice and/or icy sediments have been proposed based on subsurface radar sounder observations. Hence, accurate knowledge of both the evolution of the distribution of water and of the global water inventory is crucial to our understanding of the evolution of the climate and near-surface environments and the potential habitability of Mars. This study presents insights from hydrogen isotopes for the interactive evolution of Martian water reservoirs. In particular, based on our new measurement of the D/H ratio of 4 Ga-old Noachian water, we constrain the atmospheric loss and possible exchange of surface and subsurface water through time.

Geological and geomorphological insights into Antarctic ice sheet evolution.

PubMed

Sugden, David E; Bentley, Michael J; O Cofaigh, Colm

2006-07-15

Technical advances in the study of ice-free parts of Antarctica can provide quantitative records that are useful for constraining and refining models of ice sheet evolution and behaviour. Such records improve our understanding of system trajectory, influence the questions we ask about system stability and help to define the ice-sheet processes that are relevant on different time-scales. Here, we illustrate the contribution of cosmogenic isotope analysis of exposed bedrock surfaces and marine geophysical surveying to the understanding of Antarctic ice sheet evolution on a range of time-scales. In the Dry Valleys of East Antarctica, 3He dating of subglacial flood deposits that are now exposed on mountain summits provide evidence of an expanded and thicker Mid-Miocene ice sheet. The survival of surface boulders for approximately 14Myr, the oldest yet measured, demonstrates exceptionally low rates of subsequent erosion and points to the persistence and stability of the dry polar desert climate since that time. Increasingly, there are constraints on West Antarctic ice sheet fluctuations during Quaternary glacial cycles. In the Sarnoff Mountains of Marie Byrd Land in West Antarctica, 10Be and 26Al cosmogenic isotope analysis of glacial erratics and bedrock reveal steady thinning of the ice sheet from 10400 years ago to the present, probably as a result of grounding line retreat. In the Antarctic Peninsula, offshore analysis reveals an extensive ice sheet at the last glacial maximum. Based on radiocarbon dating, deglaciation began by 17000cal yr BP and was complete by 9500cal yr BP. Deglaciation of the west and east sides of the Antarctic Peninsula ice sheet occurred at different times and rates, but was largely complete by the Early Holocene. At that time ice shelves were less extensive on the west side of the Antarctic Peninsula than they are today. The message from the past is that individual glacier drainage basins in Antarctica respond in different and distinctive ways to global climate change, depending on the link between regional topography and climate setting.

The evolution of the North Atlantic Oscillation for the last 700 years inferred from D/H isotopes in the sedimentary record of Lake Azul (Azores archipelago, Portugal).

NASA Astrophysics Data System (ADS)

Rubio de Ingles, Maria Jesus; Shanahan, Timothy M.; Sáez, Alberto; José Pueyo, Juan; Raposeiro, Pedro M.; Gonçalves, Vitor M.; Hernández, Armand; Trigo, Ricardo; Sánchez López, Guiomar; Francus, Pierre; Giralt, Santiago

2015-04-01

The δD plant leaf wax variations provide insights on precipitation and evaporation evolution through time. This proxy has been used to reconstruct the temporal evolution of the North Atlantic Oscillation (NAO) climate mode since this mode rules most of the climate variability in the central North Atlantic area. A total lipid extraction preparation and the correspondent analyses in the IRMS have been done for 100 samples from the uppermost 1.5 m of the sedimentary infill of Lake Azul (Azores archipelago, Portugal). According to the chronological model, established by 210Pb profile and 4 AMS 14C dates, this record contains the environmental history of the last 730 years. The reconstructed precipitation variations obtained from D/H isotope values, suggest that this area has suffered significant changes in its distribution and intensity rainfall patterns through time. The end of the Medieval Climate Anomaly (MCA, 1100- 1300 AD) is characterized by a progressive enrichmentof D/H isotope values which meant decreasing arid conditions. These rainfalls' increase might be interpreted by a shift from positive to negative dominance of the NAO. The Little Ice Age (LIA, 1300 - 1850 AD) was characterized by two humid periods (1300- 1550 AD and 1650 - 1850 AD) separated by a relatively dry period. These precipitation oscillations are clearly visible by marked changes in the D/H isotope values. The LIA was followed by the persistence of the positive NAO mode, exhibited by the depletion of the D/H isotope signal, which indicated an overall decrease of the precipitation in the central North Atlantic area. Surprisingly, the D/H of the last 100 years, characterized by the present global warming and a persistent positive NAO mode, display large fluctuations most possibly linked to an enhancement of the storminess which is in concordance with the data fluctuations observed in the instrumental record for the last 80 years in the archipelago. This climatic evolution is in accordance with other NAO records of the North Atlantic region (Trouet et al., 2012) highlighting the validity of the D/H isotopes as precipitation proxy. Trouet V., Scourse J.D., Raible C.C., 2012. North Atlantic storminess and Atlantic Meridional Overturning Circulation during the last Millenium: Reconciling contradictory proxy record of NAO variability. Global and planetary change.

Evolution of the Campanian Ignimbrite Magmatic System II: Trace Element and Th Isotopic Evidence for Open-System Processes

NASA Astrophysics Data System (ADS)

Bohrson, W. A.; Spera, F. J.; Fowler, S.; Belkin, H.; de Vivo, B.

2005-12-01

The Campanian Ignimbrite, a large volume (~200 km3 DRE) trachytic to phonolitic ignimbrite was deposited at ~39.3 ka and represents the largest of a number of highly explosive volcanic events in the region near Naples, Italy. Thermodynamic modeling of the major element evolution using the MELTS algorithm (see companion contribution by Fowler et al.) provides detailed information about the identity of and changes in proportions of solids along the liquid line of descent during isobaric fractional crystallization. We have derived trace element mass balance equations that explicitly accommodate changing mineral-melt bulk distribution coefficients during crystallization and also simultaneously satisfy energy and major element mass conservation. Although major element patterns are reasonably modeled assuming closed system fractional crystallization, modeling of trace elements that represent a range of behaviors (e.g. Zr, Nb, Th, U, Rb, Sm, Sr) yields trends for closed system fractionation that are distinct from those observed. These results suggest open-system processes were also important in the evolution of the Campanian magmatic system. Th isotope data yield an apparent isochron that is ~20 kyr younger than the age of the deposit, and age-corrected Th isotope data indicate that the magma body was an open-system at the time of eruption. Because open-system processes can profoundly change isotopic characteristics of a magma body, these results illustrate that it is critical to understand the contribution that open-system processes make to silicic magma bodies prior to assigning relevance to age or timescale information derived from isotope systematics. Fluid-magma interaction has been proposed as a mechanism to change isotopic and elemental characteristics of magma bodies, but an evaluation of the mass and thermal constraints on such a process suggest large-scale fluid-melt interaction at liquidus temperatures is unlikely. In the case of the magma body associated with the Campanian Ignimbrite, the most likely source of open-system signatures is assimilation of partial melts of compositionally heterogeneous basement composed of older cumulates and intrusive equivalents of volcanic activity within the Campanian region. Additional trace element modeling, explicitly evaluating the mass and energy balance effects that fluid, solids, and melt have on trace element evolution, will further elucidate the contributions of open vs. closed system processes within the Campanian magma body.

Observation and modelling of stable isotopes in precipitation for midlatitude weather systems in Melbourne, Australia

NASA Astrophysics Data System (ADS)

Barras, Vaughan; Simmonds, Ian

2010-05-01

The application of stable water isotopes as tracers of moisture throughout the hydrological cycle is often hindered by the relatively coarse temporal and spatial resolution of observational data. Intensive observation periods (IOPs) of isotopes in precipitation have been valuable in this regard enabling the quantification of the effects of vapour recycling, convection, cloud top height and droplet reevaporation (Dansgaard, 1953; Miyake et al., 1968; Gedzelman and Lawrence, 1982; 1990; Pionke and DeWalle, 1992; Risi et al., 2008; 2009) and have been used as a basis to develop isotope models of varying complexity (Lee and Fung, 2008; Bony et al., 2008). This study took a unified approach combining observation and modelling of stable isotopes in precipitation in an investigation of three key circulation types that typically bring rainfall to southeastern Australia. The observational component of this study involved the establishment of the Melbourne University Network of Isotopes in Precipitation (MUNIP). MUNIP was devised to sample rainwater simultaneously at a number of collection sites across greater Melbourne to record the spatial and temporal isotopic variability of precipitation during the passage of particular events. Samples were collected at half-hourly intervals for three specific rain events referred to as (1) mixed-frontal, (2) convective, and (3) stratiform. It was found that the isotopic content for each event varied over both high and low frequencies due to influences from local changes in rain intensity and large scale rainout respectively. Of particular note was a positive relationship between deuterium excess and rainfall amount under convective conditions. This association was less well defined for stratiform rainfall. As a supplement to the data coverage of the observations, the events were simulated using a version of NCAR CAM3 running with an isotope hydrology scheme. This was done by periodically nudging the model dynamics with data from the NCEP Reanalysis (Noone, 2006). Results from the simulations showed that the model represented well the large scale evolution of vapour profiles of deuterium excess and 18O for the mixed-frontal and stratiform events. Reconstruction of air mass trajectories provided further detail of the evolution and structure of the vapour profiles revealing a convergence of air masses from different source regions for the mixed-frontal event. By combining observations and modelling in this way, much detail of the structure and isotope moisture history of the observed events was provided that would be unavailable from the sampling of precipitation alone. References Bony, S., C. Risi, and F. Vimeux (2008), Influence of convective processes on the isotopic composition (?18O and ?D) of precipitation and water vapor in the tropics: 1. Radiative-convective equilibrium and Tropical Ocean-Global Atmosphere-Coupled Ocean-Atmosphere Response (TOGA-COARE) simulations, J. Geophys. Res., 113, D19305, doi:10.1029/2008JD009942. Dansgaard, W. (1953), The abundance of 18O in atmospheric water and water vapor. Tellus, 5, 461-469. Gedzelman, S. D., and J. R. Lawrence (1982), The isotopic composition of cyclonic precipitation. J. App. Met., 21, 1385-1404. Gedzelman, S. D., and J. R. Lawrence (1990), The isotopic composition of precipitation from two extratropical cyclones, Mon. Weather Rev., 118 , 495-509. Lee, J., and I. Fung (2008), 'Amount effect' of water isotopes and quantitative analysis of post-condensation processes, Hydrol. Process., 22, 1-8. Miyake, Y., O. Matsubaya, and C. Nishihara (1968), An isotopic study on meteoric precipitation, Pap. Meteorol. Geophys., 19, 243-266. Noone, D. (2006), Isotopic composition of water vapor modeled by constraining global climate simulations with reanalyses, in Research activities in atmospheric and oceanic modeling, J. Côté (ed.), Report No. 36, WMO/TD-No. 1347, p. 2.37-2.38. Pionke, H. B., and D. R. DeWalle (1992), Intra- and inter-storm 18O trends for selected rainstorms in Pennsylvania. J. Hydrol., 138, 131-143. Risi, C., S. Bony, and F. Vimeux (2008), Influence of convective processes on the isotopic composition (?18O and ?D) of precipitation and water vapor in the tropics: 2. Physical interpretation of the amount effect. J. Geophys. Res., 113, D19306, doi:10.1029/2008JD009943. Risi, C., S. Bony, F. Vimeux, M. Chong, and L. Descroix (2009), Evolution of the water stable isotopic composition of the rain sampled along Sahelian squall lines, Q. J. Roy. Meteor. Soc., doi:10.1002/qj.485, (in press).

Impacts of changes in groundwater recharge on the isotopic composition and geochemistry of seasonally ice-covered lakes: insights for sustainable management

NASA Astrophysics Data System (ADS)

Arnoux, Marie; Barbecot, Florent; Gibert-Brunet, Elisabeth; Gibson, John; Noret, Aurélie

2017-11-01

Lakes are under increasing pressure due to widespread anthropogenic impacts related to rapid development and population growth. Accordingly, many lakes are currently undergoing a systematic decline in water quality. Recent studies have highlighted that global warming and the subsequent changes in water use may further exacerbate eutrophication in lakes. Lake evolution depends strongly on hydrologic balance, and therefore on groundwater connectivity. Groundwater also influences the sensitivity of lacustrine ecosystems to climate and environmental changes, and governs their resilience. Improved characterization of groundwater exchange with lakes is needed today for lake preservation, lake restoration, and sustainable management of lake water quality into the future. In this context, the aim of the present paper is to determine if the future evolution of the climate, the population, and the recharge could modify the geochemistry of lakes (mainly isotopic signature and quality via phosphorous load) and if the isotopic monitoring of lakes could be an efficient tool to highlight the variability of the water budget and quality. Small groundwater-connected lakes were chosen to simulate changes in water balance and water quality expected under future climate change scenarios, namely representative concentration pathways (RCPs) 4.5 and 8.5. Contemporary baseline conditions, including isotope mass balance and geochemical characteristics, were determined through an intensive field-based research program prior to the simulations. Results highlight that future lake geochemistry and isotopic composition trends will depend on four main parameters: location (and therefore climate conditions), lake catchment size (which impacts the intensity of the flux change), lake volume (which impacts the range of variation), and lake G index (i.e., the percentage of groundwater that makes up total lake inflows), the latter being the dominant control on water balance conditions, as revealed by the sensitivity of lake isotopic composition. Based on these model simulations, stable isotopes appear to be especially useful for detecting changes in recharge to lakes with a G index of between 50 and 80 %, but response is non-linear. Simulated monthly trends reveal that evolution of annual lake isotopic composition can be dampened by opposing monthly recharge fluctuations. It is also shown that changes in water quality in groundwater-connected lakes depend significantly on lake location and on the intensity of recharge change.

Coherent changes in relative C4 plant productivity and climate during the late Quaternary in the North American Great Plains

USGS Publications Warehouse

Nordt, L.; Von Fischer, J.; Tieszen, L.; Tubbs, J.

2008-01-01

Evolution of the mixed and shortgrass prairie of the North American Great Plains is poorly understood because of limited proxies available for environmental interpretations. Buried soils in the Great Plains provide a solution to the problem because they are widespread both spatially and temporally with their organic reservoirs serving as a link to the plants than once grew on them. Through stable carbon isotopic analysis of soil organic carbon (??13C), the percent carbon from C4 plants (%C4) can be ascertained. Because C4 plants are primarily warm season grasses responding positively to summer temperature, their representation has the added advantage of serving as a climate indicator. To better understand grassland and climate dynamics in the Great Plains during the last 12 ka (ka=1000 radiocarbon years) we developed an isotopic standardization technique by: determining the difference in buried soil ??13C and modern soil ??13C expected for that latitude (????13C), and transferring the ????13C to ??%C4 (% C4) using mass balance calculations. Our analysis reveals two isotopic stages in the mixed and shortgrass prairie of the Great Plains based on trends in ??%C4. In response to orbital forcing mechanisms, ??%C4 was persistently below modern in the Great Plains between 12 and 6.7 ka (isotopic stage II) evidently because of the cooling effect of the Laurentide ice sheet and proglacial lakes in northern latitudes, and glacial meltwater pulses cooling the Gulf of Mexico and North Atlantic Ocean. The ??%C4 after 6.7 ka (isotopic stage I) increased to modern levels as conditioned by the outflow of warm, moist air from the Gulf of Mexico and dry incursions from the west that produced periodic drought. At the millennial-scale, time series analysis demonstrates that ??%C4 oscillated with 0.6 and 1.8 ka periodicities, possibly governed by variations in solar irradiance. Our buried soil isotopic record correlates well with other environmental proxy from the Great Plains and surrounding regions. ?? 2008 Elsevier Ltd.

Multiple enrichment of the Carpathian-Pannonian mantle: Pb-Sr-Nd isotope and trace element constraints

NASA Astrophysics Data System (ADS)

Rosenbaum, Jeffrey M.; Wilson, Marjorie; Downes, Hilary

1997-07-01

Pb isotope compositions of acid-leached clinopyroxene and amphibole mineral separates from spinel peridotite mantle xenoliths entrained in Tertiary-Quaternary alkali basalts from the Carpathian-Pannonian Region of eastern Europe provide important constraints on the processes of metasomatic enrichment of the mantle lithosphere in an extensional tectonic setting associated with recent subduction. Principal component analysis of Pb-Sr-Nd isotope and rare earth element compositions of the pyroxenes is used to identify the geochemical characteristics of the original lithospheric mantle protolith and a spectrum of infiltrating metasomatic agents including subduction-related aqueous fluids and silicate melts derived from a subduction-modified mantle wedge which contains a St. Helena-type (HIMU) plume component. The mantle protolith is highly depleted relative to mid-ocean ridge basalt-source mantle with Pb-Nd-Sr isotope compositions consistent with an ancient depletion event. Silicate melt infiltration into the protolith accounts for the primary variance in the Pb-Sr-Nd isotope compositions of the xenoliths and has locally generated metasomatic amphibole. Infiltration of aqueous fluids has introduced radiogenic Pb and Sr without significantly perturbing the rare earth element signature of the protolith. The Pb isotope compositions of the fluid-modified xenoliths suggest that they reacted with aqueous fluids released from a subduction zone which had equilibrated with sediment derived from an ancient basement terrain. We propose a model for mantle lithosphere evolution consistent with available textural and geochemical data for the xenolith population. The Pb-Sr-Nd isotope compositions of both alkaline mafic magmas and rare, subduction-related, calc-alkaline basaltic andesites from the region provide important constraints for the nature of the asthenospheric mantle wedge and confirm the presence of a HIMU plume component. These silicate melts contribute to the metasomatism of the mantle lithosphere rather than being derived therefrom.

12C/13C isotopic ratios in red-giant stars of the open cluster NGC 6791

NASA Astrophysics Data System (ADS)

Szigeti, László; Mészáros, Szabolcs; Smith, Verne V.; Cunha, Katia; Lagarde, Nadège; Charbonnel, Corinne; García-Hernández, D. A.; Shetrone, Matthew; Pinsonneault, Marc; Allende Prieto, Carlos; Fernández-Trincado, J. G.; Kovács, József; Villanova, Sandro

2018-03-01

Carbon isotope ratios, along with carbon and nitrogen abundances, are derived in a sample of 11 red-giant members of one of the most metal-rich clusters in the Milky Way, NGC 6791. The selected red-giants have a mean metallicity and standard deviation of [Fe/H] = +0.39 ± 0.06 (Cunha et al. 2015). We used high-resolution H-band spectra obtained by the SDSS-IV Apache Point Observatory Galactic Evolution Experiment. The advantage of using high-resolution spectra in the H band is that lines of CO are well represented and their line profiles are sensitive to the variation of 12C/13C. Values of the 12C/13C ratio were obtained from a spectrum synthesis analysis. The derived 12C/13C ratios varied between 6.3 and 10.6 in NGC 6791, in agreement with the final isotopic ratios from thermohaline-induced mixing models. The ratios derived here are combined with those obtained for more metal poor red-giants from the literature to examine the correlation between 12C/13C, mass, metallicity, and evolutionary status.

U-Pb ages and Hf isotope compositions of zircons in plutonic rocks from the central Famatinian arc, Argentina

NASA Astrophysics Data System (ADS)

Otamendi, Juan E.; Ducea, Mihai N.; Cristofolini, Eber A.; Tibaldi, Alina M.; Camilletti, Giuliano C.; Bergantz, George W.

2017-07-01

The Famatinian arc formed around the South Iapetus rim during the Ordovician, when oceanic lithosphere subducted beneath the West Gondwana margin. We present combined in situ U-Th-Pb and Lu-Hf isotope analyses for zircon to gain insights into the origin and evolution of Famatinian magmatism. Zircon crystals sampled from four intermediate and silicic plutonic rocks confirm previous observations showing that voluminous magmatism took place during a relatively short pulse between the Early and Middle Ordovician (472-465 Ma). The entire zircon population for the four plutonic rocks yields coherent εHf negative values and spreads over several ranges of initial εHf(t) units (-0.3 to -8.0). The range of εHf units in detrital zircons of Famatinian metasedimentary rocks reflects a prolonged history of the cratonic sources during the Proterozoic to the earliest Phanerozoic. Typical tonalites and granodiorites that contain zircons with evolved Hf isotopic compositions formed upon incorporating (meta)sedimentary materials into calc-alkaline metaluminous magmas. The evolved Hf isotope ratios of zircons in the subduction related plutonic rocks strongly reflect the Hf isotopic character of the metasedimentary contaminant, even though the linked differentiation and growth of the Famatinian arc crust was driven by ascending and evolving mantle magmas. Geochronology and Hf isotope systematics in plutonic zircons allow us understanding the petrogenesis of igneous series and the provenance of magma sources. However, these data could be inadequate for computing model ages and supporting models of crustal evolution.

Characterising flow regime and interrelation between surface-water and ground-water in the Fuente de Piedra salt lake basin by means of stable isotopes, hydrogeochemical and hydraulic data

NASA Astrophysics Data System (ADS)

Kohfahl, Claus; Rodriguez, Miguel; Fenk, Cord; Menz, Christian; Benavente, Jose; Hubberten, Hans; Meyer, Hanno; Paul, Liisa; Knappe, Andrea; López-Geta, Juan Antonio; Pekdeger, Asaf

2008-03-01

SummaryThis research reports the characterisation of ground- and surface-water interaction in the Fuente de Piedra Salt lake basin in southern Spain by a combined approach using hydraulic, hydrogeochemical and stable isotope data. During three sampling campaigns (February 2004, 2005 and October 2005) ground- and surface-water samples were collected for stable isotope studies ( 18O, D) and for major and minor ion analysis. Hydraulic measurements at multilevel piezometers were carried out at four different locations around the lake edge. Conductivity logs were performed at four piezometers located along a profile at the northern lake border and at two deeper piezometers in the Miocene basin at a greater distance from the lake. To describe processes that control the brine evolution different hydrogeochemical simulations were performed. Hydrogeochemical data show a variety of brines related to thickness variations of lacustrine evaporites around the lake. Salinity profiles in combination with stable isotope and hydraulic data indicate the existence of convection cells and recycled brines. Furthermore restricted ground-water inflow into the lake was detected. Dedolomitisation processes were identified by hydrogeochemical simulations and different brine origins were reproduced by inverse modelling approaches.

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

NASA Astrophysics Data System (ADS)

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

2017-05-01

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

Chondritic xenon in the Earth’s mantle

NASA Astrophysics Data System (ADS)

Caracausi, Antonio; Avice, Guillaume; Burnard, Peter G.; Füri, Evelyn; Marty, Bernard

2016-05-01

Noble gas isotopes are powerful tracers of the origins of planetary volatiles, and the accretion and evolution of the Earth. The compositions of magmatic gases provide insights into the evolution of the Earth’s mantle and atmosphere. Despite recent analytical progress in the study of planetary materials and mantle-derived gases, the possible dual origin of the planetary gases in the mantle and the atmosphere remains unconstrained. Evidence relating to the relationship between the volatiles within our planet and the potential cosmochemical end-members is scarce. Here we show, using high-precision analysis of magmatic gas from the Eifel volcanic area (in Germany), that the light xenon isotopes identify a chondritic primordial component that differs from the precursor of atmospheric xenon. This is consistent with an asteroidal origin for the volatiles in the Earth’s mantle, and indicates that the volatiles in the atmosphere and mantle originated from distinct cosmochemical sources. Furthermore, our data are consistent with the origin of Eifel magmatism being a deep mantle plume. The corresponding mantle source has been isolated from the convective mantle since about 4.45 billion years ago, in agreement with models that predict the early isolation of mantle domains. Xenon isotope systematics support a clear distinction between mid-ocean-ridge and continental or oceanic plume sources, with chemical heterogeneities dating back to the Earth’s accretion. The deep reservoir now sampled by the Eifel gas had a lower volatile/refractory (iodine/plutonium) composition than the shallower mantle sampled by mid-ocean-ridge volcanism, highlighting the increasing contribution of volatile-rich material during the first tens of millions of years of terrestrial accretion.

Chondritic xenon in the Earth's mantle.

PubMed

Caracausi, Antonio; Avice, Guillaume; Burnard, Peter G; Füri, Evelyn; Marty, Bernard

2016-05-05

Noble gas isotopes are powerful tracers of the origins of planetary volatiles, and the accretion and evolution of the Earth. The compositions of magmatic gases provide insights into the evolution of the Earth's mantle and atmosphere. Despite recent analytical progress in the study of planetary materials and mantle-derived gases, the possible dual origin of the planetary gases in the mantle and the atmosphere remains unconstrained. Evidence relating to the relationship between the volatiles within our planet and the potential cosmochemical end-members is scarce. Here we show, using high-precision analysis of magmatic gas from the Eifel volcanic area (in Germany), that the light xenon isotopes identify a chondritic primordial component that differs from the precursor of atmospheric xenon. This is consistent with an asteroidal origin for the volatiles in the Earth's mantle, and indicates that the volatiles in the atmosphere and mantle originated from distinct cosmochemical sources. Furthermore, our data are consistent with the origin of Eifel magmatism being a deep mantle plume. The corresponding mantle source has been isolated from the convective mantle since about 4.45 billion years ago, in agreement with models that predict the early isolation of mantle domains. Xenon isotope systematics support a clear distinction between mid-ocean-ridge and continental or oceanic plume sources, with chemical heterogeneities dating back to the Earth's accretion. The deep reservoir now sampled by the Eifel gas had a lower volatile/refractory (iodine/plutonium) composition than the shallower mantle sampled by mid-ocean-ridge volcanism, highlighting the increasing contribution of volatile-rich material during the first tens of millions of years of terrestrial accretion.

Micron-scale Analysis of Carbonate-Associated Sulfate by Secondary Ionization Mass Spectrometry: Insights into Spatial Variability in δ34SCAS

NASA Astrophysics Data System (ADS)

Fike, D. A.; Jones, D. S.

2012-12-01

The proliferation of carbonate-associated sulfate (CAS) isotope analyses in recent years has revolutionized our understanding of marine sulfur cycling over much of Earth history. In marine carbonate rocks, δ34SCAS is thought to be a faithful recorder of the isotopic composition of marine sulfate (δ34SSO4). However, as the chemostratigraphic record becomes better resolved in time and space, reports of coeval but discordant δ34SCAS values are becoming increasingly common. These differences could arise in part from a) water column stratification or physiographic separations between separate ocean basins (i.e., paleoceanographic variability in δ34SSO4); b) syndepositional processes that decouple the relationship between δ34SSO4 and δ34SCAS during deposition or prior to lithification; or c) diagenetic alteration of the δ34SCAS signal following deposition. To help disentangle these processes, we have developed a microanalytical approach to determine the abundance and isotopic composition of CAS using secondary ionization mass spectrometry (SIMS). While our current precision (~1‰) cannot compete with that obtained from traditional bulk analysis on gas source isotope ratio mass spectrometers, we believe that the unparalleled spatial resolution can provide substantial insights into many of the fundamental questions that remain regarding the mechanisms by which CAS concentration and isotopic composition can be altered during carbonate precipitation and/or recrystallization. With a spatial resolution as low as ~ 5 μm, it is possible to analyze suites of primary and diagenetic phases, including individual carbonate allochems, muds, and cements. Preliminary results indicate that δ34SCAS can vary by as much as 10‰ between phases in a single sample. This scale of analysis allows for a rigorous evaluation of the susceptibility of δ34SCAS to syndepositional and diagenetic alteration, especially when coupled with parallel analysis of δ13Ccarb/δ18Ocarb and diagnostic trace element abundances. Such detailed measurements illuminate the complex relationships between the isotopic composition of individual constituents of carbonate rocks and the bulk δ34SCAS values on which much of our understanding of sulfur cycling in deep time is based. The resulting insights can be used to re-examine existing δ34SCAS records and our understanding of the evolution of sulfur cycling over Earth history.

The Operational plans for Ptolemy during the Rosetta mission

NASA Astrophysics Data System (ADS)

Morse, Andrew; Andrews, Dan; Barber, Simeon; Sheridan, Simon; Morgan, Geraint; Wright, Ian

2014-05-01

Ptolemy is a Gas Chromatography - Isotope Ratio - Mass Spectrometer (GC-IR-MS) instrument within the Philae Lander, part of ESA's Rosetta mission [1]. The primary aim of Ptolemy is to analyse the chemical and isotopic composition of solid comet samples. Samples are collected by the Sampler, Drill and Distribution (SD2) system [2] and placed into ovens for analysis by three instruments on the Lander: COSAC [3], ÇIVA[4] and/or Ptolemy. In the case of Ptolemy, the ovens can be heated with or without oxygen and the evolved gases separated by chemical and GC techniques for isotopic analysis. In addition Ptolemy can measure gaseous (i.e. coma) samples by either directly measuring the ambient environment within the mass spectrometer or by passively trapping onto an adsorbent phase in order to pre-concentrate coma species before desorbing into the mass spectrometer. At the time of this presentation the Rosetta spacecraft should have come out of hibernation and Ptolemy's Post Hibernation Commissioning phase will have been completed. During the Comet Approach phase of the mission Ptolemy will attempt to measure the coma composition both in sniffing and pre-concentration modes. Previous work has demonstrated that spacecraft outgassing is a significant component of the gaseous environment and highlighted the advantage of obtaining complementary measurements with different instruments [5]. In principle Ptolemy could study the spatial evolution of gases through the coma during the lander's descent to the comet surface, but in practice it is likely that mission resources will need to be fully directed towards ensuring a safe landing. Once on the surface of the comet the lander begins its First Science Sequence which continues until the primary batteries are exhausted after some 42 hours. SD2 will collect a sample from a depth of ~5cm and deliver it to a Ptolemy high temperature oven which will then be analysed in five temperature steps to determine the carbon isotopic composition of CO, CO2 and organics; the nitrogen isotopic composition of N2 and organics; and the oxygen isotopic composition of water. The Long Term Science phase of the lander relies on Solar power and the secondary batteries. There will be intermittent operations of Ptolemy to measure the temporal evolution of the coma gas as the comet activity increases. As sufficient power becomes available Ptolemy can continue with more detailed analyses of further comet samples extracted by SD2. [1] Glassmeier, K-H. et al. (2007) Space Sci. Rev., 128, 1 [2] Finzi, E. et al (2007) Space Sci. Rev., 128, 281 [3] Goesmann, F. et al (2007) Space Sci. Rev., 128, 257 [4] Bibring, J-P. et al. (2007) Space Sci. Rev., 128, 397 [5] Morse A.D. (2012) et al. Planetary and Space Sci., 66, 165

Martian carbon dioxide: Clues from isotopes in SNC meteorites

NASA Technical Reports Server (NTRS)

Karlsson, H. R.; Clayton, R. N.; Mayeda, T. K.; Jull, A. J. T.; Gibson, E. K., Jr.

1993-01-01

Attempts to unravel the origin and evolution of the atmosphere and hydrosphere on Mars from isotopic data have been hampered by the impreciseness of the measurements made by the Viking Lander and by Earth-based telescopes. The SNC meteorites which are possibly pieces of the Martian surface offer a unique opportunity to obtain more precise estimates of the planet's volatile inventory and isotopic composition. Recently, we reported results on oxygen isotopes of water extracted by pyrolysis from samples of Shergotty, Zagami, Nakhla, Chassigny, Lafayette, and EETA-79001. Now we describe complementary results on the stable isotopic composition of carbon dioxide extracted simultaneously from those same samples. We will also report on C-14 abundances obtained by accelerator mass spectrometry (AMS) for some of these CO2 samples.

The 12C/13C Ratio in Sgr B2(N): Constraints for Galactic Chemical Evolution and Isotopic Chemistry

NASA Astrophysics Data System (ADS)

Halfen, D. T.; Woolf, N. J.; Ziurys, L. M.

2017-08-01

A study has been conducted of 12C/13C ratios in five complex molecules in the Galactic center. H2CS, CH3CCH, NH2CHO, CH2CHCN, and CH3CH2CN and their 13C-substituted species have been observed in numerous transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the 12C species and 2-54 for 13C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found to consistently exhibit two velocity components near V LSR ˜ 64 and 73 km s-1, with column densities ranging from N tot ˜ 3 × 1014 - 4 × 1017 cm-2 and ˜2 × 1013 - 1 × 1017 cm-2 for the 12C and 13C species, respectively. Based on 14 different isotopic combinations, ratios were obtained in the range 12C/13C = 15 ± 5 to 33 ± 13, with an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the 12C/13C ratio at the Galactic center, and suggest a slightly revised isotope gradient of 12C/13C = 5.21(0.52) D GC + 22.6(3.3). As indicated by the column densities, no preferential 13C enrichment was found on the differing carbon sites of CH3CCH, CH2CHCN, and CH3CH2CN. Because of the elevated temperatures in Sgr B2(N), 13C isotopic substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.

Lipid Biomarkers and Carbon Isotope Ratios of Lipids Isolated from Acid Mine Drainage Biofilms: Dual Biosignatures for Eukaryotic Evolution and Oxygenation of Primitive Earth

NASA Astrophysics Data System (ADS)

Dasgupta, S.; Fang, J.; Zhang, L.; Li, J.

2012-12-01

Lipid analysis and carbon isotope ratios (δ13C) of lipids in biofilms in an acid mine drainage site (AMD) site in western Indiana revealed unique biogeochemical signatures of microeukaryotes, never recorded before. Dominance of photosynthetic microeukaryote Euglena was indicated by the detection of abundant phytadiene, phytol, phytanol, polyunsaturated n-alkenes, polyunsaturated fatty acids, short-chain (C25-32) wax esters (WE), ergosterol, and tocopherols. The WE were probably synthesized in mitochondria under anoxic conditions by the reverse β-oxidation pathway, whereas the sterols (ergosterol and ergosta-7,22-dien-3β-ol) were likely synthesized in the cytosol in the presence of molecular oxygen. The dual aerobic and anaerobic biosynthetic pathways of Euglena may be a response to survive the recurring anoxic and oxic conditions in primitive Earth, whereby microeukaryotes retained this mechanism of conserved compartmentalization within their physiology to evolve and diversify in extreme conditions. Hydrocarbons, including n-alkenes, phytadienes, and wax esters showed heavy δ13C values than usual. The primary cause for the 13C-enrichment can be attributed to a CO2-limiting system that exists in the AMD, which is further regulated by the pH of the AMD. Floating biofilms BF2, 4, and 6 showed more depleted δ13C values for phytadienes and n-alkenes (average of -23.6‰) as compared to benthic biofilm BF5 (average of -20.8‰), indicating that physiology plays an important role in isotopic discrimination. 13C-enriched values of the esters could result from kinetic isotope effects at two branch points (pyruvate and/or acetyl CoA) in the biosynthetic pathway. Our understanding of biogeochemical conditions in this AMD environment would allow us to identify unique sets of biosignatures that can act as a proxy in deciphering the links between eukaryotic evolutions, oxygenation of the early atmosphere, formation of BIF, and possibly iron-rich extraterrestrial environments.

The evolution of CNO isotopes: a new window on cosmic star formation history and the stellar IMF in the age of ALMA

NASA Astrophysics Data System (ADS)

Romano, D.; Matteucci, F.; Zhang, Z.-Y.; Papadopoulos, P. P.; Ivison, R. J.

2017-09-01

We use state-of-the-art chemical models to track the cosmic evolution of the CNO isotopes in the interstellar medium of galaxies, yielding powerful constraints on their stellar initial mass function (IMF). We re-assess the relative roles of massive stars, asymptotic giant branch (AGB) stars and novae in the production of rare isotopes such as 13C, 15N, 17O and 18O, along with 12C, 14N and 16O. The CNO isotope yields of super-AGB stars, novae and fast-rotating massive stars are included. Having reproduced the available isotope enrichment data in the solar neighbourhood, and across the Galaxy, and having assessed the sensitivity of our models to the remaining uncertainties, e.g. nova yields and star formation history, we show that we can meaningfully constrain the stellar IMF in galaxies using C, O and N isotope abundance ratios. In starburst galaxies, where data for multiple isotopologue lines are available, we find compelling new evidence for a top-heavy stellar IMF, with profound implications for their star formation rates and efficiencies, perhaps also their stellar masses. Neither chemical fractionation nor selective photodissociation can significantly perturb globally averaged isotopologue abundance ratios away from the corresponding isotope ones, as both these processes will typically affect only small mass fractions of molecular clouds in galaxies. Thus, the Atacama Large Millimeter Array now stands ready to probe the stellar IMF, and even the ages of specific starburst events in star-forming galaxies across cosmic time unaffected by the dust obscuration effects that plague optical/near-infrared studies.

Temporal geochemical evolution of Kilauea Volcano: Comparison of Hilina and Puna Basalt

NASA Astrophysics Data System (ADS)

Chen, C.-Y.; Frey, F. A.; Rhodes, J. M.; Eastern, R. M.

Temporal geochcmical variations in Hawaiian shield-building lavas provide important constraints on the origin and evolution of these lavas. We determined the major and trace element content, and Sr, Nd and Pb isotopic ratios of the oldest subaerially exposed lavas on Kilauea Volcano, i.e., the >25 Ka to perhaps 100 Ka, Hilina Basalt. Except for lower K2O and Rb abundances in Hilina lavas, the compositions of these prehistoric lavas overlap with historical Kilauea lavas. Although the studied Hilina lavas are not highly altered, the lower abundances of K2O and Rb may reflect post-eruptive alteration. Compared with historical Kilauea lavas, Hilina lavas have a similar range in Sr and Nd isotopic ratios, but they range to more radiogenic Pb isotopic ratios. The mantle source of Kilauea lavas is heterogeneous in isotopic ratios and perhaps in abundance ratios of some incompatible elements, but there is no evidence for systematic long-term geochemical variations in the source of Kilauea lavas. None of the prehistoric Kilauea lavas have isotopic characteristics similar to those of subaerial Mauna Loa lavas. Apparently, the sources and ascent paths of lavas forming the adjacent Kilauea and Mauna Loa shields have largely remained distinct during subaerial growth of the Kilauea shield. Compared to lavas from other Hawaiian shields, Kilauea lavas range to relatively high 206Pb/204Pb and low 87Sr/86Sr. These isotopic ratios are correlated with trace element abundance ratios that involve Nb, e.g., Zr/Nb; some Hilina lavas define the upper range in 206Pb/204Pb (˜18.82), and they have low Zr/Nb (˜8). This "Kilauea component" which has isotopic characteristics similar to the FOZO component (e.g., Hauri et al., 1994a] is an intrinsic part of the Hawaiian plume.

Accessory Mineral Records of Early Earth Crust-Mantle Systematics: an Example From West Greenland

NASA Astrophysics Data System (ADS)

Storey, C. D.; Hawkesworth, C. J.

2008-12-01

Conditions for the formation and the nature of Earth's early crust are enigmatic due to poor preservation. Before c.4 Ga the only archives are detrital minerals eroded from earlier crust, such as the Jack Hills zircons in western Australia, or extinct isotope systematics. Zircons are particularly powerful since they retain precise records of their ages of crystallisation, and the Lu-Hf radiogenic isotope and O stable isotope systematics of the reservoir from which they crystallised. In principle, this allows insight into the nature of the crust, the mantle reservoir from which the melt was extracted and any reworked material incorporated into that melt. We have used in situ methods to measure U-Pb, O and Lu-Hf within single zircon crystals from tonalitic gneisses from West Greenland in the vicinity of the Isua Supracrustal Belt. They have little disturbed ages of c.3.8 Ga, mantle-like O isotope signatures and Lu-Hf isotope signatures that lie on the CHUR evolution line at 3.8 Ga. These samples have previously been subjected to Pb isotope feldspar and 142Nd whole rock analysis and have helped constrain models in which early differentiation of a proto-crust must have occurred. The CHUR-like Lu-Hf signature, along with mantle-like O signature from these zircons suggests juvenile melt production at 3.8 Ga from undifferentiated mantle, yet the other isotope systems preclude this possibility. Alternatively, this is further strong evidence for a heterogeneous mantle in the early Earth. Whilst zircons afford insight into the nature of the early crust and mantle, it is through the Sm-Nd system that the mantle has traditionally been viewed. Titanite often contains several thousand ppm Nd, making it amenable to precise analysis, and is a common accessory phase. It has a reasonably high closure temperature for Pb and O, and it can retain cores with older ages and distinct REE chemistry. It is often the main accessory phase alongside zircon, and it is the main carrier of Nd within the whole rock such that Nd isotope analysis of titanite may be able to see-through later alteration that may have partially reset the whole rock system. We present new in-situ U-Pb, O and Sm-Nd and high-precision U-Pb ID-TIMS and Sm-Nd MC- ICPMS data from individual or fragmented titanite grains. We discuss how these data complement the zircon data and may help to resolve long-standing debates in ancient gneiss terranes, with utility to the nature and formation of crust on the early Earth.

Plutonium isotopes in the atmosphere of Central Europe: Isotopic composition and time evolution vs. circulation factors.

PubMed

Kierepko, Renata; Mietelski, Jerzy W; Ustrnul, Zbigniew; Anczkiewicz, Robert; Wershofen, Herbert; Holgye, Zoltan; Kapała, Jacek; Isajenko, Krzysztof

2016-11-01

This paper reports evidence of Pu isotopes in the lower part of the troposphere of Central Europe. The data were obtained based on atmospheric aerosol fraction samples collected from four places in three countries (participating in the informal European network known as the Ring of Five (Ro5)) forming a cell with a surface area of about 200,000km(2). We compared our original data sets from Krakow (Poland, 1990-2007) and Bialystok (Poland, 1991-2007) with the results from two other locations, Prague (Czech Republic; 1997-2004) and Braunschweig (Germany; 1990-2003) to find time evolution of the Pu isotopes. The levels of the activity concentration for (238)Pu and for ((239+240))Pu were estimated to be a few and some tens of nBqm(-3), respectively. However, we also noted some results were much higher (even about 70 times higher) than the average concentration of (238)Pu in the atmosphere. The achieved complex data sets were used to test a new approach to the problem of solving mixing isotopic traces from various sources (here up to three) in one sample. Results of our model, supported by mesoscale atmospheric circulation parameters, suggest that Pu from nuclear weapon accidents or tests and nuclear burnt-up fuel are present in the air. Copyright © 2016 Elsevier B.V. All rights reserved.

Lithospheric evolution of the Northern Arabian Shield: Chemical and isotopic evidence from basalts, xenoliths and granites

NASA Technical Reports Server (NTRS)

Stein, M.

1988-01-01

The evolution of the upper-mantle and the lower-crust (the conteinental lithosphere), is the area of Israel and Sinai was studied, using the chemical composition and the Nd-Sr isotopic systematics from mantle and crustal nodules, their host basalts, and granites. The magmatism and the metasomatism making the lithosphere are related to uprise of mantle diapirs in the uppermost mantle of the area. These diapirs heated the base of the lithosphere, eroded, and replaced it with new hot material. It caused a domal uplift of the lithosphere (and the crust). The doming resulted in tensional stresses that in turn might develop transport channels for the basalt.

Formation and Evolution of the Continental Lithospheric Mantle: Perspectives From Radiogenic Isotopes of Silicate and Sulfide Inclusions in Macrodiamonds

NASA Astrophysics Data System (ADS)

Shirey, S. B.; Richardson, S. H.

2007-12-01

Silicate and sulfide inclusions that occur in diamonds comprise the oldest (>3 Ga), deepest (>140 km) samples of mantle-derived minerals available for study. Their relevance to the evolution of the continental lithosphere is clear because terrestrial macrodiamonds are confined to regions of the Earth with continental lithospheric mantle keels. The goals of analytical work on inclusions in diamond are to obtain paragenesis constraints, radiogenic ages, and initial isotopic compositions. The purpose is to place diamond formation episodes into the broader framework of the geological processes that create and modify the continental lithosphere and to relate the source of the C and N in diamond-forming fluids to understanding the Earth's C and N cycles in the Archean. Although sulfide and silicate inclusions rarely occur in the same diamond, they both can be grouped according to their geochemical similarity with the chief rock types that comprise the mantle keel: peridotite and eclogite. Silicate inclusions are classified as harzburgitic (depleted; olivine > Fo91, garnet Cr2O3 > 3 wt% and CaO from 0 to 5 wt%), lherzolitic (fertile), or eclogitic (basaltic; garnet Cr2O3 < 2 wt% and CaO from 3 to 15 wt%, clinopyroxene with higher Na2O, Al2O3, and FeO); they are amenable for trace element study by SIMS and for Sm-Nd and Rb-Sr analysis by conventional P-TIMS after grouping by mineralogical similarity. Sulfide inclusions (chiefly FeS with lesser Ni, Cu, and Co) are classified as peridotitic (Ni > 14 wt%; Os > 2 ppm) versus eclogitic (Ni < 10 wt%; Os < 200 ppb); single sulfides are amenable for S isotopic study by SIMS or TIMS, and Re-Os analysis by N-TIMS. Work on inclusions in diamonds depends on the distribution of mined, diamond-bearing kimberlites, and the generosity of mining companies because of the extreme rarity of inclusions in suites of mostly gem-quality diamonds. Most isotopic work has been on the Kaapvaal-Zimbabwe craton with lesser work on the Slave, Siberian, and Australian cratons. Sm-Nd ages on silicate suites and Re-Os ages on sulfide suites confirm diamond formation from the Mesoarchean though the Neoproterozoic. Most important are the systematics across cratons in the context of crustal geology that lead to generalities about craton evolution. Inclusion suites date mantle keels as Mesoarchean and clearly point to subduction as the major process to form the earliest continental nuclei and to amalgamate the cratons in their present form. This is evident from the elevated initial Os isotopic compositions in 3.5 Ga Slave (Panda) and 2.9 Ga Kaapvaal (Kimberley) sulfides, the low Sm/Nd and elevated initial Sr isotopic compositions of 3.4 Ga Kaapvaal (Kimberley) harzburgitic garnets, the preponderance of 2.9 Ga eclogitic sulfides in every western Kaapvaal craton locality, and the occurrence of surficial, volcanogenic S in Kaapvaal (Orapa) sulfides. The continental lithosphere was accessible to melts and fluids from the asthenosphere throughout the Proterozoic as evident from silicate and sulfide inclusion suites of 0.9 to 2.0 Ga age in every locality studied in the Kaapvaal craton. The correspondence of silicate inclusion type with current seismic velocity structure of the Kaapvaal mantle keel shows that its structure is at least Bushveld age (2 Ga) and due to compositional differences. Seismic velocity structures of continental mantle keels may be more a function of their geologic history than current temperature distribution.

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

Garcia Ruiz, R. F.; Bissell, M. L.; Blaum, K.

Here, despite being a complex many-body system, the atomic nucleus exhibits simple structures for certain ‘magic’ numbers of protons and neutrons. The calcium chain in particular is both unique and puzzling: evidence of doubly magic features are known in 40,48Ca, and recently suggested in two radioactive isotopes, 52,54Ca. Although many properties of experimentally known calcium isotopes have been successfully described by nuclear theory, it is still a challenge to predict the evolution of their charge radii. Here we present the first measurements of the charge radii of 49,51,52Ca, obtained from laser spectroscopy experiments at ISOLDE, CERN. The experimental results aremore » complemented by state-of-the-art theoretical calculations. The large and unexpected increase of the size of the neutron-rich calcium isotopes beyond N = 28 challenges the doubly magic nature of 52Ca and opens new intriguing questions on the evolution of nuclear sizes away from stability, which are of importance for our understanding of neutron-rich atomic nuclei.« less

Isotope geochronology of the Precambrian

NASA Astrophysics Data System (ADS)

Levskii, L. K.; Levchenkov, O. A.

This symposium discusses the use of isotope methods for establishing the geochronology of Precambrian formations, with special consideration given to geochronological studies of the early phases of the earth's core evolution in the Baltic and Vitim-Aldan shields and the Enderby Land (Antarctica). Attention is also given to the Early Archean Vodlozero gneiss complex and its structural-metamorphic evolution, the influence of geological events during the Proterozoic on the state of the U-Pb and Rb-Sr systems in the Archean postkinematic granites of Karelia, the Rb-Sr systems in the andesite basalts of the Suna-Semch' region (Karelia), and the geochronology of the Karelian granite-greenstone region. Also discussed are the petrogenesis and age of the rocks from the Kola ultradeep borehole, the isotope-geochronological evidence for the early Precambrian history of the Aldan-Olekma region, the Rb-Sr systems in metasedimentary rocks of the Khani graben, and the U-Pb ages of zircons from polymetamorphic rocks of the Archean granulite complex of Enderby Land.

Evidence From Hydrogen Isotopes in Meteorites for a Martian Permafrost

NASA Technical Reports Server (NTRS)

Usui, T.; Alexander, C. M. O'D.; Wang, J.; Simon, J. I.; Jones, J. H.

2014-01-01

Fluvial landforms on Mars suggest that it was once warm enough to maintain persistent liquid water on its surface. The transition to the present cold and dry Mars is closely linked to the history of surface water, yet the evolution of surficial water is poorly constrained. We have investigated the evolution of surface water/ ice and its interaction with the atmosphere by measurements of hydrogen isotope ratios (D/H: deuterium/ hydrogen) of martian meteorites. Hydrogen is a major component of water (H2O) and its isotopes fractionate significantly during hydrological cycling between the atmosphere, surface waters, ground ice, and polar cap ice. Based on in situ ion microprobe analyses of three geochemically different shergottites, we reported that there is a water/ice reservoir with an intermediate D/H ratio (delta D = 1,000?2500 %) on Mars. Here we present the possibility that this water/ice reservoir represents a ground-ice/permafrost that has existed relatively intact over geologic time.

Isotope analysis of crystalline impact melt rocks from Apollo 16 stations 11 and 13, North Ray Crater

NASA Technical Reports Server (NTRS)

Reimold, W. U.; Nyquist, L. E.; Bansal, B. M.; Shih, C.-Y.; Weismann, H.; Wooden, J. L.; Mackinnon, I. D. R.

1985-01-01

The North Ray Crater Target Rock Consortium was formed to study a large number of rake samples collected at Apollo 16 stations 11 and 13 with comparative chemical, mineralogical, and chronological techniques in order to provide a larger data base for the discussion of lunar highland evolution in the vicinity of the Apollo 16 landing region. The present investigation is concerned with Rb-Sr and Sm-Nd isotopic analyses of a number of whole-rock samples of feldspathic microporhyritic (FM) impact melt, a sample type especially abundant among the North Ray crater (station 11) sample collection. Aspects of sample mineralogy and analytical procedures are discussed, taking into account FM impact melt rocks 6715 and 63538, intergranular impact melt rock 67775, subophitic impact melt rock 67747, subophitic impact melt rock 67559, and studies based on the utilization of electron microscopy and mass spectroscopy.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Ecosystem variability and early human habitats in eastern Africa.

PubMed

Magill, Clayton R; Ashley, Gail M; Freeman, Katherine H

2013-01-22

The role of savannas during the course of early human evolution has been debated for nearly a century, in part because of difficulties in characterizing local ecosystems from fossil and sediment records. Here, we present high-resolution lipid biomarker and isotopic signatures for organic matter preserved in lake sediments at Olduvai Gorge during a key juncture in human evolution about 2.0 Ma--the emergence and dispersal of Homo erectus (sensu lato). Using published data for modern plants and soils, we construct a framework for ecological interpretations of stable carbon-isotope compositions (expressed as δ(13)C values) of lipid biomarkers from ancient plants. Within this framework, δ(13)C values for sedimentary leaf lipids and total organic carbon from Olduvai Gorge indicate recurrent ecosystem variations, where open C(4) grasslands abruptly transitioned to closed C(3) forests within several hundreds to thousands of years. Carbon-isotopic signatures correlate most strongly with Earth's orbital geometry (precession), and tropical sea-surface temperatures are significant secondary predictors in partial regression analyses. The scale and pace of repeated ecosystem variations at Olduvai Gorge contrast with long-held views of directional or stepwise aridification and grassland expansion in eastern Africa during the early Pleistocene and provide a local perspective on environmental hypotheses of human evolution.

Ecosystem variability and early human habitats in eastern Africa

PubMed Central

Magill, Clayton R.; Ashley, Gail M.; Freeman, Katherine H.

2013-01-01

The role of savannas during the course of early human evolution has been debated for nearly a century, in part because of difficulties in characterizing local ecosystems from fossil and sediment records. Here, we present high-resolution lipid biomarker and isotopic signatures for organic matter preserved in lake sediments at Olduvai Gorge during a key juncture in human evolution about 2.0 Ma—the emergence and dispersal of Homo erectus (sensu lato). Using published data for modern plants and soils, we construct a framework for ecological interpretations of stable carbon-isotope compositions (expressed as δ13C values) of lipid biomarkers from ancient plants. Within this framework, δ13C values for sedimentary leaf lipids and total organic carbon from Olduvai Gorge indicate recurrent ecosystem variations, where open C4 grasslands abruptly transitioned to closed C3 forests within several hundreds to thousands of years. Carbon-isotopic signatures correlate most strongly with Earth’s orbital geometry (precession), and tropical sea-surface temperatures are significant secondary predictors in partial regression analyses. The scale and pace of repeated ecosystem variations at Olduvai Gorge contrast with long-held views of directional or stepwise aridification and grassland expansion in eastern Africa during the early Pleistocene and provide a local perspective on environmental hypotheses of human evolution. PMID:23267092

Isotopic evolution of Mauna Loa volcano

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kammer, David P.

1991-04-01

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

Lunar and Planetary Science XXXVI, Part 17

NASA Technical Reports Server (NTRS)

2005-01-01

The following topics were discussed: A Model for the Formation of Paterae on Io; LIBS-based Detection of As, Br, C, Cl, P, and S in the VUV Spectral Region in a Mars Atmosphere; Mass Independent Sulfur in Achondrites: Possible Evidence of Photochemistry in the Solar Nebula; Grain Size-dependent Viscosity and Oceans in Icy Satellites; Claritas Paleolake Studied from the MEX HRSC Data; Mars Express HRSC Colors of White Rock, Arabia, Mars; Lava and Flows of the Arcadia Region of Mars; Isotopic Composition of Lunar Soils and the Early Differentiation of the Moon; Trace Element Analysis of Lunar Soils by ICP-MS; Highly Siderophile Elements and Osmium Isotope Systematics in Ureilites: Are the Carbonaceous Veins Primary Components?; Evaporative Evolution of Martian Brines Based on Halogens in Nakhlites and MER Samples; Io from High-Resolution Galileo PPR Data Taken Simultaneously with SSI or NIMS Observations; Loki, Io: Groundbased Observations and a Model for Periodic Overturn; Deconstructing a Few Myths in the Interpretation of Satellite-Altitude Crustal Magnetic Field: Examples from Mars Global Surveyor; Semi-Autonomous Rover Operations: A Mars Technology Program Demonstration; Rotational Studies of Asteroids with Small Telescopes; Mineralogy and Temperature-induced Spectral Investigations of A-type Asteroids 246 Asporina and 446 Aeternitas; and Thermal History Calculations Versus Full Convection Models: Application to the Thermal Evolution of Mercury. Recent Solar-Proton Fluxes

Assessing the paleoenvironmental potential of Pliocene to Holocene tufa deposits along the Ghaap Plateau escarpment (South Africa) using stable isotopes

NASA Astrophysics Data System (ADS)

Doran, Taylor Louise; Herries, Andy I. R.; Hopley, Philip J.; Sombroek, Hank; Hellstrom, John; Hodge, Ed; Kuhn, Brian F.

2015-07-01

The tufa deposits of the Ghaap Plateau escarpment provide a rich, yet minimally explored, geological archive of climate and environmental history coincident with hominin evolution in South Africa. This study examines the sedimentary and geochemical records of ancient and modern tufas from Buxton-Norlim Limeworks, Groot Kloof, and Gorrokop, to assess the potential of these sediments for providing reliable chronologies of high-resolution, paleoenvironmental information. Chronometric dating demonstrates that tufa formation has occurred from at least the terminal Pliocene through to the modern day. The stable isotope records show a trend toward higher, more variable δ18O and δ13C values with decreasing age from the end of the Pliocene onwards. The long-term increase in δ18O values corresponds to increasingly arid conditions, while increasing δ13C values reflect the changing proportion of C3/C4 vegetation in the local environment. Analysis of the Thabaseek Tufa, in particular, provides valuable evidence for reconstructing the depositional and chronological context of the enigmatic Taung Child (Australopithecus africanus). Collectively, the results of the present study demonstrate the potential of these deposits for developing high-precision records of climate change and, ultimately, for understanding the causal processes relating climate and hominin evolution.

Shape coexistence, shape evolution and Gamow-Teller {beta}-decay of neutron-rich A Asymptotically-Equal-To 100 nuclei

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

Petrovici, A.; Schmid, K. W.; Faessler, A.

The structure of neutron-rich nuclei in the A Asymptotically-Equal-To 100 mass region relevant for the astrophysical r process manifests drastic changes in some isotopic chains and often sudden variations of particular nuclear properties have been identified. For a realistic description of the evolution in structure with increasing energy, spin, and isospin determined by shape coexistence and mixing beyond-mean-field approaches are required. Our recent studies represent an attempt to the self-consistent description of the shape coexistence phenomena in neutron-rich A Asymptotically-Equal-To 100 nuclei within the complex Excited Vampir variational model with symmetry projection before variation using a realistic effective interaction basedmore » on the Bonn A potential in a large model space. Results concerning the triple shape coexistence and the shape evolution in the N=58 Sr and Zr isotopes, the shape evolution in a chain of Zr nuclei, as well as the Gamow-Teller {beta}-decay properties of neutron-rich Zr and Tc nuclei are presented.« less

Tidal evolution of the Moon from a high-obliquity, high-angular-momentum Earth.

PubMed

Ćuk, Matija; Hamilton, Douglas P; Lock, Simon J; Stewart, Sarah T

2016-11-17

In the giant-impact hypothesis for lunar origin, the Moon accreted from an equatorial circum-terrestrial disk; however, the current lunar orbital inclination of five degrees requires a subsequent dynamical process that is still unclear. In addition, the giant-impact theory has been challenged by the Moon's unexpectedly Earth-like isotopic composition. Here we show that tidal dissipation due to lunar obliquity was an important effect during the Moon's tidal evolution, and the lunar inclination in the past must have been very large, defying theoretical explanations. We present a tidal evolution model starting with the Moon in an equatorial orbit around an initially fast-spinning, high-obliquity Earth, which is a probable outcome of giant impacts. Using numerical modelling, we show that the solar perturbations on the Moon's orbit naturally induce a large lunar inclination and remove angular momentum from the Earth-Moon system. Our tidal evolution model supports recent high-angular-momentum, giant-impact scenarios to explain the Moon's isotopic composition and provides a new pathway to reach Earth's climatically favourable low obliquity.

Marine vs. local control on seawater Nd-isotope ratios at the northwest coast of Africa during the late Cretaceous-early Eocene

NASA Astrophysics Data System (ADS)

Kocsis, L.; Gheerbrant, E.; Mouflih, M.; Cappetta, H.; Ulianov, A.; Chiaradia, M.

2013-12-01

At the northwest corner of Africa excellent conditions existed for phosphate formation (i.e., stable upwelling system) during the late Cretaceous-early Eocene. This is probably in relation to stable tectonic evolution of shallow epicontinental basins at a passive continental margin and to their paleogeographic situation between the Atlantic and Tethys marine realms. To better comprehend paleoceanic conditions in this area, radiogenic isotope ratios (87Sr/86Sr and 143Nd/144Nd) and trace element compositions of fossil biogenic apatite are investigated from Maastrichtian to Ypresian shallow marine phosphorite deposits in Morocco (Ouled Abdoun and Ganntour Basins). Rare earth elements (REE) distributions in the fossils are compatible with early diagenetic marine pore fluid represented by negative Ce-anomaly and heavy REE enrichment. An overall shift in Ce-anomaly is apparent with gradually lower values in younger fossils along three distinct assemblages that correspond to Maastrichtian, Danian-Thanetian and Ypresian periods. The temporal change can be interpreted as presence of gradually more oxygenated seawater in the basins. Strontium isotopic ratios of the fossils follow the global Sr-evolution curve. However, the latest Cretaceous and the oldest Paleocene fossils yielded slightly higher ratios than the global ocean, which could reflect minor diagenetic alteration. Neodymium isotopic ratios are quite even along the phosphate series with ɛNd(t) values ranges from -6.8 to -5.8. These values are higher than those reported for average North Atlantic deep water and Tethyan seawater (e.g., Stille et al., 1996; Thomas et al., 2003). For the origin of the stable, high 143Nd/144Nd we propose three main hypotheses: (1) contribution of continental Nd-source, (2) locally controlled deep water Nd-isotope ratios near the coast from where upwelling originated in the area and (3) possible surface marine water contribution from the Pacific across the Atlantic. Stille, P., Steinmann, M., Riggs, R.S., 1996. Nd isotope evidence for the evolution of the paleocurrents in the Atlantic and Tethys Oceans during the past 180 Ma. Earth Planet. Sci. Lett. 144, 9-19. Thomas, J.D., Bralower, T.J., Jones, E.C., 2003. Neodymium isotopic reconstruction of late Paleocene-early Eocene thermohaline circulation. Earth Planet. Sci. Lett. 209, 309-322.

The evolution of a calc-alkaline basic to silicic magma system: Geochemical and Rb-Sr, Sm-Nd, and 18O /16O isotopic evidence from the Late Hercynian Atesina-Cima d'Asta volcano-plutonic complex, northern Italy

NASA Astrophysics Data System (ADS)

Barth, Susanne; Oberli, Felix; Meier, Martin; Blattner, Peter; Bargossi, Giuseppe M.; Di Battistini, Gianfranco

1993-09-01

Geochemical and Sr-Nd-O isotopic data presented for basaltic andesitic to rhyolitic and for quartz noritic to monzogranitic rock suites from the Late Hercynian calc-alkaline Atesina volcanic complex (AVC) and the Cima d'Asta pluton (CAP), Southern Alps (northern Italy), provide information on both the primary magmatic processes and the effects of (mainly Triassic) hydrothermal overprint. Fluid infiltration led to mobilization of major and trace elements (K 2O, Na 2O, CaO, Rb, Sr, and Ba), opensystem behavior in total-rock Rb-Sr, and shift in δ18O to elevated values (total rock up to 16.6%. and volcanic matrix up to 17.8%.). Oxygen isotopic disequilibrium between quartz-feldspar pairs suggests water-rock interaction at medium/low temperatures. The δ18O values of quartz, the REE characterized by regular LREE enrichment/HREE depletion, and the Sm-Nd isotopic signatures, however, remained virtually unaffected by secondary processes. The initial ɛNd values (at 270 Ma) of the AVC and CAP magmatites are restricted to overlapping ranges of -3.6 to -6.5 and of -2.7 to -6.5, respectively, indicating significant crustal contribution; these values and associated T DM model ages of 1.1-1.6 Ga agree well with those of typical South Alpine lower crustal magmatites. The AVC and CAP rocks do not follow the "normal" trend of increasingly crustal Nd isotopic signatures with progressive degree of magma evolution expected for a single-stage AFC-type process, but instead display an inversion of this relationship. Geochemical and isotopic constraints favor a model of a large-scale MASH-type melting and mixing zone at or near the base of the continental crust. Distinct elemental enrichment/depletion and REE crossover patterns displayed by high-silica as compared to less silicic AVC rhyolites suggest subsequent magma evolution within a shallow-level compositionally zoned chamber.

Isotopic evolution of the protoplanetary disk and the building blocks of Earth and the Moon.

PubMed

Schiller, Martin; Bizzarro, Martin; Fernandes, Vera Assis

2018-03-21

Nucleosynthetic isotope variability among Solar System objects is often used to probe the genetic relationship between meteorite groups and the rocky planets (Mercury, Venus, Earth and Mars), which, in turn, may provide insights into the building blocks of the Earth-Moon system. Using this approach, it has been inferred that no primitive meteorite matches the terrestrial composition and the protoplanetary disk material from which Earth and the Moon accreted is therefore largely unconstrained. This conclusion, however, is based on the assumption that the observed nucleosynthetic variability of inner-Solar-System objects predominantly reflects spatial heterogeneity. Here we use the isotopic composition of the refractory element calcium to show that the nucleosynthetic variability in the inner Solar System primarily reflects a rapid change in the mass-independent calcium isotope composition of protoplanetary disk solids associated with early mass accretion to the proto-Sun. We measure the mass-independent 48 Ca/ 44 Ca ratios of samples originating from the parent bodies of ureilite and angrite meteorites, as well as from Vesta, Mars and Earth, and find that they are positively correlated with the masses of their parent asteroids and planets, which are a proxy of their accretion timescales. This correlation implies a secular evolution of the bulk calcium isotope composition of the protoplanetary disk in the terrestrial planet-forming region. Individual chondrules from ordinary chondrites formed within one million years of the collapse of the proto-Sun reveal the full range of inner-Solar-System mass-independent 48 Ca/ 44 Ca ratios, indicating a rapid change in the composition of the material of the protoplanetary disk. We infer that this secular evolution reflects admixing of pristine outer-Solar-System material into the thermally processed inner protoplanetary disk associated with the accretion of mass to the proto-Sun. The identical calcium isotope composition of Earth and the Moon reported here is a prediction of our model if the Moon-forming impact involved protoplanets or precursors that completed their accretion near the end of the protoplanetary disk's lifetime.

Modeling Hf-W Evolution for Earth, Moon and Mars in Grand Tack Accretion Simulations: The Isotopic Consequences of Rapid Accretion

NASA Astrophysics Data System (ADS)

Zube, N.; Nimmo, F.; Jacobson, S. A.; Fischer, R. A.

2017-12-01

Short-lived isotopes, such as the decay of lithophile 182Hf into siderophile 182W with a half-life of 9 My, can provide constraints on the timescales of planetary core formation and accretion. Classical accretion scenarios have produced Hf-W isotopic outcomes like those measured presently on the Earth [2,3]. We examine Grand Tack accretion simulations [4,5] and determine the mantle equilibration conditions necessary to produce the observed tungsten isotopic anomaly. Additionally, we follow Hf-W evolution for pairs of bodies that experience a last giant impact fitting the conditions of Earth's Moon-forming collision. In this way, we determine the likelihood of producing the observed almost indistinguishable W isotope anomalies of the Earth and Moon mantles [6]. We model Hf-W evolution for growing planets in 141 N-body simulations during late accretion in the Grand Tack scenario. For each case, we vary the equilibration factor during collisions—the fraction of impactor core that experiences re-equilibration with the entire target mantle—in steps ranging from none (cores merging) to complete equilibration. For Earth-like and Mars-like surviving planets, we find that cases with a high equilibration factor (k > 0.8) and an intermediate (2:1 - 4:1) ratio of initial embryo mass to planetesimal mass were most frequently able to approximate the observed W measurements for Earth and Mars. The equilibration factor required is more restrictive than the one found for classical accretion scenarios [2,3] and may not be consistent with fluid-dynamical predictions [7]. Moons made of impactor material from Earth's last giant impact are only able to result in an Earth-Moon pair having sufficiently similar W anomalies with a likelihood of 8% or less across all simulations. This indicates that a scenario where the Moon isotopically equilibrated with the Earth's mantle after the impact [8] may be required to explain the measured values. [1] Kleine et al. 2009 [2] Nimmo et al. 2010 [3] Rudge et al. 2010 [4] Walsh et al. 2009 [5] Jacobson et al. 2014 [6] Touboul et al., 2007 [7] Deguen et al. 2014 [8] Pahlevan and Stevenson 2007

What can hafnium isotope ratios arrays tell us about orogenic processes? An insight into geodynamic processes operating in the Alpine/Mediterranean region

NASA Astrophysics Data System (ADS)

Henderson, B.; Murphy, J.; Collins, W. J.; Hand, M. P.

2013-12-01

Over the last decade, technological advances in laser-ablation sampling techniques have resulted in an increase in the number of combined U-Pb-Hf zircon isotope studies used to investigate crustal evolution on a local, regional and global scale. Hafnium isotope arrays over large time scales (>500 myr) have been interpreted to track evolving plate tectonic configurations, and the geological outputs associated with changing plate boundaries. We use the Alpine-Mediterranean region as an example of how hafnium isotope arrays record the geodynamic processes associated with the complex geological evolution of a region. The geology of Alpine-Mediterranean region preserves a complex, semi-continuous tectonic history that extends from the Neoproterozoic to the present day. Major components of the Variscan and Alpine orogens are microcontinental ribbons derived from the northern Gondwanan margin, which were transferred to the Eurasian plate during the opening and closing of the Rheic and Paleo-Tethys Oceans. Convergence of the Eurasian and African plates commenced in the Mid-Late Cretaceous, following the destruction of the Alpine-Tethys Ocean during the terminal breakup of Pangea. In general, convergence occurred slowly and is characterised by northward accretion of Gondwanan fragments, interspersed with subduction of African lithosphere and intermittent roll-back events. A consequence of this geodynamic scenario was periods of granite-dominated magmatism in an arc-backarc setting. New Hf isotope data from the peri-Gondwanan terranes (Iberia, Meguma and Avalonia) and a compilation of existing Phanerozoic data from the Alpine-Mediterranean region, indicate ~500 myr (Cambrian-Recent) of reworking of peri-Gondwanan crust. The eHf array follows a typical crustal evolution pattern (Lu/Hf=0.015) and is considered to reflect reworking of juvenile peri-Gondwanan (Neoproterozoic) crust variably mixed with an older (~1.8-2.0 Ga) source component, probably Eburnian crust from the West Africa Craton. The Phanerozoic Hf isotopic data from Variscan and Alpine Europe suggest that slow translation of continental fragments from one continent to another produces a characteristic, long-term crustal reworking eHf array, which strongly contrasts with the Hf array defined by Phanerozoic circum-Pacific orogens.

Isotopic evolution of the protoplanetary disk and the building blocks of Earth and the Moon

NASA Astrophysics Data System (ADS)

Schiller, Martin; Bizzarro, Martin; Fernandes, Vera Assis

2018-03-01

Nucleosynthetic isotope variability among Solar System objects is often used to probe the genetic relationship between meteorite groups and the rocky planets (Mercury, Venus, Earth and Mars), which, in turn, may provide insights into the building blocks of the Earth–Moon system. Using this approach, it has been inferred that no primitive meteorite matches the terrestrial composition and the protoplanetary disk material from which Earth and the Moon accreted is therefore largely unconstrained. This conclusion, however, is based on the assumption that the observed nucleosynthetic variability of inner-Solar-System objects predominantly reflects spatial heterogeneity. Here we use the isotopic composition of the refractory element calcium to show that the nucleosynthetic variability in the inner Solar System primarily reflects a rapid change in the mass-independent calcium isotope composition of protoplanetary disk solids associated with early mass accretion to the proto-Sun. We measure the mass-independent 48Ca/44Ca ratios of samples originating from the parent bodies of ureilite and angrite meteorites, as well as from Vesta, Mars and Earth, and find that they are positively correlated with the masses of their parent asteroids and planets, which are a proxy of their accretion timescales. This correlation implies a secular evolution of the bulk calcium isotope composition of the protoplanetary disk in the terrestrial planet-forming region. Individual chondrules from ordinary chondrites formed within one million years of the collapse of the proto-Sun reveal the full range of inner-Solar-System mass-independent 48Ca/44Ca ratios, indicating a rapid change in the composition of the material of the protoplanetary disk. We infer that this secular evolution reflects admixing of pristine outer-Solar-System material into the thermally processed inner protoplanetary disk associated with the accretion of mass to the proto-Sun. The identical calcium isotope composition of Earth and the Moon reported here is a prediction of our model if the Moon-forming impact involved protoplanets or precursors that completed their accretion near the end of the protoplanetary disk’s lifetime.

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

PubMed

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

2013-04-01

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

Integrated carbon and chlorine isotope modeling: applications to chlorinated aliphatic hydrocarbons dechlorination.

PubMed

Jin, Biao; Haderlein, Stefan B; Rolle, Massimo

2013-02-05

We propose a self-consistent method to predict the evolution of carbon and chlorine isotope ratios during degradation of chlorinated hydrocarbons. The method treats explicitly the cleavage of isotopically different C-Cl bonds and thus considers, simultaneously, combined carbon-chlorine isotopologues. To illustrate the proposed modeling approach we focus on the reductive dehalogenation of chlorinated ethenes. We compare our method with the currently available approach, in which carbon and chlorine isotopologues are treated separately. The new approach provides an accurate description of dual-isotope effects regardless of the extent of the isotope fractionation and physical characteristics of the experimental system. We successfully applied the new approach to published experimental results on dehalogenation of chlorinated ethenes both in well-mixed systems and in situations where mass-transfer limitations control the overall rate of biodegradation. The advantages of our self-consistent dual isotope modeling approach proved to be most evident when isotope fractionation factors of carbon and chlorine differed significantly and for systems with mass-transfer limitations, where both physical and (bio)chemical transformation processes affect the observed isotopic values.

SFCOMPO-2.0: An OECD NEA database of spent nuclear fuel isotopic assays, reactor design specifications, and operating data

DOE PAGES

Michel-Sendis, F.; Gauld, I.; Martinez, J. S.; ...

2017-08-02

SFCOMPO-2.0 is the new release of the Organisation for Economic Co-operation and Development (OECD) Nuclear Energy Agency (NEA) database of experimental assay measurements. These measurements are isotopic concentrations from destructive radiochemical analyses of spent nuclear fuel (SNF) samples. We supplement the measurements with design information for the fuel assembly and fuel rod from which each sample was taken, as well as with relevant information on operating conditions and characteristics of the host reactors. These data are necessary for modeling and simulation of the isotopic evolution of the fuel during irradiation. SFCOMPO-2.0 has been developed and is maintained by the OECDmore » NEA under the guidance of the Expert Group on Assay Data of Spent Nuclear Fuel (EGADSNF), which is part of the NEA Working Party on Nuclear Criticality Safety (WPNCS). Significant efforts aimed at establishing a thorough, reliable, publicly available resource for code validation and safety applications have led to the capture and standardization of experimental data from 750 SNF samples from more than 40 reactors. These efforts have resulted in the creation of the SFCOMPO-2.0 database, which is publicly available from the NEA Data Bank. Our paper describes the new database, and applications of SFCOMPO-2.0 for computer code validation, integral nuclear data benchmarking, and uncertainty analysis in nuclear waste package analysis are briefly illustrated.« less

SFCOMPO-2.0: An OECD NEA database of spent nuclear fuel isotopic assays, reactor design specifications, and operating data

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

Michel-Sendis, F.; Gauld, I.; Martinez, J. S.

SFCOMPO-2.0 is the new release of the Organisation for Economic Co-operation and Development (OECD) Nuclear Energy Agency (NEA) database of experimental assay measurements. These measurements are isotopic concentrations from destructive radiochemical analyses of spent nuclear fuel (SNF) samples. We supplement the measurements with design information for the fuel assembly and fuel rod from which each sample was taken, as well as with relevant information on operating conditions and characteristics of the host reactors. These data are necessary for modeling and simulation of the isotopic evolution of the fuel during irradiation. SFCOMPO-2.0 has been developed and is maintained by the OECDmore » NEA under the guidance of the Expert Group on Assay Data of Spent Nuclear Fuel (EGADSNF), which is part of the NEA Working Party on Nuclear Criticality Safety (WPNCS). Significant efforts aimed at establishing a thorough, reliable, publicly available resource for code validation and safety applications have led to the capture and standardization of experimental data from 750 SNF samples from more than 40 reactors. These efforts have resulted in the creation of the SFCOMPO-2.0 database, which is publicly available from the NEA Data Bank. Our paper describes the new database, and applications of SFCOMPO-2.0 for computer code validation, integral nuclear data benchmarking, and uncertainty analysis in nuclear waste package analysis are briefly illustrated.« less

Antiquity of the biological sulphur cycle: evidence from sulphur and carbon isotopes in 2700 million-year-old rocks of the Belingwe Belt, Zimbabwe.

PubMed Central

Grassineau, N V; Nisbet, E G; Bickle, M J; Fowler, C M; Lowry, D; Mattey, D P; Abell, P; Martin, A

2001-01-01

Sulphur and carbon isotopic analyses on small samples of kerogens and sulphide minerals from biogenic and non-biogenic sediments of the 2.7 x 10(9) years(Ga)-old Belingwe Greenstone Belt (Zimbabwe) imply that a complex biological sulphur cycle was in operation. Sulphur isotopic compositions display a wider range of biological fractionation than hitherto reported from the Archaean. Carbon isotopic values in kerogen record fractionations characteristic of rubisco activity methanogenesis and methylotrophy and possibly anoxygenic photosynthesis. Carbon and sulphur isotopic fractionations have been interpreted in terms of metabolic processes in 2.7 Ga prokaryote mat communities, and indicate the operation of a diverse array of metabolic processes. The results are consistent with models of early molecular evolution derived from ribosomal RNA. PMID:11209879

Instrumental and atmospheric background lines observed by the SMM gamma-ray spectrometer

NASA Technical Reports Server (NTRS)

Share, G. H.; Kinzer, R. L.; Strickman, M. S.; Letaw, J. R.; Chupp, E. L.

1989-01-01

Preliminary identifications of instrumental and atmospheric background lines detected by the gamma-ray spectrometer on NASA's Solar Maximum Mission satellite (SMM) are presented. The long-term and stable operation of this experiment has provided data of high quality for use in this analysis. Methods are described for identifying radioactive isotopes which use their different decay times. Temporal evolution of the features are revealed by spectral comparisons, subtractions, and fits. An understanding of these temporal variations has enabled the data to be used for detecting celestial gamma-ray sources.

Fluctuations and symmetry energy in nuclear fragmentation dynamics.

PubMed

Colonna, M

2013-01-25

Within a dynamical description of nuclear fragmentation, based on the liquid-gas phase transition scenario, we explore the relation between neutron-proton density fluctuations and nuclear symmetry energy. We show that, along the fragmentation path, isovector fluctuations follow the evolution of the local density and approach an equilibrium value connected to the local symmetry energy. Higher-density regions are characterized by smaller average asymmetry and narrower isotopic distributions. This dynamical analysis points out that fragment final state isospin fluctuations can probe the symmetry energy of the density domains from which fragments originate.

Variable sulfur isotope composition of sulfides provide evidence for multiple sources of contamination in the Rustenburg Layered Suite, Bushveld Complex

NASA Astrophysics Data System (ADS)

Magalhães, Nivea; Penniston-Dorland, Sarah; Farquhar, James; Mathez, Edmond A.

2018-06-01

The Rustenburg Layered Suite (RLS) of the Bushveld Complex (BC) is famous for its platinum group element (PGE) ore, which is hosted in sulfides. The source of sulfur necessary to generate this type of mineralization is inferred to be the host rock of the intrusion. The RLS has a sulfur isotopic signature that indicates the presence of Archean surface-derived material (Δ33 S ≠ 0) in the magma. This signature, with an average value of Δ33 S = 0.112 ± 0.024 ‰, deviates from the expected Δ33 S value of the mantle of 0 ± 0.008 ‰. Previous work suggested that this signature is uniform throughout the RLS, which contrasts with radiogenic isotopes which vary throughout the igneous stratigraphy of the RLS. In this study, samples from key intervals within the igneous stratigraphy were analyzed, showing that Δ33 S values vary in the same stratigraphic levels as Sr and Nd isotopes. However, the variation is not consistent; in some levels there is a positive correlation and in others a negative correlation. This observation suggests that in some cases distinct magma pulses contained assimilated sulfur from different sources. Textural analysis shows no evidence for late addition of sulfur. These results also suggest that it is unlikely that large-scale assimilation and/or efficient mixing of host rock material in a single magma chamber occurred during emplacement. The data do not uniquely identify the source of sulfur in the different layers of the RLS, but the variation in sulfur isotope composition and its relationship to radiogenic isotope data calls for a reevaluation of the models for the formation and evolution of the RLS, which has the potential to impact the knowledge of how PGE deposits form.

Sm-Nd isotopic data from Archean metavolcanic rocks at Holenarsipur, South India

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

Drury, S.A.; Van Calsteren, P.C.; Reeves-Smith, G.J.

1987-11-01

Results of a Sm-Nd isotopic analysis of Archean metavolcanics in the Holenarsipur greenstone belt, Karnataka, South India, give a whole-rock isochron age of 2.62 Ga for lightly deformed metabasaltic amphibolites in the northern part of the belt. This is within error of the age of high-grade metamorphism and crustal thickening which affected areas further to the south during the late Archean. Together with the geochemical affinities of these and other metavolcanics in Karnataka, and results of regional structural analysis, this unexpected age supports a model relating volcanism and crustal thickening to northward subduction and crustal accretion during the late Archean.more » Data from basic and ultrabasic metavolcanics from the more strongly deformed and higher-grade southern arm of the Holenarsipur belt do not permit an age greater than 3.0 Ga. Previously, these rocks were regarded as part of an older supracrustal sequence that predated the local 3.0 to 3.3 Ga gneissic complex. The new dates therefore considerably simplify attempts at accounting for greenstone evolution in South India.« less

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.

Carbon isotopic studies of organic matter in Precambrian rocks.

NASA Technical Reports Server (NTRS)

Oehler, D. Z.; Schopf, J. W.; Kvenvolden, K. A.

1972-01-01

A survey has been undertaken of the carbon composition of the total organic fraction of a suite of Precambrian sediments to detect isotopic trends possibly correlative with early evolutionary events. Early Precambrian cherts of the Fig Tree and upper and middle Onverwacht groups of South Africa were examined for this purpose. Reduced carbon in these cherts was found to be isotopically similar to photosynthetically produced organic matter of younger geological age. Reduced carbon in lower Onverwacht cherts was found to be anomalously heavy; it is suggested that this discontinuity may reflect a major event in biological evolution.

Chemical evolution of Mg isotopes versus the time variation of the fine structure constant.

PubMed

Ashenfelter, T; Mathews, Grant J; Olive, Keith A

2004-01-30

We show that the synthesis of (25,26)Mg at the base of the convective envelope in low-metallicity asymptotic giant branch stars can produce the isotopic ratios needed to explain the low-z subset (with z<1.8) of the many-multiplet data from quasar absorption systems without invoking a time variation of the fine structure constant. This is supported by observations of high abundances of the neutron-rich Mg isotopes in metal-poor globular-cluster stars. We conclude that the quasar absorption spectra may be providing interesting information on the nucleosynthetic history of such systems.

Isotopic evolution of Mauna Kea volcano: Results from the initial phase of the Hawaii Scientific Drilling Project

USGS Publications Warehouse

Lassiter, J.C.; DePaolo, D.J.; Tatsumoto, M.

1996-01-01

We have examined the Sr, Nd, and Pb isotopic compositions of Mauna Kea lavas recovered by the first drilling phase of the Hawaii Scientific Drilling Project. These lavas, which range in age from ???200 to 400 ka, provide a detailed record of chemical and isotopic changes in basalt composition during the shied/postshield transition and extend our record of Mauna Kea volcanism to a late-shield period roughly equivalent to the last ???100 ka of Mauna Loa activity. Stratigraphic variations in isotopic composition reveal a gradual shift over time toward a more depleted source composition (e.g., higher 143Nd/144Nd, lower 87Sr/86Sr, and lower 3He/4He). This gradual evolution is in sharp contrast with the abrupt appearance of alkalic lavas at ???240 ka recorded by the upper 50 m of Mauna Kea lavas from the core. Intercalated tholeiitic and alkalic lavas from the uppermost Mauna Kea section are isotopically indistinguishable. Combined with major element evidence (e.g., decreasing SiO2 and increasing FeO) that the depth of melt segregation increased during the transition from tholeiitic to alkalic volcanism, the isotopic similarity of tholeiitic and alkalic lavas argues against significant lithosphere involvement during melt generation. Instead, the depleted isotopic signatures found in late shield-stage lavas are best explained by increasing the proportion of melt generated from a depleted upper mantle component entrained and heated by the rising central plume. Direct comparison of Mauna Kea and Mauna Loa lavas erupted at equivalent stages in these volcanoes' life cycles reveals persistent chemical and isotopic differences independent of the temporal evolution of each volcano. The oldest lavas recovered from the drillcore are similar to modern Kilauea lavas, but are distinct from Mauna Loa lavas. Mauna Kea lavas have higher 143Nd/144Nd and 206Pb/204Pb and lower 87Sr/86Sr. Higher concentrations of incompatible trace elements in primary magmas, lower SiO2, and higher FeO also indicate that Mauna Kea lavas formed through smaller degrees of partial melting at greater depth than Mauna Loa lavas. These chemical and isotopic differences are consistently found between volcanoes along the western "Loa" and eastern "Kea" trends and reflect large-scale variations in source composition and melting environment. We propose a simple model of a radially zoned plume centered beneath the Loa trend. Loa trend lavas generated from the hot plume axis reflect high degrees of partial melting from a source containing a mixture of enriched plume-source material and entrained lower mantle. Kea trend lavas, in contrast, are generated from the cooler, peripheral portions of the plume, record lower degrees of partial melting, and tap a source containing a greater proportion of depleted upper mantle.

Workshop on Early Crustal Genesis: Implications from Earth

NASA Technical Reports Server (NTRS)

Phinney, W. C. (Compiler)

1981-01-01

Ways to foster increased study of the early evolution of the Earth, considering the planet as a whole, were explored and recommendations were made to NASA with the intent of exploring optimal ways for integrating Archean studies with problems of planetary evolution. Major themes addressed include: (1) Archean contribution to constraints for modeling planetary evolution; (2) Archean surface conditions and processes as clues to early planetary history; and (3) Archean evidence for physical, chemical and isotopic transfer processes in early planetary crusts. Ten early crustal evolution problems are outlined.

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.

A preliminary study on isotopic evolution of ice by a melting experiment

NASA Astrophysics Data System (ADS)

Ham, J. Y.; Lee, J.; Lee, W. S.; Han, Y.; Hur, S. D.

2016-12-01

Evidences of melted snow at surface were found on some ice cores. Melted layers may generate a significant error when paleo-temperature was retrieved from ice cores using stable water isotopes. To resolve this problem, it is necessary to understand the isotopic changes of ice and its meltwater that is made during the ice and snow melting. Isotopic fractionations between liquid water and snow have been discussed by Taylor et al. (2002) and Lee et al. (2009). The goal of this work is to understand isotopic evolution of ice and its meltwater. Melting experiments in a cold room were designed and conducted with heat source (infrared lamp) to mimic solar radiation. Melting rates were calculated in terms of specific discharge (g/min). To control melting rates, distances between ice surface and heat source were adjusted in various conditions (1 cm, 10 cm and 20 cm). The experiments were conducted by three different melting rates, 1.6 g/min, 3.5 g/min and 5.8 g/min. We used cubic ice that has 3 cm in width, length and height in dimension with 1.5 kg or 2 kg of ice used totally. The total time spent melting the whole ice was 592, 783, and 1180 minutes, respectively. Cold room temperature was range of -1 to 1°C, which removes an effect of air temperature. Meltwater samples were collected and isotopic compositions of oxygen and hydrogen were determined by a cavity ring down spectrometer (Picarro L-1120) installed at the Korea Polar Research Institute. We also analyzed bulk water and bulk ice to make the ice used in the experiments (-8.20 ‰ and -58.73 ‰ for oxygen and hydrogen isotopes, respectively). The isotopic compositions of meltwater increased linearly or to a second degree polynomial. The isotopic variations were larger in the lower melting rates, compared to the higher melting rates (0.65 of lower melting rates vs. 0.35 higher melting rates for oxygen isotope). The slope of linear regression between oxygen and hydrogen ranged 6.2, 7.3 and 6.2, which is less than that of the Global Meteoric Water Line (8) and the sublimation (7.7) suggested by Earman et al. (2006). We believe that isotopic exchange between liquid water and ice plays a crucial role in the variations of isotopes for the ice and its meltwater. We will modify a physically based 1-D model used in the previous studies to better understand the isotopic compositions of ice and its meltwater.

Multi-Isotopic evidence from West Eifel Xenoliths

NASA Astrophysics Data System (ADS)

Thiemens, M. M.; Sprung, P.

2015-12-01

Mantle Xenoliths from the West Eifel intraplate volcanic field of Germany provide insights into the nature and evolution of the regional continental lithospheric mantle. Previous isotope studies have suggested a primary Paleoproterozoic depletion age, a second partial melting event in the early Cambrian, and a Variscan metasomatic overprint. Textural and Sr-Nd isotopic observations further suggest two episodes of melt infiltration of early Cretaceous and Quaternary age. We have investigated anhydrous, vein-free lherzolites from this region, focusing on the Dreiser Weiher and Meerfelder Maar localities. Hand separated spinel, olivine, ortho- and clinopryoxene, along with host and bulk rocks were dissolved and purified for Rb-Sr, Sm-Nd, and Lu-Hf analysis on the Cologne/Bonn Neptune MC-ICP-MS. We find an unexpected discontinuity between mineral separates and whole rocks. While the latter have significantly more radiogenic ɛNd and ɛHf, mineral separates imply close-to chondritic compositions. Our Lu-Hf data imply resetting of the Lu-Hf systematic after 200 Ma. Given the vein-free nature of the lherzolites, this appears to date to the second youngest metasomatic episode. We suggest that markedly radiogenic Nd and Hf were introduced during the Quarternary metasomatic episode and most likely reside on grain boundaries.

The Carbonates in ALH 84001 Record the Evolution of the Martian Atmosphere Through Multiple Formation Events

NASA Technical Reports Server (NTRS)

Shaheen, R.; Niles, P. B.; Corrgan, C.

2012-01-01

Current Martian conditions restrict the presence of liquid water due to low temperatures (approx 210K), a thin atmosphere (approx 7mb), and intense UV radiation. However, past conditions on Mars may have been different with the possibility that the ancient Martian climate was warm and wet with a dense CO2 atmosphere. The cycling of carbon on Mars through atmospheric CO2 and carbonate minerals is critical for deciphering its climate history. In particular stable isotopes contained in carbonates can provide information of their origin and formation environment as well as possibly hinting at the composition of global reservoirs such as atmospheric CO2. Martian meteorite ALH 84001 contains widely studied carbonate rosettes that have been dated to approx. 3.9 Ga and have been used to interpret climatic conditions present at that time. However, there is mount-ing evidence for multiple episodes of carbonate formation in ALH 84001 with potentially distinct isotopic compositions. This study seeks to tease out these different carbonate assemblages using stepped phosphoric acid dissolution and analysis of carbon and triple oxygen stable isotopes. In addition, we report SIMS analyses of the delta O-18 several petrographically unusual carbonate phases in the meteorite.

On the similarity and apparent cycles of isotopic variations in East Antarctic snow pits

NASA Astrophysics Data System (ADS)

Laepple, Thomas; Münch, Thomas; Casado, Mathieu; Hoerhold, Maria; Landais, Amaelle; Kipfstuhl, Sepp

2018-01-01

Stable isotope ratios δ18O and δD in polar ice provide a wealth of information about past climate evolution. Snow-pit studies allow us to relate observed weather and climate conditions to the measured isotope variations in the snow. They therefore offer the possibility to test our understanding of how isotope signals are formed and stored in firn and ice. As δ18O and δD in the snowfall are strongly correlated to air temperature, isotopes in the near-surface snow are thought to record the seasonal cycle at a given site. Accordingly, the number of seasonal cycles observed over a given depth should depend on the accumulation rate of snow. However, snow-pit studies from different accumulation conditions in East Antarctica reported similar isotopic variability and comparable apparent cycles in the δ18O and δD profiles with typical wavelengths of ˜ 20 cm. These observations are unexpected as the accumulation rates strongly differ between the sites, ranging from 20 to 80 mm w. e. yr-1 ( ˜ 6-21 cm of snow per year). Various mechanisms have been proposed to explain the isotopic variations individually at each site; however, none of these are consistent with the similarity of the different profiles independent of the local accumulation conditions.Here, we systematically analyse the properties and origins of δ18O and δD variations in high-resolution firn profiles from eight East Antarctic sites. First, we confirm the suggested cycle length (mean distance between peaks) of ˜ 20 cm by counting the isotopic maxima. Spectral analysis further shows a strong similarity between the sites but indicates no dominant periodic features. Furthermore, the apparent cycle length increases with depth for most East Antarctic sites, which is inconsistent with burial and compression of a regular seasonal cycle. We show that these results can be explained by isotopic diffusion acting on a noise-dominated isotope signal. The firn diffusion length is rather stable across the Antarctic Plateau and thus leads to similar power spectral densities of the isotopic variations. This in turn implies a similar distance between isotopic maxima in the firn profiles.Our results explain a large set of observations discussed in the literature, providing a simple explanation for the interpretation of apparent cycles in shallow isotope records, without invoking complex mechanisms. Finally, the results underline previous suggestions that isotope signals in single ice cores from low-accumulation regions have a small signal-to-noise ratio and thus likely do not allow the reconstruction of interannual to decadal climate variations.

To See a World in a Grain of Sand: Insights into Solar System Formation and Evolution from Isotopic Analyses of Planetary Materials

NASA Astrophysics Data System (ADS)

Wadhwa, M.

2016-12-01

The last few decades have seen revolutionary advances in the planetary sciences through remote observations (by spacecraft and Earth-based observatories) of many Solar System destinations and, in more recent years, even exoplanets around other stars. In parallel with this, ground-breaking developments in analytical capabilities and access to a greater variety of Solar System materials (through systematic and sustained meteorite collection programs as well as sample return missions) have led to significant insights that are complementary to those from remote observations and measurements. I will discuss two examples where the combination of remote observations and sample analyses has the potential to provide a more holistic picture of Solar System formation and evolution: 1) High-precision analyses of radiogenic isotopes in primitive and differentiated meteoritic materials, which are yielding a detailed high-resolution chronology of the first 10 million years of Solar System history. Such investigations are providing the chronological framework for the formation and evolution of small bodies (including comets, asteroids and Kuiper Belt Objects) in our Solar System that are the targets of recent spacecraft missions such as NASA's Dawn and New Horizons missions and ESA's Rosetta mission. 2) In-situ analyses of hydrogen isotope compositions and H2O abundances in meteorites from Mars and Vesta, which are giving constraints on the inventory and source of water and other volatiles in these planetary bodies. These studies are providing insights complementary to those about Mars from NASA's Mars Science Laboratory and Mars Atmosphere and Volatile Evolution (MAVEN) missions, and about Vesta from NASA's Dawn mission.

Evolution of depleted mantle: The lead perspective

NASA Astrophysics Data System (ADS)

Tilton, George R.

1983-07-01

Isotopic data have established that, compared to estimated bulk earth abundances, the sources of oceanic basaltic lavas have been depleted in large ion lithophile elements for at least several billions of years. Various data on the Tertiary-Mesozoic Gorgona komatiite and Cretaceous Oka carbonatite show that those rocks also sample depleted mantle sources. This information is used by analogy to compare Pb isotopic data from 2.6 billion year old komatiite and carbonatite from the Suomussalmi belt of eastern Finland and Munro Township, Ontario that are with associated granitic rocks and ores that should contain marked crustal components. Within experimental error no differences are detected in the isotopic composition of initial Pb in either of the rock suites. These observations agree closely with Sr and Nd data from other laboratories showing that depleted mantle could not have originated in those areas more than a few tenths of billions of years before the rocks were emplaced. On a world-wide basis the Pb isotope data are consistent with production of depleted mantle by continuous differentiation processes acting over approximately the past 3 billion years. The data show that Pb evolution is more complex than the simpler models derived from the Rb-Sr and Sm-Nd systems. The nature of the complexity is still poorly understood.

Mass Dependency of Isotope Fractionation of Gases Under Thermal Gradient and Its Possible Implications for Planetary Atmosphere Escaping Process

NASA Technical Reports Server (NTRS)

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard

2014-01-01

Physical processes that unmix elements/isotopes of gas molecules involve phase changes, diffusion (chemical or thermal), effusion and gravitational settling. Some of those play significant roles for the evolution of chemical and isotopic compositions of gases in planetary bodies which lead to better understanding of surface paleoclimatic conditions, e.g. gas bubbles in Antarctic ice, and planetary evolution, e.g. the solar-wind erosion induced gas escaping from exosphere on terrestrial planets.. A mass dependent relationship is always expected for the kinetic isotope fractionations during these simple physical processes, according to the kinetic theory of gases by Chapman, Enskog and others [3-5]. For O-bearing (O16, -O17, -O18) molecules the alpha O-17/ alpha O-18 is expected at 0.5 to 0.515, and for S-bearing (S32,-S33. -S34, -S36) molecules, the alpha S-33/ alpha S-34 is expected at 0.5 to 0.508, where alpha is the isotope fractionation factor associated with unmixing processes. Thus, one isotope pair is generally proxied to yield all the information for the physical history of the gases. However, we recently] reported the violation of mass law for isotope fractionation among isotope pairs of multiple isotope system during gas diffusion or convection under thermal gradient (Thermal Gradient Induced Non-Mass Dependent effect, TGI-NMD). The mechanism(s) that is responsible to such striking observation remains unanswered. In our past studies, we investigated polyatomic molecules, O2 and SF6, and we suggested that nuclear spin effect could be responsible to the observed NMD effect in a way of changing diffusion coefficients of certain molecules, owing to the fact of negligible delta S-36 anomaly for SF6.. On the other hand, our results also showed that for both diffusion and convection under thermal gradient, this NMD effect is increased by lower gas pressure, bigger temperature gradient and lower average temperature, which indicate that the nuclear spin effect may not be the significant contributor as the energies involved in the hyperfine effect are much smaller than those with molecular collisions, especially under convective conditions.

Mg Isotope Evolution During Water-Rock Interaction in a Carbonate Aquifer

NASA Astrophysics Data System (ADS)

Zhang, Z.; Jacobson, A. D.; Lundstrom, C. C.; Huang, F.

2008-12-01

To better understand how Mg isotopes behave during weathering and aqueous transport, we used a Nu Plasma MC-ICP-MS to measure δ26Mg values (relative to DSM-3) in water samples along a 236 km flow path in the Madison aquifer of South Dakota, a confined carbonate aquifer recharging in the igneous Black Hills. We also analyzed local granite and dolomite samples to characterize the Mg isotope composition of source rocks constituting the recharge zone and aquifer, respectively. Repeated analyses of Mg standard solutions yielded external precisions (2σ) better than 0.1 permil for δ26Mg(CAM-1, - 2.584±0.071, n=13; UIMg-1, -2.217±0.087, n=9.). The Madison aquifer provides a unique opportunity to quantify Mg isotope effects during water-rock interaction because (1) fluids and rock have chemically equilibrated over a much longer timescale (up to ~15 kyr) than can be simulated in laboratory experiments and (2) previous studies have determined the rates and mass-balances of de- dolomitization and other geochemical reactions controlling solute evolution along the flow path. Reactions important for changing the concentration and isotope composition of Mg include dolomite dissolution, Mg-for- Na ion exchange, calcite precipitation, and isotope exchange. δ26Mg values within the recharge region (0-17 km along flow path) vary between -1.08 and -1.63 permil, and then remain essentially constant at -1.408±0.010 permil(1σ, 5 samples) from 17 to 189 km. A final sample at 236 km shows an increase to -1.09 permil. Either mixing between different recharge waters or rapid isotope exchange between infiltrating waters and dolomite could control δ26Mg variability between 0 and 17 km. Likewise, reactive transport modeling suggests that preferential uptake of 24Mg during Mg-for-Na ion exchange might cause an increase in δ26Mg between 189 and 236 km. However, unchanging δ26Mg values observed throughout most of the aquifer clearly demonstrate that Mg isotopes are not fractionated during reactive transport. This suggests that Mg isotopes can conservatively trace weathering inputs and groundwater flow in dolomite-rich aquifers.

Constraints of lithium isotopes on petrogenesis of the Northern Luzon arc in Eastern Taiwan

NASA Astrophysics Data System (ADS)

Hsiao, C. C.; Chu, M. F.; Lai, Y. M.; Lin, T. H.

2017-12-01

Lithium stable isotopes have great potential as a tracer of terrestrial materials in crust-mantle recycling. However, the causes of their variations in arc magmatism remain controversial. The Northern Luzon arc has long been demonstrated incorporation of the sediment melt into its sub-arc mantle. The Li isotopes of volcanic rocks in the Coastal Range, located in Eastern Taiwan, thus are studied to examine the effects of sediment melt on the evolution of Li isotopes in subduction zone and also to constrain the petrogenesis of the northernmost part of Northern Luzon arc. It is worth to note that we had ruled out samples that were significantly influenced by crustal contamination according to the proportion of inherited zircons, trace-elemental and Sr-Nd isotopic geochemistry. Concerning that Li isotopic fractionation is negligible during fractional crystallization and partial melting, the variation of Li/Y and δ7Li in rock samples of this study mainly reflects the geochemistry of magma sources. The overall range of δ7Li is very restricted (δ7Li = +2.9 +5.8) and consistent with that of N-MORB. In addition, ɛNd of the Coastal Range volcanic rocks lowers not only with increasing values of sediment-melt indicators (e.g., Th/Ce, Th/Yb and La/Sm), but also Li/Y (from 0.5 to 1.1 ppm). This suggests the involvement of sediment melt with equivalent δ7Li to and higher Li/Y than those of N-MORB, in magma source of the Coastal Range arc volcanism. In summary, the Li isotopic compositions of the Coastal Range volcanic rocks demonstrate that (1) Li/Y commonly treated as a tracer of fluid in arc magmatism indeed can be significantly affected by the input of sediment melt as well, and (2) sediment melt played a key role in the evolution of Li/Y and lithium isotopes in the mantle wedge, but showed least influence on Li isotopic variation possibly as a result of the similarity between δ7Li of sediments subducted and of the upper mantle.

Geochemistry of Intra-Transform Lavas from the Galápagos Transform Fault

NASA Astrophysics Data System (ADS)

Morrow, T. A.; Mittelstaedt, E. L.; Harpp, K. S.

2013-12-01

The Galápagos plume has profoundly affected the development and evolution of the nearby (<250 km) Galápagos Transform Fault (GTF), a ~100km right-stepping offset in the Galápagos Spreading Center (GSC). The GTF can be divided into two sections that represent different stages of transform evolution: the northern section exhibits fully developed transform fault morphology, whereas the southern section is young, and deformation is more diffuse. Both segments are faulted extensively and include numerous small (<0.5km3) monogenetic volcanic cones, though volcanic activity is more common in the south. To examine the composition of the mantle source and melting conditions responsible for the intra-transform lavas, as well as the influence of the plume on GTF evolution, we present major element, trace element, and radiogenic isotope analysis of samples collected during SON0158, EWI0004, and MV1007 cruises. Radiogenic isotope ratio variations in the Galápagos Archipelago require four distinct mantle reservoirs across the region: PLUME, DM, FLO, and WD. We find that Galápagos Transform lavas are chemically distinct from nearby GSC lavas and neighboring seamounts. They have radiogenic isotopic compositions that lie on a mixing line between DM and PLUME, with little to no contribution from any other mantle reservoirs despite their geographic proximity to WD-influenced lavas erupted along the GSC and at nearby (<50km away) seamounts. Within the transform, lavas from the northern section are more enriched in radiogenic isotopes than lavas sampled in the southern section. Transform lavas are anomalously depleted in incompatible trace elements (ITEs) relative to GSC lavas, suggesting unique melting conditions within the transform. Isotopic variability along the transform axis indicates that mantle sources and/or melting mechanisms vary between the northern and southern sections, which may relate to their distances from the plume or the two-stage development and evolution of the Galápagos Transform Fault. We present a melting model that reproduces GTF lava chemistry from a mixture of two partial melts of PLUME and DM. We assume that the DM source has an ITE composition similar to the depleted upper mantle, melting is purely fractional, and lavas do not fractionate during ascent. Solutions were achieved using a Metropolis algorithm and constrained by observed GTF lava chemistry. Model results predict that GTF lavas are produced by a mixture of a ~3%×1% partial melt of the PLUME source and a ~5%×4% partial melt of the DM source. Our model predicts that a larger proportion of PLUME melts contribute to GTF lavas than DM melts. Absence of the WD component and relatively low concentrations of ITEs may indicate that lavas in the GTF are produced from a source that has already undergone partial melting and is being re-melted beneath the TF. Re-melting may be caused by extension across the GTF, or development of the southern section of the GTF via the ~1Ma ridge jump.

A combined geodynamical-geochemical modelling approach to investigating the Lu-Hf isotopic evolution of the terrestrial mantle and crust

NASA Astrophysics Data System (ADS)

Jones, R.; Van Keken, P. E.; Hauri, E.; Vervoort, J. D.; Ballentine, C. J.

2017-12-01

The chemical and isotopic evolution of the Earth's mantle is largely influenced by the formation of oceanic and continental crust at spreading ridges and through arc volcanism, and the subsequent recycling of this crust back into the mantle via subduction. In this study we use a combined geodynamical-geochemical modelling approach to investigate the Lu-Hf isotopic evolution of the terrestrial mantle and crust. We utilise the geodynamic mantle convection model developed by Brandenburg et al., 2008. This model satisfies the geophysical constraints of oceanic heat flow and average plate velocities, as well as geochemical observations such as 40Ar in the atmosphere. It has also been shown to reproduce the observed geochemical distributions in multiple isotope systems (U-Th-Pb, Rb-Sr, Sm-Nd, and Re-Os) that define the DMM, HIMU and EM1 mantle endmembers. We go on to extend this application to investigate the Lu-Hf isotope system, specifically in combination with Sm-Nd. The model has been updated to include a self-consistent reorganisation of the plates with regions of up-/down-wellings. The model is initiated at 4.55 Ga, assumes continental crust is produced from 4 Ga and that a transition from `dry' to `wet' subduction occurs at 3 Ga. The results of the geodynamic model suggest that the ƐHf composition and evolution of the upper mantle can be generated through the extraction and recycling of oceanic crust, which creates an enriched and radiogenic reservoir at the core-mantle boundary. The formation of continental crust, which is extracted at each time-step from the oceanic crust to imitate subduction zone processes, and the recycling of this continental crust as sediments, plays a lesser role. Depending on the selected partition coefficients DMM, FOZO and HIMU mantle endmember compositions are also produced via the simple extraction and recycling of oceanic crust. The formation of continental crust produces spread in the ƐNd vs. ƐHf array and extends the model values into the HIMU region of the terrestrial array. We go on to use this geodynamic-geochemical model to investigate different models of continental growth, by observing the effects on the coupled crustal-mantle reservoirs. Brandenburg, J.P., Hauri, E.H., van Keken, P.E., Ballentine, C.J., 2008. Earth and Planetary Science Letters 276, 1-13.

Impact of nuclear transmutations on the primary damage production: The example of Ni based steels

NASA Astrophysics Data System (ADS)

Luneville, Laurence; Sublet, Jean Christphe; Simeone, David

2018-07-01

The recent nuclear evaluations describe more accurately the elastic and inelastic neutron-atoms interactions and allow calculating more realistically primary damage induced by nuclear reactions. Even if these calculations do not take into account relaxation processes occurring at the end of the displacement cascade (calculations are performed within the Binary Collision Approximation), they can accurately describe primary and recoil spectra in different reactors opening the door for simulating aging of nuclear materials with Ion Beam facilities. Since neutrons are only sensitive to isotopes, these spectra must be calculated weighting isotope spectra by the isotopic composition of materials under investigation. To highlight such a point, primary damage are calculated in pure Ni exhibiting a meta-stable isotope produced under neutron flux by inelastic neutron-isotope processes. These calculations clearly point out that the instantaneous primary damage production, the displacement per atom rate (dpa/s), responsible for the micro-structure evolution, strongly depends on the 59N i isotopic fractions closely related to the inelastic neutron isotope processes. Since the isotopic composition of the meta-stable isotope vanishes for large fluences, the long term impact of this isotope does not largely modify drastically the total dpa number in Ni based steels materials irradiate in nuclear plants.

Prospects for improved understanding of isotopic reactor antineutrino fluxes

NASA Astrophysics Data System (ADS)

Gebre, Y.; Littlejohn, B. R.; Surukuchi, P. T.

2018-01-01

Predictions of antineutrino fluxes produced by fission isotopes in a nuclear reactor have recently received increased scrutiny due to observed differences in predicted and measured inverse beta decay (IBD) yields, referred to as the "reactor antineutrino flux anomaly." In this paper, global fits are applied to existing IBD yield measurements to produce constraints on antineutrino production by individual plutonium and uranium fission isotopes. We find that fits including measurements from highly U 235 -enriched cores and fits including Daya Bay's new fuel evolution result produce discrepant best-fit IBD yields for U 235 and Pu 239 . This discrepancy can be alleviated in a global analysis of all data sets through simultaneous fitting of Pu 239 , U 235 , and U 238 yields. The measured IBD yield of U 238 in this analysis is (7.02 ±1.65 )×10-43 cm2/fission , nearly two standard deviations below existing predictions. Future hypothetical IBD yield measurements by short-baseline reactor experiments are examined to determine their possible impact on the global understanding of isotopic IBD yields. It is found that future improved short-baseline IBD yield measurements at both high-enriched and low-enriched cores can significantly improve constraints for U 235 , U 238 , and Pu 239 , providing comparable or superior precision to existing conversion- and summation-based antineutrino flux predictions. Systematic and experimental requirements for these future measurements are also investigated.

Cenozoic climate changes: A review based on time series analysis of marine benthic δ18O records

NASA Astrophysics Data System (ADS)

Mudelsee, Manfred; Bickert, Torsten; Lear, Caroline H.; Lohmann, Gerrit

2014-09-01

The climate during the Cenozoic era changed in several steps from ice-free poles and warm conditions to ice-covered poles and cold conditions. Since the 1950s, a body of information on ice volume and temperature changes has been built up predominantly on the basis of measurements of the oxygen isotopic composition of shells of benthic foraminifera collected from marine sediment cores. The statistical methodology of time series analysis has also evolved, allowing more information to be extracted from these records. Here we provide a comprehensive view of Cenozoic climate evolution by means of a coherent and systematic application of time series analytical tools to each record from a compilation spanning the interval from 4 to 61 Myr ago. We quantitatively describe several prominent features of the oxygen isotope record, taking into account the various sources of uncertainty (including measurement, proxy noise, and dating errors). The estimated transition times and amplitudes allow us to assess causal climatological-tectonic influences on the following known features of the Cenozoic oxygen isotopic record: Paleocene-Eocene Thermal Maximum, Eocene-Oligocene Transition, Oligocene-Miocene Boundary, and the Middle Miocene Climate Optimum. We further describe and causally interpret the following features: Paleocene-Eocene warming trend, the two-step, long-term Eocene cooling, and the changes within the most recent interval (Miocene-Pliocene). We review the scope and methods of constructing Cenozoic stacks of benthic oxygen isotope records and present two new latitudinal stacks, which capture besides global ice volume also bottom water temperatures at low (less than 30°) and high latitudes. This review concludes with an identification of future directions for data collection, statistical method development, and climate modeling.

Nanogeochronology of discordant zircon measured by atom probe microscopy of Pb-enriched dislocation loops

PubMed Central

Peterman, Emily M.; Reddy, Steven M.; Saxey, David W.; Snoeyenbos, David R.; Rickard, William D. A.; Fougerouse, Denis; Kylander-Clark, Andrew R. C.

2016-01-01

Isotopic discordance is a common feature in zircon that can lead to an erroneous age determination, and it is attributed to the mobilization and escape of radiogenic Pb during its post-crystallization geological evolution. The degree of isotopic discordance measured at analytical scales of ~10 μm often differs among adjacent analysis locations, indicating heterogeneous distributions of Pb at shorter length scales. We use atom probe microscopy to establish the nature of these sites and the mechanisms by which they form. We show that the nanoscale distribution of Pb in a ~2.1 billion year old discordant zircon that was metamorphosed c. 150 million years ago is defined by two distinct Pb reservoirs. Despite overall Pb loss during peak metamorphic conditions, the atom probe data indicate that a component of radiogenic Pb was trapped in 10-nm dislocation loops that formed during the annealing of radiation damage associated with the metamorphic event. A second Pb component, found outside the dislocation loops, represents homogeneous accumulation of radiogenic Pb in the zircon matrix after metamorphism. The 207Pb/206Pb ratios measured from eight dislocation loops are equivalent within uncertainty and yield an age consistent with the original crystallization age of the zircon, as determined by laser ablation spot analysis. Our results provide a specific mechanism for the trapping and retention of radiogenic Pb during metamorphism and confirm that isotopic discordance in this zircon is characterized by discrete nanoscale reservoirs of Pb that record different isotopic compositions and yield age data consistent with distinct geological events. These data may provide a framework for interpreting discordance in zircon as the heterogeneous distribution of discrete radiogenic Pb populations, each yielding geologically meaningful ages. PMID:27617295

A reconstruction of atmospheric carbon dioxide and its stable carbon isotopic composition from the penultimate glacial maximum to the last glacial inception

NASA Astrophysics Data System (ADS)

Schneider, R.; Schmitt, J.; Köhler, P.; Joos, F.; Fischer, H.

2013-11-01

The reconstruction of the stable carbon isotope evolution in atmospheric CO2 (δ13Catm), as archived in Antarctic ice cores, bears the potential to disentangle the contributions of the different carbon cycle fluxes causing past CO2 variations. Here we present a new record of δ13Catm before, during and after the Marine Isotope Stage 5.5 (155 000 to 105 000 yr BP). The dataset is archived on the data repository PANGEA® (www.pangea.de) under 10.1594/PANGAEA.817041. The record was derived with a well established sublimation method using ice from the EPICA Dome C (EDC) and the Talos Dome ice cores in East Antarctica. We find a 0.4‰ shift to heavier values between the mean δ13Catm level in the Penultimate (~ 140 000 yr BP) and Last Glacial Maximum (~ 22 000 yr BP), which can be explained by either (i) changes in the isotopic composition or (ii) intensity of the carbon input fluxes to the combined ocean/atmosphere carbon reservoir or (iii) by long-term peat buildup. Our isotopic data suggest that the carbon cycle evolution along Termination II and the subsequent interglacial was controlled by essentially the same processes as during the last 24 000 yr, but with different phasing and magnitudes. Furthermore, a 5000 yr lag in the CO2 decline relative to EDC temperatures is confirmed during the glacial inception at the end of MIS5.5 (120 000 yr BP). Based on our isotopic data this lag can be explained by terrestrial carbon release and carbonate compensation.

Role of deep-Earth water cycling in the growth and evolution of continental crust: Constraints from Cretaceous magmatism in southeast China

NASA Astrophysics Data System (ADS)

Li, Zhen; Wang, Xuan-Ce; Wilde, Simon A.; Liu, Liang; Li, Wu-Xian; Yang, Xuemei

2018-03-01

The late Mesozoic igneous province in southeast China provides an excellent opportunity to understand the processes that controlled the growth and evolution of Phanerozoic continental crust. Here we report petrological, whole-rock geochemical and isotopic data, and in situ zircon U-Pb-Lu-Hf isotopic data from granitoids and associated gabbros in the Pingtan and Tong'an complexes, southeast China. Through combining the new results with published datasets in southeast China, we show that the Early Cretaceous magmatic rocks are dominated by juvenile Nd-Hf isotopic compositions, whereas the Late Cretaceous ones display less radiogenic Nd-Hf isotope signatures. Furthermore, Nd-Hf isotope systematics are coupled with decreasing abundance of hydrous minerals and an increase of zircon saturation temperatures. Compiled zircon Hf-O data indicates that the 117-116 Ma granites have zircon δ18O values ranging from mantle values (close to 5.3‰) to as low as 3.9‰, but with dominantly positive initial epsilon Hf (εHf(t)) values. Zircon grains from 105 to 98 Ma rocks have δ18O values plotting within the mantle-like range (6.5‰ - 4.5‰), but mainly with negative εHf(t) values. Zircon grains from ca. 87 Ma rocks have positive εHf(t) values (+ 9.8 to + 0.7) and a large range of δ18O values (6.3‰ - 3.5‰). The variations in Hf-Nd-O isotopic compositions are correlated with decreasing abundance of magma water contents, presenting a case that water-fluxed melting generated large-scale granitic magmatism. Deep-Earth water cycling provides an alternative or additional mechanism to supply volatiles (e.g., H2O) for hydrous basaltic underplating, continental crustal melting, and magmatic differentiation.

The application of chemical and isotopic tracers to characterize aerosol sources and processing in marine air

NASA Astrophysics Data System (ADS)

Turekian, Vaughan Charles

2000-12-01

Aerosol production, transport, chemical and physical evolution and deposition impact the environment by influencing radiation budgets, altering the composition of the atmosphere, and delivering nutrients to marine and terrestrial ecosystems. The objective of this research was to combine high-resolution chemical measurements with stable isotopic analysis in order to characterize the sources and processing of carbon, nitrogen and sulfur bearing compounds, associated with sized aerosols on Bermuda, during spring. Chemical tracers combined with forward and backward trajectories demonstrated the transport of biomass burning products from North America to Bermuda. The size distributions of NH4+ from 1998 differed from those during spring, 1997, a year without the large-scale burning. These results suggest that transport of biomass burning products altered the pH of the aerosols. Marine and continentally derived carbon was associated with all aerosol size fractions. Supermicron radius sea- salt aerosol was enriched in marine derived carbon by 2 orders of magnitude compared to bulk surface seawater. Enrichments of oxalate relative to methanesulfonic acid (MSA) in supermicron radius aerosol suggested in situ formation of oxalate within the sea-salt solution, or direct injection from the organic rich surface microlayer. Compound specific isotope analysis of oxalic acid, indicated a marine source for all aerosol size fractions, indicating formation from in the gas phase for the submicron radius aerosol. Stable sulfur isotopes indicated that the biogenic non- sea-salt (nss) SO42-/MSA ratio varied with aerosol size indicating that MSA may not be a conservative tracer of biogenic nss SO4 2- in bulk aerosol sampling. The calculated biogenic nss SO 42-/MSA based on stable isotopes and sized aerosol sampling, was 3 times lower than previous estimates for Bermuda. Stable nitrogen isotope values for submicron and supermicron aerosol where significantly different, consistent with their different chemical compositions. Results suggested that HNO3 incorporation into supermicron aerosol was essentially unidirectional whereas submicron aerosol was both a source and a sink for NH3(g). Variable aerosol liquid water content over the relatively longer atmospheric lifetimes of submicron aerosol may lead to multiple NH3 phase changes. This study was the first to combine sized aerosol sampling, high-resolution chemical analysis and multiple stable isotopes to characterize both the sources and the processing of aerosols in marine air. The results of this study, therefore, provide crucial information for source apportionment of environmentally important atmospheric species in continentally impacted, marine air.

An extended version of the SERPENT-2 code to investigate fuel burn-up and core material evolution of the Molten Salt Fast Reactor

NASA Astrophysics Data System (ADS)

Aufiero, M.; Cammi, A.; Fiorina, C.; Leppänen, J.; Luzzi, L.; Ricotti, M. E.

2013-10-01

In this work, the Monte Carlo burn-up code SERPENT-2 has been extended and employed to study the material isotopic evolution of the Molten Salt Fast Reactor (MSFR). This promising GEN-IV nuclear reactor concept features peculiar characteristics such as the on-line fuel reprocessing, which prevents the use of commonly available burn-up codes. Besides, the presence of circulating nuclear fuel and radioactive streams from the core to the reprocessing plant requires a precise knowledge of the fuel isotopic composition during the plant operation. The developed extension of SERPENT-2 directly takes into account the effects of on-line fuel reprocessing on burn-up calculations and features a reactivity control algorithm. It is here assessed against a dedicated version of the deterministic ERANOS-based EQL3D procedure (PSI-Switzerland) and adopted to analyze the MSFR fuel salt isotopic evolution. Particular attention is devoted to study the effects of reprocessing time constants and efficiencies on the conversion ratio and the molar concentration of elements relevant for solubility issues (e.g., trivalent actinides and lanthanides). Quantities of interest for fuel handling and safety issues are investigated, including decay heat and activities of hazardous isotopes (neutron and high energy gamma emitters) in the core and in the reprocessing stream. The radiotoxicity generation is also analyzed for the MSFR nominal conditions. The production of helium and the depletion in tungsten content due to nuclear reactions are calculated for the nickel-based alloy selected as reactor structural material of the MSFR. These preliminary evaluations can be helpful in studying the radiation damage of both the primary salt container and the axial reflectors.

Seasonal progression of uranium series isotopes in subglacial meltwater: Implications for subglacial storage time

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

Arendt, Carli A.; Aciego, Sarah M.; Sims, Kenneth W. W.

The residence time of subglacial meltwater impacts aquifer recharge, nutrient production, and chemical signals that reflect underlying bedrock/substrate, but is inaccessible to direct observation. We report the seasonal evolution of subglacial meltwater chemistry from the 2011 melt season at the terminus of the Athabasca Glacier, Canada. We also measured major and trace analytes and U-series isotopes for twenty-nine bulk meltwater samples collected over the duration of the melt season. This dataset, which is the longest time-series record of ( 234U/ 238U) isotopes in a glacial meltwater system, provides insight into the hydrologic evolution of the subglacial system during active melting.more » Meltwater samples, measured from the outflow, were analyzed for ( 238U), ( 222Rn) and ( 234U/ 238U)activity, conductivity, alkalinity, pH and major cations. Subglacial meltwater varied in [238U] and (222Rn) from 23 to 832 ppt and 9 to 171 pCi/L, respectively. Activity ratios of ( 234U/ 238U) ranged from 1.003 to 1.040, with the highest ( 238U), ( 222Rn) and ( 234U/ 238U)activity values occurring in early May when delayed-flow basal meltwater composed a significant portion of the bulk melt. Furthemore, from the chemical evolution of the meltwater, we posit that the relative subglacial water residence times decrease over the course of the melt season. This decrease in qualitative residence time during active melt is consistent with prior field studies and model-predicted channel switching from a delayed, distributed network to a fast, channelized network flow. As such, our study provides support for linking U-series isotopes to storage lengths of meltwater beneath glacial systems as subglacial hydrologic networks evolve with increased melting and channel network efficiency.« less

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.

Thermal Evolution of Charon and the Major Satellites of Uranus: Constraints on Early Differentiation

NASA Astrophysics Data System (ADS)

Spohn, T.; Multhaup, K.

2007-12-01

A thermal history model developed for medium-sized icy satellites containing silicate rock at low volume fractions is applied to Charon and the satellites of Uranus Ariel, Umbriel, Titania, Oberon and Miranda. The model assumes homogeneously accreted satellites. To calculate the initial temperature profile we assume that infalling planetesimals deposit a fraction h of their kinetic energy as heat at the instantaneous surface of the growing satellites. The parameter h is varied between models. The model continuously checks for convectively unstable shells in the interior by updating the temperature profile and calculating the Rayleigh number and the temperature-dependent viscosity. The viscosity parameter values are taken as those of ice I although the satellites under consideration likely contain admixtures of lighter constituents. Their effects and those of rock on the viscosity are discussed. Convective heat transport is calculated assuming the stagnant lid model for strongly temperature dependent viscosity. In convectively stable regions heat transfer is by conduction with a temperature dependent thermal conductivity. Thermal evolution calculations considering radiogenic heating by the long-lived radiogenic isotopes of U, Th, and K suggest that Ariel, Umbriel, Titania, Oberon and Charon may have started to differentiate after a few hundred million years of evolution. With short-lived isotopes -- if present in sizeable concentrations -- this time will move earlier. Results for Miranda -- the smallest satellite of Uranus -- indicate that it never convected or differentiated if heated by the said long-lived isotopes only. Miranda's interior temperature was found to be not even close to the melting temperatures of reasonable mixtures of water and ammonia. This finding is in contrast to its heavily modified surface and supports theories that propose alternative heating mechanisms such as the decay of short-lived isotopes or early tidal heating.

Pulsed oxidation and biological evolution in the Ediacaran Doushantuo Formation

PubMed Central

McFadden, Kathleen A.; Huang, Jing; Chu, Xuelei; Jiang, Ganqing; Kaufman, Alan J.; Zhou, Chuanming; Yuan, Xunlai; Xiao, Shuhai

2008-01-01

Recent geochemical data from Oman, Newfoundland, and the western United States suggest that long-term oxidation of Ediacaran oceans resulted in progressive depletion of a large dissolved organic carbon (DOC) reservoir and potentially triggered the radiation of acanthomorphic acritarchs, algae, macroscopic Ediacara organisms, and, subsequently, motile bilaterian animals. However, the hypothesized coupling between ocean oxidation and evolution is contingent on the reliability of continuous geochemical and paleontological data in individual sections and of intercontinental correlations. Here we report high-resolution geochemical data from the fossil-rich Doushantuo Formation (635–551 Ma) in South China that confirm trends from other broadly equivalent sections and highlight key features that have not been observed in most sections or have received little attention. First, samples from the lower Doushantuo Formation are characterized by remarkably stable δ13Corg (carbon isotope composition of organic carbon) values but variable δ34SCAS (sulfur isotope composition of carbonate-associated sulfate) values, which are consistent with a large isotopically buffered DOC reservoir and relatively low sulfate concentrations. Second, there are three profound negative δ13Ccarb (carbon isotope composition of carbonate) excursions in the Ediacaran Period. The negative δ13Ccarb excursions in the middle and upper Doushantuo Formation record pulsed oxidation of the deep oceanic DOC reservoir. The oxidation events appear to be coupled with eukaryote diversity in the Doushantuo basin. Comparison with other early Ediacaran basins suggests spatial heterogeneity of eukaryote distribution and redox conditions. We hypothesize that the distribution of early Ediacaran eukaryotes likely tracked redox conditions and that only after ≈551 Ma (when Ediacaran oceans were pervasively oxidized) did evolution of oxygen-requiring taxa reach global distribution. PMID:18299566

Geochemistry of mineral waters and associated gases of the Sakhalin Island (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chelnokov, George A.; Bragin, Ivan V.; Kharitonova, Natalia A.

2018-04-01

Isotopic and chemical data on the mineral water, mud volcanoes fluid and associated gases from the biggest Russian island Sakhalin, together with previous stable isotope data (d18O, dD, 13C), allow elucidation of their origin and general evolution. The water fluid circulation is mainly related to marine environment inducing three distinct types: Na-HCO3-Cl alkali carbonate groundwaters, Na-Cl-HCO3 highly evolved saline and Na-Cl mature groundwaters, indicating different evolution. Chemical evolution of groundwater on Sakhalin Island demonstrated cation exchange and salinization as dominant evolutionary pathways. Isotopic composition of groundwaters varies from meteoric to metamorphic waters. These metamorphic waters consist of water hydration from the clay and seawater are traced in fluids of Yuzhno-Sakhalin mud volcano despite modification by mixing with meteoric waters and water-rock interaction processes. Fault systems that define the areas of highly mineralized water circulation appear to play a major role in the CO2 migration to the surface and CH4 generation. The δ13C(CO2) values have pointed that gas phase in high-pCO2 waters mostly consists of mantle-derived CO2. The carbon isotope signature of methane δ13C(CH4) and δD(CH4) indicates its distinct origin which is specified by tectonics. Methane manifestation in the south of the Sakhalin Island is mainly related to thermogenic reservoirs as they are more often dislocate by tectonics, and crossed by active and permeable faults. The sources of biogenous methane in the north of Sakhalin Island is related to younger and shallower reservoirs, and less affected by tectonic processes. The determinations of 222Rn have allowed observing that maximal radon flux is associated with high pCO2 waters.

Evolution of Early Paleoproterozoic Ocean Chemistry as Recorded by Black Shales

NASA Astrophysics Data System (ADS)

Scott, C.; Bekker, A.; Lyons, T. W.; Planavsky, N. J.; Wing, B. A.

2010-12-01

In recent years, Precambrian biogeochemists have focused largely on the abundance, speciation and isotopic composition of major and trace elements preserved in organic carbon-rich black shales in order to track the co-evolution of ocean chemistry and life on Earth. Despite the fact that the period from 2.5 to 2.0 Ga hosted major events in Earth’s history, such as the Great Oxidation Event (GOE), an era of global glaciations, a massive and long-lived carbon isotope excursion and the end to banded iron formation (BIF) deposition, each with the potential to directly alter global biogeochemical cycles, it is perhaps best known for its unknowns. In order to help close this gap in our understanding of the evolution of Precambrian ocean chemistry we present a detailed biogeochemical study of Paleoproterozoic black shales deposited between 2.5 and 2.0 Ga. Our study integrates Fe speciation, trace metal chemistry and C, S and N isotope analyses to provide a thorough characterization of marine biogeochemical cycles as they responded to the GOE and set the stage for the demise of BIFs at ca. 1.8 Ga. Our data reveal an ocean that was both surprising similar to, and demonstrably different from, Archean and later Proterozoic oceans. Of particular interest, we find that ferruginous and euxinic conditions co-existed during this period and that sea water trace metal inventories fluctuated dramatically in conjunction with major carbon isotope excursions. By comparing our Paleoproterozoic contribution with recent biogeochemical studies of other Precambrian black shales we can begin to track first order changes in ocean chemistry without the major time gaps that have plagued previous attempts.

Seasonal progression of uranium series isotopes in subglacial meltwater: Implications for subglacial storage time

DOE PAGES

Arendt, Carli A.; Aciego, Sarah M.; Sims, Kenneth W. W.; ...

2017-07-31

The residence time of subglacial meltwater impacts aquifer recharge, nutrient production, and chemical signals that reflect underlying bedrock/substrate, but is inaccessible to direct observation. We report the seasonal evolution of subglacial meltwater chemistry from the 2011 melt season at the terminus of the Athabasca Glacier, Canada. We also measured major and trace analytes and U-series isotopes for twenty-nine bulk meltwater samples collected over the duration of the melt season. This dataset, which is the longest time-series record of ( 234U/ 238U) isotopes in a glacial meltwater system, provides insight into the hydrologic evolution of the subglacial system during active melting.more » Meltwater samples, measured from the outflow, were analyzed for ( 238U), ( 222Rn) and ( 234U/ 238U)activity, conductivity, alkalinity, pH and major cations. Subglacial meltwater varied in [238U] and (222Rn) from 23 to 832 ppt and 9 to 171 pCi/L, respectively. Activity ratios of ( 234U/ 238U) ranged from 1.003 to 1.040, with the highest ( 238U), ( 222Rn) and ( 234U/ 238U)activity values occurring in early May when delayed-flow basal meltwater composed a significant portion of the bulk melt. Furthemore, from the chemical evolution of the meltwater, we posit that the relative subglacial water residence times decrease over the course of the melt season. This decrease in qualitative residence time during active melt is consistent with prior field studies and model-predicted channel switching from a delayed, distributed network to a fast, channelized network flow. As such, our study provides support for linking U-series isotopes to storage lengths of meltwater beneath glacial systems as subglacial hydrologic networks evolve with increased melting and channel network efficiency.« less

The hydrothermal evolution of the Kawerau geothermal system, New Zealand

NASA Astrophysics Data System (ADS)

Milicich, S. D.; Chambefort, I.; Wilson, C. J. N.; Charlier, B. L. A.; Tepley, F. J.

2018-03-01

Hydrothermal alteration zoning and processes provide insights into the evolution of heat source(s) and fluid compositions associated with geothermal systems. Traditional petrological techniques, combined with hydrothermal alteration studies, stable isotope analyses and geochronology can resolve the nature of the fluids involved in hydrothermal processes and their changes through time. We report here new findings along with previous unpublished works on alteration patterns, fluid inclusion measurements and stable isotope data to provide insights into the thermal and chemical evolution of the Kawerau geothermal system, New Zealand. These data indicate the presence of two hydrothermal events that can be coupled with chronological data. The earlier period of hydrothermal activity was initiated at 400 ka, with the heat driving the hydrothermal system inferred to be from the magmatic system that gave rise to rhyolite lavas and sills of the Caxton Formation. Isotopic data fingerprint fluids attributed to this event as meteoric, indicating that the magma primarily served as a heat source driving fluid circulation, and was not releasing magmatic fluids in sufficient quantity to affect the rock mineralogy and thus inferred fluid compositions. The modern Kawerau system was initiated at 16 ka with hydrothermal eruptions linked to shallow intrusion of magma at the onset of activity that gave rise to the Putauaki andesite cone. Likely associated with this later event was a pulse of magmatic CO2, resulting in large-scale deposition of hydrothermal calcite enriched in 18O. Meteoric water-dominated fluids subsequently overwhelmed the magmatic fluids associated with this 18O-rich signature, and both the fluid inclusion microthermometry and stable isotope data reflect a change to the present-day fluid chemistry of low salinity, meteoric-dominated waters.

Phase-specific Geochemistry of Ni: a Tracer of Geosphere-Biosphere Co-evolution?

NASA Astrophysics Data System (ADS)

Ciscato, E. R.; Vance, D.; Bontognali, T. R. R.; Poulton, S.

2016-12-01

Metalloproteome analyses and culturing studies have suggested that trace metals, such as Cu, Fe, Mo, Ni, and Zn, were selectively utilized by different organisms and specific metabolisms throughout the evolution of the biosphere. Methanogens have a particular requirement for Ni and culturing studies have shown that they fractionate Ni isotopes upon uptake. It is not clear, however, whether a resulting Ni isotopic signal can be preserved in the geological record. We have developed a new approach that enables us to analyze phase-specific authigenic trace metal enrichments, and their respective isotopic signatures, in (predominantly organic-rich) sediments from the geological record. An acid digestion step followed by high-pressure ashing allows us to separate an `organic matter + Pyrite' phase from an `HF-extractable' phase. We have applied this approach to investigate the distribution of Ni isotopes in a variety of modern sediments, including organic-rich sediments from upwelling margins and a hypersaline lagoonal setting where methanogenesis is likely to be an active process. Preliminary results on geological record samples show a δ60Ni for the `HF-extractable' phases that agrees with the average continental crust, whereas the `organic matter + Pyrite' phases are heavier and shifted in the direction of modern seawater. By combining this data with our δ60Ni dataset from modern sediments, we investigate the dynamics of Ni cycling in environments with different O2 and H2S availabilities both in the modern and throughout the past 3.2 billion years. Our phase-specific δ60Ni record is of instrumental importance in determining whether a biologically induced fractionation imparted by methanogens is indeed observable, and if it can be used as a biosignature for tracing the predominance of methanogenic pathways throughout the co-evolution of the geosphere and biosphere.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, I

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, I, included the following reports:Oxygen in the Solar System: Origins of Isotopic and Redox Complexity; The Origin of Oxygen Isotope Variations in the Early Solar System; Solar and Solar-Wind Oxygen Isotopes and the Genesis Mission; Solar 18O/17O and the Setting for Solar Birth; Oxygen Isotopes in Early Solar System Materials: A Perspective Based on Microbeam Analyses of Chondrules from CV Carbonaceous Chondrites; Insight into Primordial Solar System Oxygen Reservoirs from Returned Cometary Samples; Tracing Meteorites to Their Sources Through Asteroid Spectroscopy; Redox Conditions Among the Terrestrial Planets; Redox Complexity in Martian Meteorites: Implications for Oxygen in the Terrestrial Planets; Implications of Sulfur Isotopes for the Evolution of Atmospheric Oxygen; Oxygen in the Outer Solar System; and On the Oxidation States of the Galilean Satellites: Implications for Internal Structures.

Oxygen isotopes in nitrite: Analysis, calibration, and equilibration

USGS Publications Warehouse

Casciotti, K.L.; Böhlke, J.K.; McIlvin, M.R.; Mroczkowski, S.J.; Hannon, J.E.

2007-01-01

Nitrite is a central intermediate in the nitrogen cycle and can persist in significant concentrations in ocean waters, sediment pore waters, and terrestrial groundwaters. To fully interpret the effect of microbial processes on nitrate (NO3-), nitrite (NO2-), and nitrous oxide (N2O) cycling in these systems, the nitrite pool must be accessible to isotopic analysis. Furthermore, because nitrite interferes with most methods of nitrate isotopic analysis, accurate isotopic analysis of nitrite is essential for correct measurement of nitrate isotopes in a sample that contains nitrite. In this study, nitrite salts with varying oxygen isotopic compositions were prepared and calibrated and then used to test the denitrifier method for nitrite oxygen isotopic analysis. The oxygen isotopic fractionation during nitrite reduction to N2O by Pseudomonas aureofaciens was lower than for nitrate conversion to N2O, while oxygen isotopic exchange between nitrite and water during the reaction was similar. These results enable the extension of the denitrifier method to oxygen isotopic analysis of nitrite (in the absence of nitrate) and correction of nitrate isotopes for the presence of nitrite in “mixed” samples. We tested storage conditions for seawater and freshwater samples that contain nitrite and provide recommendations for accurate oxygen isotopic analysis of nitrite by any method. Finally, we report preliminary results on the equilibrium isotope effect between nitrite and water, which can play an important role in determining the oxygen isotopic value of nitrite where equilibration with water is significant.

Compound- and position-specific carbon isotopic signatures of abiogenic hydrocarbons from on-land serpentinite-hosted Hakuba Happo hot spring in Japan

NASA Astrophysics Data System (ADS)

Suda, Konomi; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Ueno, Yuichiro

2017-06-01

It has been proposed that serpentinite-hosted hydrothermal/hot spring systems played a significant role in the origin and early evolution of life on early Earth because abiogenic synthesis of organic compounds may accompany serpentinization. However, production mechanisms for apparently abiogenic hydrocarbons that have been observed in the ongoing serpentinizing systems are still poorly constrained. We report a new geochemical study of hydrocarbons in an on-land serpentinite-hosted hot spring in Hakuba Happo, Japan. We have conducted both compound-specific and position-specific carbon isotopic analyses of the observed C1 to C5 hydrocarbons. A positive linear relationship between the δ13C values and the inverse carbon number is found in C1 to C5 straight-chain alkanes in the Happo sample. This isotopic trend is consistent with a simple polymerization model developed in this study. Our model assumes that, for any particular alkane, all of the subsequently added carbons have the same isotopic composition, and those are depleted in 13C with respect to the first carbon in the growing carbon chain. The fit of this model suggests that Happo alkanes can be produced via polymerization from methane with a constant kinetic isotopic fractionation of -8.9 ± 1.0‰. A similar carbon isotopic relationship among alkanes has been observed in some serpentinite-hosted seafloor hydrothermal systems, indicating that the same process is responsible for the abiological hydrocarbon in general serpentinization fields, not only in the Hakuba Happo hot spring. Moreover, our model is also applicable to other potentially abiogenic natural gases and experimentally synthesized hydrocarbon products. For the first time, the intramolecular 13C composition of propane from a natural sample derived from a serpentinite-hosted system was determined. The intramolecular 13C distribution in propane shows the important potential to identify different polymerization mechanisms that cannot be discriminated by compound-specific isotopic analysis.

Early Triassic fluctuations of the global carbon cycle: New evidence from paired carbon isotopes in the western USA basin

NASA Astrophysics Data System (ADS)

Caravaca, Gwénaël; Thomazo, Christophe; Vennin, Emmanuelle; Olivier, Nicolas; Cocquerez, Théophile; Escarguel, Gilles; Fara, Emmanuel; Jenks, James F.; Bylund, Kevin G.; Stephen, Daniel A.; Brayard, Arnaud

2017-07-01

In the aftermath of the catastrophic end-Permian mass extinction, the Early Triassic records recurrent perturbations in the carbon isotope signal, most notably during the Smithian and through the Smithian/Spathian Boundary (SSB; 1.5 myr after the Permian/Triassic boundary), which show some of the largest excursions of the Phanerozoic. The late Smithian also corresponds to major biotic turnovers and environmental changes, such as temperature fluctuations, that deeply impacted the recovery after the end-Permian mass extinction. Here we document the paired carbon isotope signal along with an analysis of the trace and major elements at the long-known Hot Springs section (southeastern Idaho, USA). This section records Early Triassic sediments from the Griesbachian-Dienerian up to the lower Spathian. We show that the organic and carbonate δ13C variations mirror the signals identified at a global scale. Particularly, the middle Smithian-SSB event represented by a negative-positive isotopic couplet is well identified and is not of diagenetic origin. We also document a positive excursion potentially corresponding to the Dienerian/Smithian Boundary. Observed Smithian-Spathian excursions are recorded similarly in both the organic and carbonate reservoirs, but the organic matter signal systematically shows unexpectedly dampened variations compared to its carbonate counterpart. Additionally, we show that variations in the net isotopic effect (i.e., Δ13C) probably resulted from a complex set of forcing parameters including either a mixing between terrestrial and marine organic matter depending on the evolution of the depositional setting, or variations in the biological fractionation. We establish that the Δ13C signal cannot be directly related to CO2-driven temperature variations at Hot Springs. Even though the carbon isotope signal mirrors the Early Triassic variations known at the global scale, the Hot Springs signal probably also reflects local influences on the carbon isotopes that are neither diagenetic nor representative of the global exogenic carbon cycle.

Stratigraphic and structural controls on groundwater flow in an outcropping fossil fan delta: the case of Sant Llorenç del Munt range (NE Spain)

NASA Astrophysics Data System (ADS)

Anglés, Marc; Folch, Albert; Oms, Oriol; Maestro, Eudald; Mas-Pla, Josep

2017-12-01

Hydrogeological models of mountain regions present the opportunity to understand the role of geological factors on groundwater resources. The effects of sedimentary facies and fracture distribution on groundwater flow and resource exploitation are studied in the ancient fan delta of Sant Llorenç de Munt (central Catalonia, Spain) by integrating geological field observations (using sequence stratigraphy methods) and hydrogeological data (pumping tests, hydrochemistry and environmental isotopes). A comprehensive analysis of data portrays the massif as a single unit, constituted by different compartments determined by specific layers and sets of fractures. Two distinct flow systems—local and regional—are identified based on pumping test analysis as well as hydrochemical and isotopic data. Drawdown curves derived from pumping tests indicate that the behavior of the saturated layers, whose main porosity is given by the fracture network, corresponds to a confined aquifer. Pumping tests also reflect a double porosity within the system and the occurrence of impervious boundaries that support a compartmentalized model for the whole aquifer system. Hydrochemical data and associated spatial evolution show the result of water-rock interaction along the flow lines. Concentration of magnesium, derived from dolomite dissolution, is a tracer of the flow-path along distinct stratigraphic units. Water stable isotopes indicate that evaporation (near a 5% loss) occurs in a thick unsaturated zone within the massif before infiltration reaches the water table. The hydrogeological analysis of this outcropping system provides a methodology for the conceptualization of groundwater flow in similar buried systems where logging and hydrogeological information are scarce.

Presolar stardust in meteorites: recent advances and scientific frontiers

NASA Astrophysics Data System (ADS)

Nittler, Larry R.

2003-04-01

Grains of stardust that formed in stellar outflows prior to the formation of the solar system survive intact as trace constituents of primitive meteorites. The presolar origin of the grains is indicated by enormous isotopic ratio variations compared to solar system materials. Identified presolar phases include diamond, silicon carbide, graphite, silicon nitride, corundum, spinel, hibonite, titanium oxide, and, most recently, silicates. Sub-grains of refractory carbides (e.g. TiC), and Fe-Ni metal have also been observed within individual presolar graphite grains. Isotopic compositions indicate that the grains formed in red giants, asymptotic giant branch (AGB) stars, supernovae and novae; thus they provide unique insights into the evolution of and nucleosynthesis within these environments. Some of the isotopic variations also reflect the chemical evolution of the galaxy and can be used to constrain corresponding models. Presolar grain microstructures provide information about physical and chemical conditions of dust formation in stellar environments; recent studies have focused on graphite grains from supernovae as well as SiC and corundum from AGB stars. The survival of presolar grains in different classes of meteorites has important implications for early solar system evolution. Recent analytical developments, including resonance ionization mass spectrometry, high spatial resolution secondary ion mass spectrometry and site-selective ion milling, should help solve many outstanding problems but are likely to also introduce new surprises.

Efficient mixing of the solar nebula from uniform Mo isotopic composition of meteorites.

PubMed

Becker, Harry; Walker, Richard J

2003-09-11

The abundances of elements and their isotopes in our Galaxy show wide variations, reflecting different nucleosynthetic processes in stars and the effects of Galactic evolution. These variations contrast with the uniformity of stable isotope abundances for many elements in the Solar System, which implies that processes efficiently homogenized dust and gas from different stellar sources within the young solar nebula. However, isotopic heterogeneity has been recognized on the subcentimetre scale in primitive meteorites, indicating that these preserve a compositional memory of their stellar sources. Small differences in the abundance of stable molybdenum isotopes in bulk rocks of some primitive and differentiated meteorites, relative to terrestrial Mo, suggest large-scale Mo isotopic heterogeneity between some inner Solar System bodies, which implies physical conditions that did not permit efficient mixing of gas and dust. Here we report Mo isotopic data for bulk samples of primitive and differentiated meteorites that show no resolvable deviations from terrestrial Mo. This suggests efficient mixing of gas and dust in the solar nebula at least to 3 au from the Sun, possibly induced by magnetohydrodynamic instabilities. These mixing processes must have occurred before isotopic fractionation of gas-phase elements and volatility-controlled chemical fractionations were established.

Stable isotope paleoaltimetry and the evolution of landscapes and life

NASA Astrophysics Data System (ADS)

Mulch, Andreas

2016-01-01

Reconstructing topography of our planet not only advances our knowledge of the geodynamic processes that shape the Earth's surface; equally important it adds a key element towards understanding long-term continental moisture transport, atmospheric circulation and the distribution of biomes and biodiversity. Stable isotope paleoaltimetry exploits systematic decreases in the oxygen (δ18O) or hydrogen (δD) isotopic composition of precipitation along a mountain front when the interaction of topography and advected moist air masses induces orographic precipitation. These changes in δ18O or δD can be recovered from the geologic record and recent geochemical and modeling advances allow a broad range of proxy materials to be evaluated. Over the last 10 yr stable isotope paleoaltimetry has witnessed rapidly expanding research activities and has produced a broad array of fascinating tectonic and geomorphologic studies many of which have concentrated on determining the elevation history of continental plateau regions. These single-site studies have greatly expanded what used to be very sparse global paleoaltimetric data. The challenge now lies in disentangling the surface uplift component from the impact of climate change on δ18O and δD in precipitation. The robustness of stable isotope paleoaltimetry can be enhanced when high-elevation δ18O or δD data are referenced against low-elevation sites that track climate-modulated sea level δ18O or δD of precipitation through time (' δ- δ approach'). Analysis of central Andean paleosols documents that differences in δ18O of soil carbonate between the Subandean foreland and the Bolivian Altiplano are small between 11 and 7 Ma but rise rapidly to ca. 2.9‰ after 7 Ma, corroborating the magnitude of late Miocene change in δ18O on the Altiplano. Future advances in stable isotope paleoaltimetry will greatly benefit from addressing four key challenges: (1) Identifying topographically-induced changes in atmospheric circulation and associated teleconnections in the global climate system that affect δ18O or δD of precipitation; (2) Evaluating on a case-by-case basis if temporal and spatial changes in isotope lapse rates influence interpretations of paleoelevation; (3) Interfacing with phylogenetic techniques to evaluate competing hypotheses with respect to the timing of surface uplift and the diversification of lineages; (4) Characterizing feedbacks between changes in surface elevation and atmospheric circulation as these are likely to be equally important to the diversification of lineages than changes in surface elevation alone. Tackling these challenges will benefit from the accelerating pace of improved data-model comparisons and rapidly evolving geochemical techniques for reconstructing precipitation patterns. Most importantly, stable isotope paleoaltimetry has the potential to develop into a truly interdisciplinary field if innovative tectonic/paleoclimatic and evolutionary biology/phylogenetic approaches are integrated into a common research framework. It therefore, opens new avenues to study the long-term evolution of landscapes and life.

Enhanced E3 Excitations in 144,146Ba and the Evolution of Octupole Collectivity

NASA Astrophysics Data System (ADS)

Bucher, B.; Zhu, S.; ANL, LLNL, LBNL, INL, UAM, Rochester, Maryland Collaboration

2017-09-01

Recent Coulomb excitation studies on 144,146Ba using the GRETINA-CHICO2 detection system with post-accelerated CARIBU beams have confirmed the existence of enhanced E3 transitions in these isotopes which are centered in a region that has long been predicted to exhibit stable octupole-deformed shapes. Furthermore, the widely-varying E1 strength observed between these isotopes is well-accounted for by models having octupole-deformed potentials, and the variation has been linked to increased occupancies of specific single-particle orbitals in the reflection-asymmetric potential. This talk will summarize the most recent experimental and theoretical results. In addition, data on octupole-related properties in the surrounding isotopes will be discussed in an attempt to better understand the origin and evolution of octupole collectivity in this mass region. This work is supported by the U.S. Department of Energy, Office of Nuclear Physics, under Contract No. DE-AC02-06CH11357 (ANL), DE-AC02-05CH11231 (LBNL, GRETINA), DOE DE-AC52-07NA27344 (LLNL), DE-AC07-05ID14517 (INL), and MINECO (Spain).

Isotopic Abundances as Tracers of the Processes of Lunar Formation

NASA Astrophysics Data System (ADS)

Pahlevan, K.

2011-12-01

Ever since Apollo, isotopic abundances have been used as tracers to study lunar formation, in particular, to study the sources of the lunar material. In the last decade, however, a number of isotopic similarities have been observed between the lunar samples and the Earth's mantle such that these two reservoirs are now known to be indistinguishable from one another to high precision for a variety of isotopic tracers. This occurs against the backdrop of a Solar System that exhibits widespread heterogeneity with respect to these tracers, a situation that strongly argues that the source of the lunar material is the silicate Earth. To reconcile this observation with the fact that the Moon is thought to result from the collision of two isotopically distinct planetary bodies, a scenario has emerged in which the material from the Moon-forming impactor and the proto-Earth are homogenized in the aftermath of the giant impact. This takes place via turbulent mixing in the time after the giant impact but before lunar accretion while the Earth-Moon system exists in the form of a continuous, high-temperature fluid. Importantly, this high-temperature phase of the evolution occurs in the presence of at least two phases (liquid + vapor) making possible chemical and isotopic fractionation. While equilibrium isotopic fractionation tends to zero at high temperatures, and the post giant impact environment experiences some of the highest temperatures encountered in the Earth sciences, there are several factors that nevertheless make equilibrium isotope effects important probes of this early evolution. (1) Because the vaporization of silicates involves decomposition reactions, the bonding environment for elements in the liquid is often very different from that in the vapor. This difference makes the magnitude of isotopic fractionation intrinsically large, even at the relevant temperatures. (2) Since the isotopic composition of a silicate liquid and co-existing vapor are distinctly different, if the Moon preferentially forms from the liquid or vapor relative to the Earth, mass-dependent isotopic differences at the planetary scale may arise. The large density contrast between liquid and vapor makes phase separation possible. (3) The precision with which planetary isotopic compositions can be determined has increased such that measurements are sensitive to even small degrees of high-temperature phase separation. Using thermodynamic models of silicate liquids to determine the partial vaporization behavior of the major elements, we will present calculations of isotopic fractionation due to liquid-vapor separation for the elements iron, magnesium, silicon, and oxygen. Improvements in analytical precision have largely settled the question of the source of the lunar material - the Earth's mantle - and isotopic measurements are now beginning to yield insight into the high-temperatures processes operating during lunar formation.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Quadrupole collectivity beyond N = 50 in neutron- rich Se and Kr isotopes

NASA Astrophysics Data System (ADS)

Elman, Brandon; Gade, A.; Barofsky, D.; Bender, P. C.; Bowry, M.; Hjorth-Jensen, M.; Kemper, K. W.; Lipschutz, S.; Lunderberg, E.; Sachmpazidi, N.; Terpstra, N.; Walters, W. B.; Weisshaar, D.; Westerberg, A.; Williams, S. J.; Wimmer, K.

2017-09-01

We will present results on measuring the B (E 2 ;01+ ->2n+) strength for the neutron-rich 88,90Kr and 86Se isotopes from intermediate-energy Coulomb excitation. The electric quadrupole transition strengths to the first 2+ state complete, with considerably improved uncertainties, the evolution of quadrupole collectivity in the Kr and Se isotopes approaching N = 60 , for which 90Kr and 86Se had previously been the most uncertain. We also report significant excitation strength to several higher lying 2+ states in the krypton isotopes. The results confirm shell model calculations in the π (fpg) - ν (sdg) shell with only a minimally tuned shell model setup that is based on a nucleon-nucleon interaction derived from effective field theory with effective charges adjusted to 86Kr.

Mantle heterogeneity and crustal recycling in Archean granite-greenstone belts - Evidence from Nd isotopes and trace elements in the Rainy Lake area, Superior Province, Ontario, Canada

NASA Technical Reports Server (NTRS)

Shirey, Steven B.; Hanson, Gilbert N.

1986-01-01

Crustal evolution in the Rainy Lake area, Ontario is studied in terms of geochemical characteristics. The Nd isotope data are examined for heterogeneity of the Archean mantle, and the Sm/Nd depletion of the mantle is analyzed. The Nd isotope systematics of individual rock suites is investigated in order to understand the difference between crust and mantle sources; the precursors and petrogenetic processes are discussed. The correlation between SiO2 content and Nd values is considered. Rapid recycling of crustal components, which were previously derived from depleted mantle sources, is suggested based on the similarity of the initial Nd isotopic composition for both mantle-derived and crustally-derived rocks.

Multiple S and O isotope constraints on O2 at 2.25 Ga

NASA Astrophysics Data System (ADS)

Killingsworth, B.; Sansjofre, P.; Philippot, P.; Thomazo, C.; Cartigny, P.; Lalonde, S.

2017-12-01

The composition of Earth's atmosphere around the time of the Great Oxidation Event (GOE) at the Archean-Proterozoic boundary is of great interest for reconstructing the redox evolution of the Earth. Sulfate has been shown to be a valuable recorder of isotopic signals of atmospheric O2 but its records are sparse around the time of the GOE. To constrain O2 around the GOE, we have measured quadruple sulfur and triple oxygen isotopes of sulfate from barite in sedimentary drill core from the Turee Creek Group, Australia from 2.25 Ga. A combined sulfur and oxygen approach for estimating the triple oxygen isotope composition of O2 at 2.25 Ga will be presented and its implications for the Paleoproterozoic atmosphere will be discussed.

First detection of 3He+ in the planetary nebula IC 418

NASA Astrophysics Data System (ADS)

Guzman-Ramirez, L.; Rizzo, J. R.; Zijlstra, A. A.; García-Miró, C.; Morisset, C.; Gray, M. D.

2016-07-01

The 3He isotope is important to many fields of astrophysics, including stellar evolution, chemical evolution, and cosmology. The isotope is produced in low-mass stars which evolve through the planetary nebula (PN) phase. 3He abundances in PNe can help test models of the chemical evolution of the Galaxy. We present the detection of the 3He+ emission line using the single dish Deep Space Station 63, towards the PN IC 418. We derived a 3He/H abundance in the range 1.74 ± 0.8 × 10-3 to 5.8 ± 1.7 × 10-3, depending on whether part of the line arises in an outer ionized halo. The lower value for 3He/H ratio approaches values predicted by stellar models which include thermohaline mixing, but requires that large amounts of 3He are produced inside low-mass stars which enrich the interstellar medium (ISM). However, this overpredicts the 3He abundance in H II regions, the ISM, and protosolar grains, which is known to be of the order of 10-5. This discrepancy questions our understanding of the evolution of the 3He, from circumstellar environments to the ISM.

Additional Sr Isotopic Heterogeneity in Zagami Olivine-Rich Lithology

NASA Technical Reports Server (NTRS)

Misawa, K.; Niihara, T.; Shih, C.-Y; Reese, Y. D.; Nyquist, L. E.; Yoneda, S.; Yamashita, H.

2012-01-01

Prior isotopic analyses of Zagami have established differing initial Sr-87/Sr-86 (ISr) ratios of among Zagami lithologies, fine-grained (FG), coarse-grained (CG), and dark mottled lithologies (DML)]. The Zagami sample (KPM-NLH000057) newly allocated from the Kanagawa Prefectural Museum of Natural History contained DML and the Ol-rich lithology which included more ferroan olivines (Ol-rich: Fa(sub 97- 99) vs late-stage melt pockets: Fa(sub 90-97)]). We have combined mineralogy-petrology and Rb-Sr isotopic studies on the Kanagawa Zagami sample, which will provide additional clues to the genesis of enriched shergottites and to the evolution of Martian crust and mantle

Meteoritic Stardust and the Presolar History of the Solar Neighborhood

NASA Astrophysics Data System (ADS)

Nittler, Larry R.

Presolar stardust is present at low levels in meteorites and cometary dust and identified as ancient stellar matter by unusual isotopic compositions reflecting nuclear processes in stellar interiors and galactic chemical evolution. Most grains originated in winds from asymptotic giant branch (AGB) stars and supernova and their isotopic compositions provide important constraints on models of evolution and nucleosynthesis in these environments. The presolar grains from AGB stars appear to have formed in a lower-mass population of stars than predicted by GCE models. A merger of the Milky Way with a dwarf galaxy some 1 Gyr before the birth of the Solar System may explain this and other grain observations and the data thus can provide a unique window into the presolar history of the solar neighborhood.

Petrology and Physics of Magma Ocean Crystallization

NASA Technical Reports Server (NTRS)

Elkins-Tanton, Linda T.; Parmentier, E. M.; Hess, P. C.

2003-01-01

Early Mars is thought to have been melted significantly by the conversion of kinetic energy to heat during accretion of planetesimals. The processes of solidification of a magma ocean determine initial planetary compositional differentiation and the stability of the resulting mantle density profile. The stability and compositional heterogeneity of the mantle have significance for magmatic source regions, convective instability, and magnetic field generation. Significant progress on the dynamical problem of magma ocean crystallization has been made by a number of workers. The work done under the 2003 MFRP grant further explored the implications of early physical processes on compositional heterogeneity in Mars. Our goals were to connect early physical processes in Mars evolution with the present planet's most ancient observable characteristics, including the early, strong magnetic field, the crustal dichotomy, and the compositional characteristics of the SNC meteorite's source regions as well as their formation as isotopically distinct compositions early in Mars's evolution. We had already established a possible relationship between the major element compositions of SNC meteorite sources and processes of Martian magma ocean crystallization and overturn, and under this grant extended the analysis to the crucial trace element and isotopic SNC signatures. This study then demonstrated the ability to create and end the magnetic field through magma ocean cumulate overturn and subsequent cooling, as well as the feasibility of creating a compositionally- and volumetrically-consistent crustal dichotomy through mode-1 overturn and simultaneous adiabatic melting.

Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

NASA Astrophysics Data System (ADS)

Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

2014-12-01

Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring in the ocean (e.g., biological activity) instead of abiotic redox reactions on the continent. References: 1.Martin (1990) Paleoceanography. 2.Fantle and DePaolo (2004) EPSL. 3. Gaschnig et al. (2014) EPSL. 4. Dauphas et al. (2009) EPSL.

Tracing the secular evolution of the UCC using the iron isotope composition of ancient glacial diamictites

NASA Astrophysics Data System (ADS)

Liu, X. M.; Gaschnig, R. M.; Rudnick, R. L.; Hazen, R. M.; Shahar, A.

2015-12-01

Iron is the fourth most abundant element in the continental crust and influences global climate and biogeochemical cycles in the ocean1. Continental inputs, including river waters, sediments and atmospheric dust are dominant sources (>95%) of iron into the ocean2. Therefore, understanding how continental inputs may have changed through time is important in understanding the secular evolution of the marine Fe cycle. We analysed the Fe isotopic composition of twenty-four glacial diamictite composites, upper continental crust (UCC) proxies, with ages ranging from the Mesoarchean to the Paleozoic eras to characterize the secular evolution of the UCC. The diamictites all have elevated chemical index of alteration (CIA) and other characteristics of weathered regolith (e.g., strong depletion in soluble elements such as Sr), which they inherited from their upper crustal source region3. δ56Fe in the diamictite composites range from -0.59 to +0.23‰, however, most diamictites cluster with an average δ56Fe of 0.11± 0.20 (2s), overlapping juvenile continental material such as island arc basalts (IABs), which show a narrow range in δ56Fe from -0.04 to +0.14 ‰4. There is no obvious correlation between δ56Fe of the glacial diamictites and the CIA, except that the diamictite with the lowest δ56Fe at -0.59 ‰ also has the highest CIA = 89 (the Paleoproterozoic Makganyene Fm.). The data suggest that the Fe isotope compositions in the upper continental crust did not vary throughout Earth history. Interestingly, chemical weathering and sedimentary transport likely play only a minor role in producing Fe isotope variations in the upper continental crust. Anoxic weathering pre-GOE (Great Oxidation Event) does not seem to generate different Fe isotopic signatures from the post-GOE oxidative weathering environment in the upper continental crust. Therefore, large Fe isotopic fractionations observed in various marine sedimentary records are likely due to other processes occurring in the ocean (e.g., biological activity) instead of abiotic redox reactions on the continent. References: 1.Martin (1990) Paleoceanography. 2.Fantle and DePaolo (2004) EPSL. 3. Gaschnig et al. (2014) EPSL. 4. Dauphas et al. (2009) EPSL.

Surface studies of water isotopes in Antarctica for quantitative interpretation of deep ice core data

NASA Astrophysics Data System (ADS)

Landais, Amaelle; Casado, Mathieu; Prié, Frédéric; Magand, Olivier; Arnaud, Laurent; Ekaykin, Alexey; Petit, Jean-Robert; Picard, Ghislain; Fily, Michel; Minster, Bénédicte; Touzeau, Alexandra; Goursaud, Sentia; Masson-Delmotte, Valérie; Jouzel, Jean; Orsi, Anaïs

2017-07-01

Polar ice cores are unique climate archives. Indeed, most of them have a continuous stratigraphy and present high temporal resolution of many climate variables in a single archive. While water isotopic records (δD or δ18O) in ice cores are often taken as references for past atmospheric temperature variations, their relationship to temperature is associated with a large uncertainty. Several reasons are invoked to explain the limitation of such an approach; in particular, post-deposition effects are important in East Antarctica because of the low accumulation rates. The strong influence of post-deposition processes highlights the need for surface polar research programs in addition to deep drilling programs. We present here new results on water isotopes from several recent surface programs, mostly over East Antarctica. Together with previously published data, the new data presented in this study have several implications for the climatic reconstructions based on ice core isotopic data: (1) The spatial relationship between surface mean temperature and mean snow isotopic composition over the first meters in depth can be explained quite straightforwardly using simple isotopic models tuned to d-excess vs. δ18O evolution in transects on the East Antarctic sector. The observed spatial slopes are significantly higher (∼ 0.7-0.8‰·°C-1 for δ18O vs. temperature) than seasonal slopes inferred from precipitation data at Vostok and Dome C (0.35 to 0.46‰·°C-1). We explain these differences by changes in condensation versus surface temperature between summer and winter in the central East Antarctic plateau, where the inversion layer vanishes in summer. (2) Post-deposition effects linked to exchanges between the snow surface and the atmospheric water vapor lead to an evolution of δ18O in the surface snow, even in the absence of any precipitation event. This evolution preserves the positive correlation between the δ18O of snow and surface temperature, but is associated with a much slower δ18O-vs-temperature slope than the slope observed in the seasonal precipitation. (3) Post-deposition effects clearly limit the archiving of high-resolution (seasonal) climatic variability in the polar snow, but we suggest that sites with an accumulation rate of the order of 40 kg.m-2.yr-1 may record a seasonal cycle at shallow depths.

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.

Effects of Low-Molecular-Weight Organic Acids on the Dissolution of Hydroxyapatite Nanoparticles in Batch and Column Experiments: A Perspective from Phosphate Oxygen Isotope Fractionation

NASA Astrophysics Data System (ADS)

Wang, D.; Jaisi, D. P.; Jin, Y.

2015-12-01

Hydroxyapatite nanoparticles (HANPs) are increasingly being advocated as an efficient and environment-friendly "green" phosphorus nanofertilizer attributed to their nanoscale dimension, large reactive surface area, and low leaching potential. However, knowledge of how naturally occurring low-molecular-weight organic acids (LMWOAs) that are secreted by plant roots mediate the dissolution of HANPs (releasing PO43- ion for plant growth) is nonexistent. Here three most commonly encountered LMWOAs (acetic acid, oxalic acid, and citric acid) at environmentally relevant concentration (1 mM) were evaluated for their effects on HANPs' dissolution in static batch and dynamic column systems. Particularly, phosphate oxygen isotope fractionation of HANPs during dissolution was examined to disentangle mechanisms controlling the evolution of O-isotopic composition of dissolved PO43- ion. Our results reveal that in batch experiments the dissolution of HANPs was fast but the overall dissolution efficiency of HANPs was limited (≤30%). In contrast, ~100% HANPs were dissolved in columns where LMWOAs were continuously injected. The limited dissolution of HANPs in static batch systems was due primarily to pH buffer effect (pH increased sharply when LMWOA was added in HANPs suspension), whereas in dynamic column systems the HANPs were continuously dissolved by low pH LMWOAs and leached away. Regardless of LMWOA type and experimental system, the isotopically light phosphate (P16O4) was preferentially released during dissolution and the O-isotopic composition of dissolved PO43- ion increased gradually with increasing dissolution due to equilibrium isotope effect between dissolved PO43- ion and HANPs. However, the overall magnitude of O-isotopic fractionation of dissolved PO43- ion was less in batch than in column systems, due to less mass transfer between dissolved PO43- ions and HANPs in batch relative to column experiments. Our findings provide new insights into bioavailability, transformation, and evolution of O-isotopic signatures of phosphate-based nanoparticles in agricultural soils particularly in the rhizosphere where such LMWOAs are ubiquitous.

Detecting Isotopic Signatures and Measuring Isotopic Ratios on Solid Icy Surfaces:Implications for Origin and Evolution

NASA Astrophysics Data System (ADS)

Clark, R. N.; Brown, R. H.; Swayze, G. A.; Cruikshank, D. P.

2017-12-01

Infrared spectroscopy has long been used to detect isotopes in planetaryatmospheres and in the galaxy. Given sufficient spectral resolution,or large enough changes in mass, isotopes are also detectable in solids.Gas absorption lines can be quite narrow, but in some solids, e.g. H2Oice, absorptions are very broad with little to no fine structure. H2O icehas broad absorptions due to its orientationally disordered structure butmany ices, minerals, and other compounds display sufficiently narrowabsorptions to enable detection of isotopes with small mass changes atmoderate spectral resolution.D2O ice and HDO ice also show orientationally-disordered spectra withvery broad absorption bands. But as deuterium decreases to low levelsdeuterium apparently goes into ordered sites in the H2O ice structure,producing narrow absorptions and shifting to longer wavelengths.Trace D2O condensed on basalt at 80 Kelvin shows an O-D stretch at 4.0microns, but at D/H 0.1 or less in H2O ice, the D-O stretch occursnear 4.13 microns with a width in reflectance decreasing to 0.027 micronas D/H decreases. The narrow D-O stretch absorption shows an absorptioncoefficient of 80,000 cm^-1 enabling detection below Vienna Standard MeanOcean Water (VSMOW) with achievable S/N in the lab and from spacecraft.Isotopes of carbon have been detected in CO2 on Saturn's satelliteswith 16 nm FWHM using the VIMS instrument on the Cassini spacecraft.Deuterium has been detected at close to terrestrial levels in Saturn'srings and on Rhea, and an apparent enhancement on Phoebe using VIMSdata. The ocean world Enceladus is currently being analyzed. We alsodetect an enhancement in 13C on Phoebe, but not on Iapetus or Rhea,consistent with the suggestion from previous studies that suggest Phoebe'sorigin might be external to the Saturn system. The MISE instrumenton the Europa Clipper mission has the capability to detect deuteriumand carbon isotopes in the Jupiter system. The higher temperaturesin the Jupiter system may result in more fractionation, depending upona given isotope and the physical processes involved, potentially withimplications for origin and evolution.

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.

Temporal evolution of granitic magmas in the Luanchuan metallogenic belt, east Qinling Orogen, central China: Implications for Mo metallogenesis

NASA Astrophysics Data System (ADS)

Li, Dong; Han, Jiangwei; Zhang, Shouting; Yan, Changhai; Cao, Huawen; Song, Yaowu

2015-11-01

The Luanchuan metallogenic belt, located within the eastern part of the Qinling Orogen, central China, hosts a number of world-class Mo deposits that are closely related to small late Mesozoic granitic plutons. Zircon U-Pb dating of distinct plutons in the Luanchuan metallogenic belt has yielded ages of 153 ± 1, 154 ± 2, 152 ± 2, and 148 ± 1 Ma. Molybdenite Re-Os isotopic compositions of Yuku ore district in the southern part of Luanchuan metallogenic belt has yielded an isochron age of 146 ± 1 Ma, which is consistent with the large-scale mineralization ages in the northern part of the Luanchuan metallogenic belt. A combination of previous studies and new geochronological and isotopic data show a concordant temporal and genetic link between granitic magmatism and Mo mineralization in the Luanchuan metallogenic belt, suggesting that this mineralization episode formed the most extensive Mo mineralization belt in the east Qinling Orogen. Zircon grains from Mo-related granitic plutons show similar trace element distributions. High-precision Multi Collector-Inductively Coupled Plasma-Mass Spectrometry (MC-ICP-MS) Pb isotope analysis of K-feldspar megacrysts from mineralization-related granites suggest that they were derived from the lower crust. Similarly, the Pb isotopic compositions of pyrite coprecipitated with molybdenite also suggest that the metals were derived form the lower crust, with probably minor mantle contribution. A continuum mineralization model that describes the sourcing of Mo from an evolving granitic magma over successive differentiation events, possibly in separate but connected magma chambers, could explain the remarkable Mo enrichment in the Luanchuan metallogenic belt. The volatile- and Mo-bearing granitic magmas ascended as diapirs from the deep crust, and were emplaced as dikes in the upper crust. Lithological differences between these Mo-bearing granites may relate to different stages in the evolution of individual magmas. Finally, ore-forming fluids were exsolved from the granitic melts in shallow-crustal magma chambers, resulting in the formation of the Mo deposits of the Luanchuan metallogenic belt. This model may account for the widespread late Mesozoic Mo deposits of eastern China.

Proton scattering from the unstable nuclei 30S and 34Ar: structural evolution along the sulfur and argon isotopic chains*

NASA Astrophysics Data System (ADS)

Khan, E.; Suomijärvi, T.; Blumenfeld, Y.; Van Giai, Nguyen; Alamanos, N.; Auger, F.; Bauge, E.; Beaumel, D.; Delaroche, J. P.; Delbourgo-Salvador, P.; Drouart, A.; Fortier, S.; Frascaria, N.; Gillibert, A.; Girod, M.; Jouanne, C.; Kemper, K. W.; Lagoyannis, A.; Lapoux, V.; Lépine-Szily, A.; Lhenry, I.; Libert, J.; Maréchal, F.; Maison, J. M.; Musumarra, A.; Ottini-Hustache, S.; Piattelli, P.; Pita, S.; Pollacco, E. C.; Roussel-Chomaz, P.; Santonocito, D.; Sauvestre, J. E.; Scarpaci, J. A.; Zerguerras, T.

2001-11-01

Proton elastic and inelastic scattering angular distributions to the 2 1+ and 3 1- collective states of the proton-rich nuclei 30S and 34Ar were measured at 53 MeV/ A and 47 MeV/ A, respectively, using secondary beams from the GANIL facility and the MUST silicon strip detector array. Data for the stable 32S nucleus were also obtained at 53 MeV/ A for comparison. A phenomenological analysis was used to deduce the deformation parameters βp,p' for the low-lying collective excitations. A microscopic analysis was performed by generating matter and transition densities from self-consistent QRPA calculations. Configuration mixing calculations based on a collective Bohr Hamiltonian were also performed. DWBA and coupled-channel calculations using microscopic optical potentials built from these densities and the JLM interaction are compared to the data. There is no indication for the presence of proton skins in these nuclei. The microscopic calculations are extended to the even-even sulfur and argon isotopes from A=30 to A=40, and A=34 to A=44, respectively, and compared to available experimental results. On the basis of this analysis predictions are made for the 42,44S and 46Ar nuclei concerning ground state and transition densities.

Elemental and stable isotope analysis in the assessment of fluvio-marine interactions over the last 5000 years

NASA Astrophysics Data System (ADS)

Martins, J.; Portela, P.; Soares, A.; Ramos-Pereira, A.; Trindade, J.

2012-04-01

The estuarine environment are one of the most sensitive areas in the climatic change framework and sea level rise scenarios as they are an interface between fluvial and marine influence and they support not only important wetland biodiversity but also strategic economic activities. These environments record marine sea level changes as well as hydrogeomorphological and land cover changes of the drainage basins, natural and man induced. Over the last 5000 years different trends of sea level, climatic fluctuations, Bond events or humid episodes have been recorded in the Iberian Peninsula, as well as the increase of the human intervention in the landscape, particularly sensitive since the Middle Bronze Age, all imprinted in the filling up of the alluvial plain estuaries. To assess the evolution of interface environments along the Portuguese coast, three mesotidal estuaries with alluvial plain and medium drainage basins in different geological and geomorphological frameworks were selected and the sedimentary organic matter characterized by geochemical methods, including elemental (C, N) and stable isotope analysis (δ13C, δ15N). Organic matter from marine environments is usually enriched in 13C, presenting δ13C values ranging from -20 to -24‰, while organic matter from terrestrial origin may present δ13C values between -25 and -28‰ being, therefore, depleted in 13C (Lamb et al. 2006). For C/N ratio, according to its value (normally increasing with terrestrial influence) and its relation with δ13C, the nature of organic matter present in the sediments can be inferred. One of the estuaries was the Alcabrichel river estuary. A sedimentary core (AlcMac3) was collected and the preliminary results present a down-core variation of δ13C, ranging from -24.0 ‰ to -27.0 ‰. Regarding the C/N ratios the results range from 8.7 to 22.7. According to this preliminary data concerning the evolution of these proxies along the sedimentary record it is possible to identify variations in the predominant sedimentary sources, the evolution of fluvial and marine influences, the responses to climatic events and the impact of land use changes in the different estuarine environmental conditions over the last 5000 years. Keywords: Stable isotopes, C/N ratios, Environmental changes, Fluvio-marine interactions. Acknowledgements This research was funded by the research project, PTDC/CTE-GIX/104035/2008 - FMI 5000: Environmental changes: Fluvio-marine interactions over the last 5000 yrs, from Portuguese Science and Technology Foundation (FCT-MCTES). J. Martins acknowledges the PhD grant SFRH/BD/45528/2008 from the same institution.

The evolution of 17O-excess in surface water of the arid environment during recharge and evaporation.

PubMed

Surma, J; Assonov, S; Herwartz, D; Voigt, C; Staubwasser, M

2018-03-21

This study demonstrates the potential of triple O-isotopes to quantify evaporation with recharge on a salt lake from the Atacama Desert, Chile. An evaporative gradient was found in shallow ponds along a subsurface flow-path from a groundwater source. Total dissolved solids (TDS) increased by 177 g/l along with an increase in δ 18 O by 16.2‰ and in δD by 65‰. 17 O-excess decreased by 79 per meg, d-excess by 55‰. Relative humidity (h), evaporation over inflow (E/I), the isotopic composition of vapor ( * R V ) and of inflowing water ( * R WI ) determine the isotope distribution in 17 O-excess over δ 18 O along a well-defined evaporation curve as the classic Craig-Gordon model predicts. A complementary on-site simple (pan) evaporation experiment over a change in TDS, δ 18 O, and 17 O-excess by 392 g/l, 25.0‰, and -130 per meg, respectively, was used to determine the effects of sluggish brine evaporation and of wind turbulence. These effects translate to uncertainty in E/I rather than h. The local composition of * R V relative to * R WI pre-determines the general ability to resolve changes in h. The triple O-isotope system is useful for quantitative hydrological balancing of lakes and for paleo-humidity reconstruction, particularly if complemented by D/H analysis.

Seventh Annual V. M. Goldschmidt Conference

NASA Technical Reports Server (NTRS)

1997-01-01

Topics considered include: Subduction of the Aseismic Cocos Ridge Displaced Magma Sources Beneath the Cordillera de Talamanca, Costa Rica; Topography of Transition Zone Discontinuities: A Measure of 'Olivine' Content and Evidence for Deep Cratonic Roots; Uranium Enrichment in Lithospheric Mantle: Case Studies from French Massif Central; Rare-Earth-Element Anomalies in the Decollement Zone of the nankai Accretionary Prism, Japan: Evidence of Fluid Flow?; Rare Earth Elements in Japanese Mudrocks: The Influence of Provenance; The Evolution of Seawater Strontium Isotopes in the Last Hundred Million Years: Reinterpretation and Consequences for Erosion and Climate Models; From Pat to Tats: The Lead Isotope Legacy in the Studies of the Continental Crust-Upper Mantle System; Geochronology of the Jack Hills Detrital Zircons by Precise Uranium-Lead Isotope-Dilution Analysis of Crystal Fragments; Iridium in the Oceans; The Helium-Heat-Lead Paradox; Control of Distribution Patterns of Heavy Metals in Ganga Plain Around Kanpur Region, India, by Fluvial Geomorphic Domains; Geochemical and Isotopic Features of Ferrar Magmatic Provience (Victoria Land, Antarctica); Rare Earth Elements in Marine Fine-Grained Sediments from the Northwestern Portuguese Shelf (Atlantic); Aspects of Arc Fluxes; General Kinetic Model for Dolomite Precipitation Rate with Application to the Secular History of Seawater Composition; High-Precision Uranium-series Chronology from Speleothems; Trace-Element Modeling of Aqueous Fluid-Peridotite Interaction in the Mantle Wedge of Subduction Zones; Rainfall Variations in Southeastern Australia over the Last 500,000 Years from Speleothem Deposition; The Role of Water in High-Pressure Fluids; The Kinetic Conditions of Metamorphic Minearogenesis: Evidence from Minerals and Assemblages.

Coordinated Chemical and Isotopic Imaging of Bells (CM2) Meteorite Matrix

NASA Technical Reports Server (NTRS)

Clemett, S. J.; Messenger, S.; Naklamura-Messenger, K.; Thomas-Keprta, K. L.

2014-01-01

Meteoritic organic matter is a complex conglomeration of species formed in distinct environments and processes in circumstellar space, the interstellar medium, the Solar Nebula and asteroids. Consequently meteorites constitute a unique record of primordial organic chemical evolution. While bulk chemical analysis has provided a detailed description of the range and diversity of organic species present in carbonaceous chondrites, there is little information as to how these species are spatially distributed and their relationship to the host mineral matrix. The distribution of organic phases is nevertheless critical to understanding parent body processes. The CM and CI chondrites all display evidence of low temperature (< 350K) aqueous alteration that may have led to aqueous geochromatographic separation of organics and synthesis of new organics coupled to aqueous mineral alteration. Here we present the results of the first coordinated in situ isotopic and chemical mapping study of the Bells meteorite using a newly developed two-step laser mass spectrometer (mu-L(sup 2)MS) capable of measuring a broad range of organic compounds.

Stable Isotopes Reveal Rapid Enamel Elongation (Amelogenesis) Rates for the Early Cretaceous Iguanodontian Dinosaur Lanzhousaurus magnidens.

PubMed

Suarez, Celina A; You, Hai-Lu; Suarez, Marina B; Li, Da-Qing; Trieschmann, J B

2017-11-10

Lanzhousaurus magnidens, a large non-hadrosauriform iguanodontian dinosaur from the Lower Cretaceous Hekou Group of Gansu Province, China has the largest known herbivorous dinosaur teeth. Unlike its hadrosauriform relatives possessing tooth batteries of many small teeth, Lanzhousaurus utilized a small number (14) of very large teeth (~10 cm long) to create a large, continuous surface for mastication. Here we investigate the significance of Lanzhousaurus in the evolutionary history of iguanodontian-hadrosauriform transition by using a combination of stable isotope analysis and CT imagery. We infer that Lanzhousaurus had a rapid rate of tooth enamel elongation or amelogenesis at 0.24 mm/day with dental tissues common to other Iguanodontian dinosaurs. Among ornithopods, high rates of amelogenesis have been previously observed in hadrosaurids, where they have been associated with a sophisticated masticatory apparatus. These data suggest rapid amelogenesis evolved among non-hadrosauriform iguanodontians such as Lanzhousaurus, representing a crucial step that was exapted for the evolution of the hadrosaurian feeding mechanism.

Neogene geomorphic and climatic evolution of the central San Juan Mountains, Colorado: K/Ar age and stable isotope data on supergene alunite and jarosite from the Creede mining district

USGS Publications Warehouse

Rye, Robert O.; Bethke, Philip M.; Lanphere, Marvin A.; Steven, Thomas A.

2000-01-01

K/Ar age determinations or supergene alunite and jarosite, formed during Neogene weathering of the epithermal silver and base-metal ores of the Creede mining district, have been combined with geologic evidence to estimate the timing of regional uplift of the southern Rocky Mountains and related canyon cutting. In addition, oxygen and hydrogen isotopic studies suggest climate changes in the central San Juan Mountains during the past 5 m.y. Alunite [ideally (K,Na)Al3(SO4)2(OH)6] and jarosite [ideally KFe3(SO4)2(OH)6] can be dated by K/Ar or 40Ar/39Ar techniques and both contain OH and SO4 sites that enable four stable isotope analyses (δD, δ18OOH, and δ34S) to be made. This supergene alunite and jarosite formed by weathering of sulfide-rich ore bodies may record the evolution of the chemical and hydrologic processes affecting ancient oxidized acid ground water, as well as details of climate history and geomorphic evolution. Fine-grained (1-10 μm) supergene alunite and jarosite occur in minor fractures in the upper, oxidized parts of the 25 Ma sulfide-bearing veins of the Creede mining district, and jarosite also occurs in adjacent oxidized Ag-bearing clastic sediments. K/Ar ages for alunite range from 4.8 to 3.1 Ma, and for jarosite range from 2.6 to 0.9 Ma. The δD values for alunite and jarosite show opposite correlations with elevation, and values for jarosite correlate with age. Calculated δDH2O values of alunite fluids approach but are larger than those of present-day meteoric water. Calculated δDH2O values for jarosite fluids are more variable; the values of the youngest jarosites are lowest and are similar to those of present-day meteoric water in the district. The narrow δD-δ18OSO4 values of alunites reflects oxidation of sulfide below the water table. The greater range in these values for jarosites reflects oxidation of sulfide under vadose conditions. The ages of alunite mark the position of the paleo-water table at the end of a period of moderate erosion from ca. 25 to 5 Ma that exposed the tops of the ore bodies to oxidation. The younger jarosite formed in the vadose zone during or following subsequent canyon cutting related to regional uplift of the southern Rocky Mountains, The δD values suggest that climates in the area were similar to those of the present day prior to regional uplift but went through a warm period before returning to present conditions during or after regional uplift. The results of this study indicate that the combined stable and radiogenic isotope analysis of supergene alunite and jarosite has broad application in understanding climate and geomorphic evolution of selected areas.

A comparison of chemical compositions of reported altered oceanic crusts and global MORB data set: implication for isotopic heterogeneity of recycled materials

NASA Astrophysics Data System (ADS)

Shimoda, G.; Kogiso, T.

2017-12-01

Chemical composition of altered oceanic crust is one of important constraints to delineate chemical heterogeneity of the mantle. Accordingly, many researchers have been studied to determine bulk chemical composition of altered oceanic crust mainly based on chemical compositions of old oceanic crusts at Site 801 and Site 417/418, and young crust at Site 504 (e.g., Staudigel et al., 1996; Bach et al. 2003; Kuo et al., 2016). Their careful estimation provided reliable bulk chemical compositions of these Sites and revealed common geochemical feature of alteration. To assess effect of recycling of altered oceanic crust on chemical evolution of the mantle, it might be meaningful to discuss whether the reported chemical compositions of altered oceanic crusts can represent chemical composition of globally subducted oceanic crusts. Reported chemical compositions of fresh glass or less altered samples from Site 801, 417/418 and 504 were highly depleted compared to that of global MORB reported by Gale et al. (2013), suggesting that there might be sampling bias. Hence, it could be important to consider chemical difference between oceanic crusts of these three Sites and global MORB to discuss effect of recycling of oceanic crust on isotopic heterogeneity of the mantle. It has been suggested that one of controlling factors of chemical variation of oceanic crust is crustal spreading rate because different degree of partial melting affects chemical composition of magmas produced at a mid-ocean ridge. Crustal spreading rate could also affect intensity of alteration. Namely, oceanic crusts produced at slow-spreading ridges may prone to be altered due to existence of larger displacement faults compared to fast spreading ridges which have relatively smooth topography. Thus, it might be significant to evaluate isotopic evolution of oceanic crusts those were produced at different spreading rates. In this presentation, we will provide a possible chemical variation of altered oceanic crusts based on reported bulk chemical compositions of altered oceanic crusts and global data sets of MORB. On the basis of the chemical variation, we will discuss isotopic evolution of altered oceanic crusts to delineate isotopic variation of recycled oceanic crusts.

Evaluating the provenance of Permian-Triassic and Palaeocene-Eocene ash beds by high precision U-Pb and Lu-Hf isotopic analyses of zircons: linking local sedimentary records to global events

NASA Astrophysics Data System (ADS)

Eivind Augland, Lars; Jones, Morgan; Planke, Sverre; Svensen, Henrik; Tegner, Christian

2016-04-01

Zircons are a powerful tool in geochronology and isotope geochemistry, as their affinity for U and Hf in the crystal structure and the low initial Pb and Lu allow for precise and accurate dating by U-Pb ID-TIMS and precise and accurate determination of initial Hf isotopic composition by solution MC-ICP-MS analysis. The U-Pb analyses provide accurate chronostratigraphic controls on the sedimentary successions and absolute age frames for the biotic evolution across geological boundaries. Moreover, the analyses of Lu-Hf by solution MC-ICP-MS after Hf-purification column chemistry provide a powerful and robust fingerprinting tool to test the provenance of individual ash beds. Here we focus on ash beds from Permian-Triassic and Palaeocene successions in Svalbard and from the Palaeocene-Eocene Thermal Maximum (PETM) in Fur, Denmark. Used in combination with whole rock geochemistry from the ash layers and the available geochemical and isotopic data from potential source volcanoes, these data are used to evaluate the provenance of the Permian-Triassic and Palaeocene ashes preserved in Svalbard and PETM ashes in Denmark. If explosive eruptions from volcanic centres such as the Siberian Traps and the North Atlantic Igneous Province (NAIP) can be traced to distal basins as ash layers, they provide robust tests of hypotheses of global synchronicity of environmental changes and biotic crises. In addition, the potential correlation of ash layers with source volcanoes will aid in constraining the extent of explosive volcanism in the respective volcanic centres. The new integrated data sets will also contribute to establish new reference sections for the study of these boundary events when combined with stable isotope data and biostratigraphy.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Investigation of Gamow Teller transition properties in 56-64Ni isotopes using QRPA methods

NASA Astrophysics Data System (ADS)

Cakmak, Sadiye; Nabi, Jameel-Un; Babacan, Tahsin

2018-02-01

Weak rates in nickel isotopes play an integral role in the dynamics of supernovae. Electron capture and β-decay of nickel isotopes, dictated by Gamow-Teller transitions, significantly alter the lepton fraction of the stellar matter. In this paper we calculate Gamow-Teller (GT) transitions for isotopes of nickel, Ni6456-, using QRPA methods. The GT strength distributions were calculated using four different QRPA models. Our results are also compared with previous theoretical calculations and measured strength distributions wherever available. Our investigation concluded that amongst all RPA models, the pn-QRPA(C) model best described the measured GT distributions (including total GT strength and centroid placement). It is hoped that the current investigation of GT properties would prove handy and may lead to a better understanding of the presupernova evolution of massive stars.

Large sulfur-isotope anomaly in nonvolcanic sulfate aerosol and its implications for the Archean atmosphere.

PubMed

Shaheen, Robina; Abaunza, Mariana M; Jackson, Teresa L; McCabe, Justin; Savarino, Joël; Thiemens, Mark H

2014-08-19

Sulfur-isotopic anomalies have been used to trace the evolution of oxygen in the Precambrian atmosphere and to document past volcanic eruptions. High-precision sulfur quadruple isotope measurements of sulfate aerosols extracted from a snow pit at the South Pole (1984-2001) showed the highest S-isotopic anomalies (Δ(33)S = +1.66‰ and Δ(36)S = +2‰) in a nonvolcanic (1998-1999) period, similar in magnitude to Pinatubo and Agung, the largest volcanic eruptions of the 20th century. The highest isotopic anomaly may be produced from a combination of different stratospheric sources (sulfur dioxide and carbonyl sulfide) via SOx photochemistry, including photoexcitation and photodissociation. The source of anomaly is linked to super El Niño Southern Oscillation (ENSO) (1997-1998)-induced changes in troposphere-stratosphere chemistry and dynamics. The data possess recurring negative S-isotope anomalies (Δ(36)S = -0.6 ± 0.2‰) in nonvolcanic and non-ENSO years, thus requiring a second source that may be tropospheric. The generation of nonvolcanic S-isotopic anomalies in an oxidizing atmosphere has implications for interpreting Archean sulfur deposits used to determine the redox state of the paleoatmosphere.

Mn-53-Cr-53 Systematics of R-Chondrite NWA 753

NASA Technical Reports Server (NTRS)

Jogo, K.; Shih, C-Y.; Reese, Y. D.; Nyquist, L. E.

2006-01-01

Chondrules and chondrites are interpreted as objects formed in the early solar system, and it is important to study them in order to elucidate its evolution. Here, we report the study of the Mn-Cr systematics of the R-Chondrite NWA753 and compare the results to other chondrite data. The goal was to determine Cr isotopic and age variations among chondrite groups with different O-isotope signatures. The Mn-53-Cr-53 method as applied to individual chondrules [1] or bulk chondrites [2] is based on the assumption that 53Mn was initially homogeneously distributed in that portion the solar nebula where the chondrules and/or chondrites formed. However, different groups of chondrites formed from regions of different O-isotope compositions. So, different types of chondrites also may have had different initial Mn-53 abundances and/or Cr isotopic compositions. Thus, it is important to determine the Cr isotopic systematics among chondrites from various chondrite groups. We are studying CO-chondrite ALH83108 and Tagish Lake in addition to R-Chondrite NWA753. These meteorites have very distinct O-isotope compositions (Figure 1).

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

NASA Technical Reports Server (NTRS)

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

2014-01-01

Wark-Lovering (WL) rims [1] surrounding many refractory inclusions represent marker events in the early evolution of the Solar System in which many inclusions were exposed to changes in pressure [2], temperature [3], and isotopic reservoirs [4-7]. The effects of these events can be complex, not only producing mineralogical variability of WL rims [2], but also leading to mineralogical [8-10] and isotopic [7, 11, 12] changes within inclusion interiors. Extreme oxygen isotopic heterogeneity measured in CAIs has been explained by mixing between distinct oxygen gas reservoirs in the nebula [13]. Some WL rims contain relatively simple mineral layering and/or are isotopically homogeneous [14, 15]. As part of a larger effort to document and understand the modifications observed in some CAIs, an inclusion (L6) with a complex WL rim from Leoville, a member of the reduced CV3 subgroup was studied. Initial study of the textures and mineral chemistry was presented by [16]. Here we present NanoSIMS oxygen isotopic measurements to complement these petrologic observations.

Isotope composition and volume of Earth's early oceans.

PubMed

Pope, Emily C; Bird, Dennis K; Rosing, Minik T

2012-03-20

Oxygen and hydrogen isotope compositions of Earth's seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen's was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth's oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH(4) and CO(2) concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth.

Isotope composition and volume of Earth’s early oceans

PubMed Central

Pope, Emily C.; Bird, Dennis K.; Rosing, Minik T.

2012-01-01

Oxygen and hydrogen isotope compositions of Earth’s seawater are controlled by volatile fluxes among mantle, lithospheric (oceanic and continental crust), and atmospheric reservoirs. Throughout geologic time the oxygen mass budget was likely conserved within these Earth system reservoirs, but hydrogen’s was not, as it can escape to space. Isotopic properties of serpentine from the approximately 3.8 Ga Isua Supracrustal Belt in West Greenland are used to characterize hydrogen and oxygen isotope compositions of ancient seawater. Archaean oceans were depleted in deuterium [expressed as δD relative to Vienna standard mean ocean water (VSMOW)] by at most 25 ± 5‰, but oxygen isotope ratios were comparable to modern oceans. Mass balance of the global hydrogen budget constrains the contribution of continental growth and planetary hydrogen loss to the secular evolution of hydrogen isotope ratios in Earth’s oceans. Our calculations predict that the oceans of early Earth were up to 26% more voluminous, and atmospheric CH4 and CO2 concentrations determined from limits on hydrogen escape to space are consistent with clement conditions on Archaean Earth. PMID:22392985

Earth science: Extraordinary world

NASA Astrophysics Data System (ADS)

Day, James M. D.

2016-09-01

The isotopic compositions of objects that formed early in the evolution of the Solar System have been found to be similar to Earth's composition -- overturning notions of our planet's chemical distinctiveness. See Letters p.394 & p.399

Potential energy surfaces of Polonium isotopes

NASA Astrophysics Data System (ADS)

Nerlo-Pomorska, B.; Pomorski, K.; Schmitt, C.; Bartel, J.

2015-11-01

The evolution of the potential energy landscape is analysed in detail for ten even-even polonium isotopes in the mass range 188\\lt A\\lt 220 as obtained within the macroscopic-microscopic approach, relying on the Lublin-Strasbourg drop model and the Yukawa-folded single-particle energies for calculating the microscopic shell and pairing corrections. A variant of the modified Funny-Hills nuclear shape parametrization is used to efficiently map possible fission paths. The approach explains the main features of the fragment partition as measured in low-energy fission along the polonium chain. The latter lies in a transitional region of the nuclear chart, and will be essential to consistently understand the evolution of fission properties from neutron-deficient mercury to heavy actinides. The ability of our method to predict fission observables over such an extended region looks promising.

The Influence of Indian Ocean Atmospheric Circulation on Warm Pool Hydroclimate During the Holocene Epoch

NASA Technical Reports Server (NTRS)

Tierney, J.E.; Oppo, D. W.; LeGrande, A. N.; Huang, Y.; Rosenthal, Y.; Linsley, B. K.

2012-01-01

Existing paleoclimate data suggest a complex evolution of hydroclimate within the Indo-Pacific Warm Pool (IPWP) during the Holocene epoch. Here we introduce a new leaf wax isotope record from Sulawesi, Indonesia and compare proxy water isotope data with ocean-atmosphere general circulation model (OAGCM) simulations to identify mechanisms influencing Holocene IPWP hydroclimate. Modeling simulations suggest that orbital forcing causes heterogenous changes in precipitation across the IPWP on a seasonal basis that may account for the differences in time-evolution of the proxy data at respective sites. Both the proxies and simulations suggest that precipitation variability during the September-November (SON) season is important for hydroclimate in Borneo. The preeminence of the SON season suggests that a seasonally lagged relationship between the Indian monsoon and Indian Ocean Walker circulation influences IPWP hydroclimatic variability during the Holocene.

Earth's early atmosphere as seen from carbon and nitrogen isotopic analysis of Archean sediments

NASA Technical Reports Server (NTRS)

Gibson, E. K., Jr.; Carr, L. P.; Gilmour, I.; Pillinger, C. T.

1986-01-01

The origin and evolution of the Earth's early atmosphere has long been a topic of great interest but determination of actual compositions over geologic time is a difficult problem. However, recent systematic studies of stromatolite deposits (Precambrian Paleobiology Research Group) has extended our knowledge of Archean ecosystems. It has been shown that many stromatolite deposits have undergone negligible alteration since their time of formation. The discovery of primary fluid inclusions within unaltered 3.5 b.y. old Archiean sediments and the observation that the 3.3 b.y. old Barberton cherts have remained closed to argon loss and have not been subjected to thermal metamorphism suggests that an opportunity exists for the direct measurement of the volatile constituents present at their time of formation. Of primary interest to this study was the possibility that the stromatolites and other Archean sediments might retain a vestige of the atmosphere and thus afford an indication of the variations in carbon dioxide and nitrogen isotopic compositions with time. A suite of essentially unaltered Archean stromatolites and the cherts of different ages and geologic sites have been analyzed for their trapped carbon dioxide and nitrogen compositions by the stepped combustion extraction tech nique utilizing static mass spectrometers for the isotope measurements.

Lead isotope relations in oceanic Ridge basalts from the Juan de Fuca-Gorda Ridge area N.E. Pacific Ocean

USGS Publications Warehouse

Church, S.E.; Tatsumoto, M.

1975-01-01

Lead isotopic analyses of a suite of basaltic rocks from the Juan de Fuca-Gorda Ridge and nearby seamounts confirm an isotopically heterogeneous mantle known since 1966. The process of mixing during partial melting of a heterogeneous mantle necessarily produces linear data arrays that can be interpreted as secondary isochrons. Moreover, the position of the entire lead isotope array, with respect to the geochron, requires that U/Pb and Th/Pb values are progressively increased over the age of the earth. Partial melting theory also dictates analogous behavior for the other incompatible trace elements. This process explains not only the LIL element character of MOR basalts, but also duplicates the spread of radiogenic lead data collected from alkali-rich oceanic basalts. This dynamic, open-system model of lead isotopic and chemical evolution of the mantle is believed to be the direct result of tectonic flow and convective overturn within the mantle and is compatible with geophysical models of a dynamic earth. ?? 1975 Springer-Verlag.

The Chlorine Isotopic Composition Of Lunar UrKREEP

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Tartese, R.; Anand, M.; McCubbin, F. M.; Neal, C. R.; Franchi, I. A.

2016-01-01

Since the long standing paradigm of an anhydrous Moon was challenged there has been a renewed focus on investigating volatiles in a variety of lunar samples. However, the current models for the Moon’s formation have yet to fully account for its thermal evolution in the presence of H2O and other volatiles. When compared to chondritic meteorites and terrestrial rocks, lunar samples have exotic chlorine isotope compositions, which are difficult to explain in light of the abundance and isotopic composition of other volatile species, especially H, and the current estimates for chlorine and H2O in the bulk silicate Moon. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed a comprehensive in situ high precision study of chlorine isotopes, using NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) of lunar apatite from a suite of Apollo samples covering a range of geochemical characteristics and petrologic types.

High-spin level structure and Ground-state phase transition in the odd-mass 103-109Rh isotopes in the framework of exactly solvable sdg interacting boson-fermion model

NASA Astrophysics Data System (ADS)

Ghapanvari, M.; Ghorashi, A. H.; Ranjbar, Z.; Jafarizadeh, M. A.

2018-03-01

In this article, the negative-parity states in the odd-mass 103 - 109Rh isotopes in terms of the sd and sdg interacting-boson fermion models were studied. The transitional interacting boson-fermion model Hamiltonians in sd and sdg-IBFM versions based on affine SU (1 , 1) Lie Algebra were employed to describe the evolution from the spherical to deformed gamma unstable shapes along with the chain of Rh isotopes. In this method, sdg-IBFM Hamiltonian, which is a three level pairing Hamiltonian was determined easily via the exactly solvable method. Some observables of the shape phase transitions such as energy levels, the two neutron separation energies, signature splitting of the γ-vibrational band, the α-decay and double β--decay energies were calculated and examined for these isotopes. The present calculation correctly reproduces the spherical to gamma-soft phase transition in the Rh isotopes. Some comparisons were made with sd-IBFM.

Intramolecular carbon and nitrogen isotope analysis by quantitative dry fragmentation of the phenylurea herbicide isoproturon in a combined injector/capillary reactor prior to GC separation.

PubMed

Penning, Holger; Elsner, Martin

2007-11-01

Potentially, compound-specific isotope analysis may provide unique information on source and fate of pesticides in natural systems. Yet for isotope analysis, LC-based methods that are based on the use of organic solvents often cannot be used and GC-based analysis is frequently not possible due to thermolability of the analyte. A typical example of a compound with such properties is isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea), belonging to the worldwide extensively used phenylurea herbicides. To make isoproturon accessible to carbon and nitrogen isotope analysis, we developed a GC-based method during which isoproturon was quantitatively fragmented to dimethylamine and 4-isopropylphenylisocyanate. Fragmentation occurred only partially in the injector but was mainly achieved on a heated capillary column. The fragments were then chromatographically separated and individually measured by isotope ratio mass spectrometry. The reliability of the method was tested in hydrolysis experiments with three isotopically different batches of isoproturon. For all three products, the same isotope fractionation factors were observed during conversion and the difference in isotope composition between the batches was preserved. This study demonstrates that fragmentation of phenylurea herbicides does not only make them accessible to isotope analysis but even enables determination of intramolecular isotope fractionation.

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

Modeling the isotopic evolution of snowpack and snowmelt: Testing a spatially distributed parsimonious approach.

PubMed

Ala-Aho, Pertti; Tetzlaff, Doerthe; McNamara, James P; Laudon, Hjalmar; Kormos, Patrick; Soulsby, Chris

2017-07-01

Use of stable water isotopes has become increasingly popular in quantifying water flow paths and travel times in hydrological systems using tracer-aided modeling. In snow-influenced catchments, snowmelt produces a traceable isotopic signal, which differs from original snowfall isotopic composition because of isotopic fractionation in the snowpack. These fractionation processes in snow are relatively well understood, but representing their spatiotemporal variability in tracer-aided studies remains a challenge. We present a novel, parsimonious modeling method to account for the snowpack isotope fractionation and estimate isotope ratios in snowmelt water in a fully spatially distributed manner. Our model introduces two calibration parameters that alone account for the isotopic fractionation caused by sublimation from interception and ground snow storage, and snowmelt fractionation progressively enriching the snowmelt runoff. The isotope routines are linked to a generic process-based snow interception-accumulation-melt model facilitating simulation of spatially distributed snowmelt runoff. We use a synthetic modeling experiment to demonstrate the functionality of the model algorithms in different landscape locations and under different canopy characteristics. We also provide a proof-of-concept model test and successfully reproduce isotopic ratios in snowmelt runoff sampled with snowmelt lysimeters in two long-term experimental catchment with contrasting winter conditions. To our knowledge, the method is the first such tool to allow estimation of the spatially distributed nature of isotopic fractionation in snowpacks and the resulting isotope ratios in snowmelt runoff. The method can thus provide a useful tool for tracer-aided modeling to better understand the integrated nature of flow, mixing, and transport processes in snow-influenced catchments.

3He Abundances in Planetary Nebulae

NASA Astrophysics Data System (ADS)

Guzman-Ramirez, Lizette

2017-10-01

Determination of the 3He isotope is important to many fields of astrophysics, including stellar evolution, chemical evolution, and cosmology. The isotope is produced in stars which evolve through the planetary nebula phase. Planetary nebulae are the final evolutionary phase of low- and intermediate-mass stars, where the extensive mass lost by the star on the asymptotic giant branch is ionised by the emerging white dwarf. This ejecta quickly disperses and merges with the surrounding ISM. 3He abundances in planetary nebulae have been derived from the hyperfine transition of the ionised 3He, 3He+, at the radio rest frequency 8.665 GHz. 3He abundances in PNe can help test models of the chemical evolution of the Galaxy. Many hours have been put into trying to detect this line, using telescopes like the Effelsberg 100m dish of the Max Planck Institute for Radio Astronomy, the National Radio Astronomy Observatory (NRAO) 140-foot telescope, the NRAO Very Large Array, the Arecibo antenna, the Green Bank Telescope, and only just recently, the Deep Space Station 63 antenna from the Madrid Deep Space Communications Complex.

Origin and thermal evolution of Mars

NASA Technical Reports Server (NTRS)

Schubert, G.; Solomon, Sean C.; Turcotte, D. L.; Drake, M. J.; Sleep, N. H.

1993-01-01

The thermal evolution of Mars is governed by subsolidus mantle convection beneath a thick lithosphere. Models of the interior evolution are developed by parameterizing mantle convective heat transport in terms of mantle viscosity, the superadiabatic temperature rise across the mantle and mantle heat production. Geological, geophysical, and geochemical observations of the composition and structure of the interior and of the timing of major events in Martian evolution, such as global differentiation, atmospheric outgassing and the formation of the hemispherical dichotomy and Tharsis, are used to constrain the model computations. Isotope systematics of SNC meteorites suggest core formation essentially contemporaneously with the completion of accretion. Other aspects of this investigation are discussed.

The symmetry energy, neutron skin thickness and isovector dipole response of neutron-rich nuclei

NASA Astrophysics Data System (ADS)

Horvat, A.; Paar, N.

2015-04-01

The isotopic evolution of the relationship between the symmetry energy at saturation density of nuclear matter (J), neutron skin thickness (ΔR) and relevant observables related to isovector dipole excitations in neutron rich 116-136Sn isotopes has been investigated in the framework of relativistic nuclear energy density functional theory. The description employs a family of effective interactions with density dependent meson-nucleon couplings (DDME) spanning the range of values J = 30 - 38 MeV.

Carbon Isotope Chemistry in Molecular Clouds

NASA Technical Reports Server (NTRS)

Robertson, Amy N.; Willacy, Karen

2012-01-01

Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

Isotope chirality in long-armed multifunctional organosilicon ("Cephalopod") molecules.

PubMed

Barabás, Béla; Kurdi, Róbert; Zucchi, Claudia; Pályi, Gyula

2018-07-01

Long-armed multifunctional organosilicon molecules display self-replicating and self-perfecting behavior in asymmetric autocatalysis (Soai reaction). Two representatives of this class were studied by statistical methods aiming at determination of probabilities of natural abundance chiral isotopomers. The results, reported here, show an astonishing richness of possibilities of the formation of chiral isotopically substituted derivatives. This feature could serve as a model for the evolution of biological chirality in prebiotic and early biotic stereochemistry. © 2018 Wiley Periodicals, Inc.

Meteoritic Sulfur Isotopic Analysis

NASA Technical Reports Server (NTRS)

Thiemens, Mark H.

1996-01-01

Funds were requested to continue our program in meteoritic sulfur isotopic analysis. We have recently detected a potential nucleosynthetic sulfur isotopic anomaly. We will search for potential carriers. The documentation of bulk systematics and the possible relation to nebular chemistry and oxygen isotopes will be explored. Analytical techniques for delta(sup 33), delta(sup 34)S, delta(sup 36)S isotopic analysis were improved. Analysis of sub milligram samples is now possible. A possible relation between sulfur isotopes and oxygen was detected, with similar group systematics noted, particularly in the case of aubrites, ureilites and entstatite chondrites. A possible nucleosynthetic excess S-33 has been noted in bulk ureilites and an oldhamite separate from Norton County. High energy proton (approximately 1 GeV) bombardments of iron foils were done to experimentally determine S-33, S-36 spallogenic yields for quantitation of isotopic measurements in iron meteorites. Techniques for measurement of mineral separates were perfected and an analysis program initiated. The systematic behavior of bulk sulfur isotopes will continue to be explored.

Neodymium Isotopic Compositions of the Titanite Reference Materials Used in U-Pb Geochronology

NASA Astrophysics Data System (ADS)

Ma, Q.; Yang, Y.; Zhao, Z.

2017-12-01

Titanite (CaTiSiO5) is a widespread mineral and preferentially incorporates considerable uranium and significant light rare earth elements (LREEs) in its structure. Geochronology based upon U-Pb and Pb-Pb analyses of titanite has proven to be useful for understanding the P-T-t evolution of many igneous, metamorphic and hydrothermally altered rock samples (Scott and St-Onge, 1995). In the meantime, Sm-Nd isotopic composition in single titanite can be used to obtain initial Nd isotope composition at the time of titanite crystallization when combined with its U-Pb age, making titanite the most versatile mineral for dating metamorphism and tracing hydrothermal source (Amelin et al., 2009). The widely utilized in situ analyses by SIMS and LA-(MC)-ICP-MS have emphasized the significance for uniform and homogeneous reference materials for external correction (Liu et al., 2012, Sun et al., 2012, Yang et al., 2014). Here, we present U-Pb ages and Sm-Nd isotope analyses of twelve natural titanite crystals (12YQ82, T004, Ontario, BLR-1, OLT1, Khan, Qinghu, TLS-36, NW-IOA, C253, Pakistan and MKED1) acquired by Agilent 7500a Q-ICP-MS and Neptune MC-ICP-MS, respectively, combined a 193 nm ArF excimer laser ablation system. For U-Pb dating, elemental fractionation and instrumental drift were externally corrected using MKED1 titanite standard, showing results of U-Pb analyses all within error of those recommended values. With respect to Sm-Nd isotopes, we employed the interference-free 147Sm/149Sm to deduct 144Sm isobaric interference on 144Nd, and the fractionation between 147Sm and 144Nd was calibrated using BLR-1 titanite, which is proved homogenous in Sm-Nd isotopic system. The obtained Sm-Nd isotopic compositions for natural titanite samples are all consistent with those values determined by isotope dilution (ID) MC-ICP-MS, demonstrating the precision and accuracy currently available for in situ Sm-Nd analyses. Our results demonstrate that BLR-1, OLT1 and Ontario titanites are relatively uniform and homogeneous in Sm-Nd isotopic system and thus can serve as ideal reference materials for external calibration during in situ Sm-Nd analysis.

Early diagenesis of recently deposited organic matter: a 9-yr time-series study of a flood deposit

NASA Astrophysics Data System (ADS)

Tesi, T.; Goñi, M. A.; Langone, L.; Wheatcroft, R. A.; Miserocchi, S.; Bertotti, L.

2012-04-01

Because the preservation of organic carbon (OC) in river-dominated margins accounts for a significant fraction of OC burial in the ocean, biochemical studies must find novel ways to explicitly address the non-steadiness of these settings. In this study, we approached this issue by collecting event-beds soon after their emplacement (event-response sampling) and following their evolution with time (time-series analysis). In Fall 2000, the Po River (Italy) experienced a 100-yr return period flood that resulted in a thick deposit in the adjacent prodelta. Cores collected in the central prodelta after the flood event and over the following 9 years (8 sediment cores), allowed characterization of the event-strata in their initial state and documentation of their subsequent evolution. The characterization of sedimentary organic matter (OM) collected soon after the flood deposit emplacement and the description of its subsequent evolution with time provided extraordinary opportunity to investigate the reactivity of OM on a 9-yr time scale. Our analysis included the evaluation of the whole spectrum of CuO reaction products such as lignin phenols, p-hydroxy benzenes, benzoic acids, cutin-derived products, dicarboxylic acids, and fatty acids, as well as bulk organic carbon, nitrogen and carbon stable isotopes. Sedimentological characteristics were investigated using x-radiographs and sediment texture analyses whereas the evolution of sedimentary OM was evaluated via inventories of bulk elements and biomarkers. Remineralization of organic nitrogen and organic carbon occurred at similar rates (% change ~-17%) indicating that the overall elemental composition of sedimentary OM remained stable with time. This steadiness was confirmed by lack of temporal changes of the OC/TN ratio. Despite the steady OC/TN ratio, changes in δ13C revealed preferential loss of isotopically enriched organic material. Biomarker inventories indicated selective degradation during diagenesis, consistent with the reactivity spectrum observed in laboratory and field studies (% change from -~9 to -~60%). Among terrigenous biomarkers, lignin phenols were better preserved than hydroxy fatty acids derived from plant cuticles (% change ~-10 vs ~-50 %, respectively). Aromatic CuO reaction products, such as benzoic acids and p-hydroxy benzenes, were better preserved than lipid-derived biomarkers, especially for those compounds having a terrestrially-derived source. The largest part of dicarboxylic acids was derived from plant cuticles and exhibited reactivities coherent with cutin-derived products (% change ~-50%).

Advances and limitations on interpreting the erosional record from isotopic analysis of single detrital mineral grains

NASA Astrophysics Data System (ADS)

Parrish, Randall

2010-05-01

The analysis of provenance of clastic sediments is useful for reconstructing the characteristics and rates of exhumation of source areas, and sometimes placing minimum age constraints on depositional age. Due largely to increased availability and ease of access to LA-ICP-MS instrumentation, the analysis of provenance using single detrital accessory minerals has grown very rapidly over recent years. With this however is a culture of casual users who may not fully appreciate subtleties of measurement and isotope interpretation. The isotopic provenance literature is dominated by zircon-centric studies that use U-Pb dating and Hf isotope measurements of single zircons, but unfortunately an increasing number of these studies appear to lack sufficient understanding of U-Pb and Hf systematics; misleading interpretations are increasingly common. The inherent information contained in detrital accessory minerals is potentially immense, scientifically, but comprehensive interpretations attempting to reconstruct the geological make-up and evolution of sources require dating of multiple types of accessory minerals (i.e. zircon, titanite, monazite, garnet inclusions, micas, allanite, rutile, apatite) by various methods (U-Pb, fission track, Ar-Ar…) at times accompanied by isotope geochemical data (Lu-Hf, Sm-Nd, Rb-Sr) of phases where Sr, Hf, or REE comprise a major element (≥0.5%). Many approaches have been demonstrated but the mix of methodologies needs to be tailored to the problem, in view of the variable effort and expense needed to acquire good datasets. To date there are few comprehensive multi-mineral, multi-isotope system applications, and too many studies that follow a prescriptive cookbook that lacks innovation and fails to address a problem. The field needs to focus effort on the approaches that can solve a problem well rather than doing either just the easy methods or too many methods only moderately well. Zircon studies require strategies that reduce or eliminate discordance, collect sufficient data on each grain to make a robust age interpretation, improve accuracy of data by more attention to standards and uncertainties, can analyze thin overgrowths that reveal the magmatic or metamorphic age, and minimize sample consumption, not an easy task for the vast majority of laboratories doing provenance applications. Detrital monazite, monazite-in garnet, titanite and rutile can reveal much of the higher temperature metamorphic time-temperature path, and coupled U-Pb and fission track studies of single zircon and apatite grains can be useful for determining lower temperature exhumation rates. Isotope geochemistry (Hf-Nd-Sr-O) is more time consuming but can be pivotal to distinguish subtle differences in sources and to test specific hypotheses. Examples of improved methods and applications will be presented to illustrate the presentation.

Thermal evolution of old white dwarfs

NASA Astrophysics Data System (ADS)

Kozhberov, Andrew

2017-11-01

This work is devoted to a description of thermodynamic properties of Coulomb crystals which are expected to form in white dwarf interiors. Effects of magnetic field, isotopic impurities, polarization of the electron background and crystal lattice type on the thermal evolution of white dwarfs are discussed. It is shown that the electron polarization could play a noticeable role in the cooling process. While other parameters in concern do not make a significant impact.

Modelling and intepreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2012-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, droplet size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

Modelling and interpreting the isotopic composition of water vapour in convective updrafts

NASA Astrophysics Data System (ADS)

Bolot, M.; Legras, B.; Moyer, E. J.

2013-08-01

The isotopic compositions of water vapour and its condensates have long been used as tracers of the global hydrological cycle, but may also be useful for understanding processes within individual convective clouds. We review here the representation of processes that alter water isotopic compositions during processing of air in convective updrafts and present a unified model for water vapour isotopic evolution within undiluted deep convective cores, with a special focus on the out-of-equilibrium conditions of mixed-phase zones where metastable liquid water and ice coexist. We use our model to show that a combination of water isotopologue measurements can constrain critical convective parameters, including degree of supersaturation, supercooled water content and glaciation temperature. Important isotopic processes in updrafts include kinetic effects that are a consequence of diffusive growth or decay of cloud particles within a supersaturated or subsaturated environment; isotopic re-equilibration between vapour and supercooled droplets, which buffers isotopic distillation; and differing mechanisms of glaciation (droplet freezing vs. the Wegener-Bergeron-Findeisen process). As all of these processes are related to updraft strength, particle size distribution and the retention of supercooled water, isotopic measurements can serve as a probe of in-cloud conditions of importance to convective processes. We study the sensitivity of the profile of water vapour isotopic composition to differing model assumptions and show how measurements of isotopic composition at cloud base and cloud top alone may be sufficient to retrieve key cloud parameters.

The history of Martian volatiles

NASA Astrophysics Data System (ADS)

Jakosky, Bruce M.; Jones, John H.

The behavior of water and other volatiles on Mars is key to understanding the evolution of the climate. The early climate played a fundamental role in producing the observed surface morphology and possibly in enabling the existence of an early biosphere. Geochemical and isotopic data can be used to infer the history of volatiles. On the basis of the isotopic data from the atmosphere and from components of the surface (as measured in meteorites that come from Mars), there appear to be at least two reservoirs of volatiles, one that has undergone exchange with the atmosphere and has been isotopically fractionated, and a second that is unfractionated and may represent juvenile gases. The fractionation of the atmospheric component has occurred primarily through the escape of gas to space. In addition, the atmospheric gases have mixed substantially with crustal reservoirs of volatiles. Such exchange may have occurred in aqueous or hydrothermal environments. The history of escape to space, as driven by the properties of the Sun through time, is consistent with the surface geomorphology. Together, they suggest an early environment that was substantially different from the present one and the evolution through time to a colder, dryer climate.

Isotope geochemistry of recent magmatism in the Aegean arc: Sr, Nd, Hf, and O isotopic ratios in the lavas of Milos and Santorini-geodynamic implications

USGS Publications Warehouse

Briqueu, L.; Javoy, M.; Lancelot, J.R.; Tatsumoto, M.

1986-01-01

In this comparative study of variations in the isotopic compositions (Sr, Nd, O and Hf) of the calc-alkaline magmas of the largest two volcanoes, Milos and Santorini, of the Aegean arc (eastern Mediterranean) we demonstrate the complexity of the processes governing the evolution of the magmas on the scale both of the arc and of each volcano. On Santorini, the crustal contamination processes have been limited, effecting the magma gradually during its differentiation. The most differentiated lavas (rhyodacite and pumice) are also the most contaminated. On Milos, by contrast, these processes are very extensive. They are expressed in the 143Nd/144Nd vs. 87Sr/86Sr diagram as a continuous mixing curve between a mantle and a crustal end member pole defined by schists and metavolcanic rocks outcropping on these volcanoes. In contrast with Santorini, the least differentiated lavas on Milos are the most contaminated. These isotopic singularities can be correlated with the geodynamic evolution of the Aegean subduction zone, consisting of alternating tectonic phases of distension and compression. The genesis of rhyolitic magmas can be linked to the two phases of distension, and the contamination of the calc-alkaline mantle-derived magmas with the intermediate compressive phase. The isotopic characteristics of uncontaminated calc-alkaline primitive magmas of Milos and Santorini are directly comparable to those of magmas generated in subduction zones for which a contribution of subducted sediments to partial melts from the mantle is suggested, such as in the Aleutian, Sunda, and lesser Antilles island arcs. However, in spite of the importance of the sediment pile in the eastern Mediterranen oceanic crust (6-10 km), the contribution of the subducted terrigenous materials remains of limited amplitude. ?? 1986.

A Formation Timescale of the Galactic Halo from Mg Isotopes in Dwarf Stars

NASA Astrophysics Data System (ADS)

Carlos, Marília; Karakas, Amanda I.; Cohen, Judith G.; Kobayashi, Chiaki; Meléndez, Jorge

2018-04-01

We determine magnesium isotopic abundances of metal-poor dwarf stars from the galactic halo, to shed light on the onset of asymptotic giant branch (AGB) star nucleosynthesis in the galactic halo and constrain the timescale of its formation. We observed a sample of eight new halo K dwarfs in a metallicity range of ‑1.9 < [Fe/H] < ‑0.9 and 4200 < T eff(K) < 4950, using the HIRES spectrograph at the Keck Observatory (R ≈ 105 and 200 ≤ S/N ≤ 300). We obtain magnesium isotopic abundances by spectral synthesis on three MgH features and compare our results with galactic chemical evolution models. With the current sample, we almost double the number of metal-poor stars with Mg isotopes determined from the literature. The new data allow us to determine the metallicity when the 26Mg abundances start to become important, [Fe/H] ∼ ‑1.4 ± 0.1. The data with [Fe/H] > ‑1.4 are somewhat higher (1–3σ) than previous chemical evolution model predictions, indicating perhaps higher yields of the neutron-rich isotopes. Our results using only AGB star enrichment suggest a timescale for formation for the galactic halo of about 0.3 Gyr, but considering also supernova enrichment, the upper limit for the timescale formation is about 1.5 Gyr. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a scientific partnership among the California Institute of Technology, the University of California and the National Aeronautics and Space Administration. The Observatory was made possible by the generous financial support of the W. M. Keck Foundation.

Isotopic Evidence for Platform Exposure and Diagenesis in the Miocene: Implications for South-East Asian Platform Evolution.

NASA Astrophysics Data System (ADS)

Prince, K.; Laya, J. C.; Betzler, C.; Eberli, G. P.; Zarikian, C.; Swart, P. K.; Blättler, C. L.; Reolid, J.; Reijmer, J.

2017-12-01

The Maldives record nearly continuous carbonate deposition from the Eocene to the Holocene, and its stable tectonic regime and lack of clastic input make it an ideal example for understanding the depositional and diagenetic dynamics of isolated carbonate platforms. The Kardiva platform ultimately drowned, but the amplitude and frequency of sea-level changes in the Miocene make it likely that subaerial exposure occurred during its evolution. Abundant moldic porosity has been interpreted as meteoric diagenesis, but stable isotope evidence to support this has not been reported. Using bulk stable isotope analyses and petrographic methods, we sought to identify evidence of meteoric diagenesis by investigating the variations in grains, cements, porosity, δ13C, and δ18O at IODP Sites U1645, U1469, and U1470. Within the platform, grain distribution is variable with algae, benthic foraminifera, and corals representing the most abundant grain types. Cement abundance generally increases while porosity decreases with depth, with some variability. δ18O and δ13C range from -7.0‰ to 3.2‰ and -7‰ to 2.5‰, respectively. Petrography and isotope values show evidence for subaerial exposure and alteration by meteoric fluids, with a cross-plot of δ13C and δ18O showing the characteristic inverted "J" trend associated with dissolution and precipitation reactions mediated by meteoric fluids, resulting in more negative values. These results are compared to isotopic values for unaltered red algae and corals to account for the possibility of vital effects, but vital effects alone do not yield such low values. This evidence for meteoric diagenesis of the Kardiva Platform indicates variation between wet and dry periods, and also potential high-amplitude sea-level fluctuations during the Miocene in the Indo-Pacific region.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Pb isotopic constraints on the formation of the Dikulushi Cu-Pb-Zn-Ag mineralisation, Kundelungu Plateau (Democratic Republic of Congo)

NASA Astrophysics Data System (ADS)

Haest, Maarten; Schneider, Jens; Cloquet, Christophe; Latruwe, Kris; Vanhaecke, Frank; Muchez, Philippe

2010-04-01

Base metal-Ag mineralisation at Dikulushi and in other deposits on the Kundelungu Plateau (Democratic Republic of Congo) developed during two episodes. Subeconomic Cu-Pb-Zn-Fe polysulphide ores were generated during the Lufilian Orogeny (c. 520 Ma ago) in a set of E-W- and NE-SW-oriented faults. Their lead has a relatively unradiogenic and internally inhomogeneous isotopic composition (206Pb/204Pb = 18.07-18.49), most likely generated by mixing of Pb from isotopically heterogeneous clastic sources. These sulphides were remobilised and enriched after the Lufilian Orogeny, along reactivated and newly formed NE-SW-oriented faults into a chalcocite-dominated Cu-Ag mineralisation of high economic interest. The chalcocite samples contain only trace amounts of lead and show mostly radiogenic Pb isotope signatures that fall along a linear trend in the 207Pb/204Pb vs. 206Pb/204Pb diagram (206Pb/204Pb = 18.66-23.65; 207Pb/204Pb = 15.72-16.02). These anomalous characteristics reflect a two-stage evolution involving admixture of both radiogenic lead and uranium during a young fluid event possibly c. 100 Ma ago. The Pb isotope systematics of local host rocks to mineralisation also indicate some comparable young disturbance of their U-Th-Pb systems, related to the same event. They could have provided Pb with sufficiently radiogenic compositions that was added to less radiogenic Pb remobilised from precursor Cu-Pb-Zn-Fe polysulphides, whereas the U most likely originated from external sources. Local metal sources are also suggested by the 208Pb/204Pb-206Pb/204Pb systematics of combined ore and rock lead, which indicate a pronounced and diversified lithological control of the immediate host rocks on the chalcocite-dominated Cu-Ag ores. The Pb isotope systematics of polysulphide mineralisation on the Kundelungu Plateau clearly record a diachronous evolution.

Thermal and chemical evolution in the early Solar System as recorded by FUN CAIs: Part II - Laboratory evaporation of potential CMS-1 precursor material

NASA Astrophysics Data System (ADS)

Mendybaev, Ruslan A.; Williams, Curtis D.; Spicuzza, Michael J.; Richter, Frank M.; Valley, John W.; Fedkin, Alexei V.; Wadhwa, Meenakshi

2017-03-01

We present the results of laboratory experiments in which a forsterite-rich melt estimated to be a potential precursor of Allende CMS-1 FUN CAI was evaporated into vacuum for different lengths of time at 1900 °C. The evaporation of this melt resulted in residues that define trajectories in chemical as well as magnesium, silicon and oxygen isotopic composition space and come very close to the measured properties of CMS-1. The isotopic composition of the evaporation residues was also used to determine the kinetic isotopic fractionation factors [α2,1 (vapor-melt) defined as the ratio of isotopes 2 and 1 of a given element in the evaporating gas divided by their ratio in the evaporating source] for evaporation of magnesium (α25,24 for 25Mg/24Mg), silicon (α29,28 for 29Si/28Si) and oxygen (α18,16 for 18O/16O) from the forsterite-rich melt at 1900 °C. The values of α25,24 = 0.98383 ± 0.00033 and α29,28 = 0.99010 ± 0.00038 are essentially independent of change in the melt composition as evaporation proceeds. In contrast, α18,16 changes from 0.9815 ± 0.0016 to ∼0.9911 when the residual melt composition changes from forsteritic to melilitic. Using the determined values of α25,24 and α29,28 and present-day bulk chemical composition of the CMS-1, the composition of the precursor of the inclusion was estimated to be close to the clinopyroxene + spinel + forsterite assemblage condensed from a solar composition gas. The correspondence between the chemical composition and isotopic fractionation of experimental evaporation residues and the present-day bulk chemical and isotopic compositions of CMS-1 is evidence that evaporation played a major role in the chemical evolution of CMS-1.

Paloma: In-situ Measurement of The Elemental and Isotopic Composition of The Mars Atmosphere

NASA Astrophysics Data System (ADS)

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Correia, J.-J.; Covinhes, J.; Goulpeau, G.; Leblanc, F.; Malique, Ch.; Sarda, P.; Schaetzel, P.; Sabroux, J.-C.; Ferry, C.; Richon, P.; Pineau, J.-F.; Desjean, M.-C.

The PALOMA instrument, presently under study in the frame of the NASA/CNES Mars exploration program, is devoted to the accurate measurement of isotopic and el- emental ratios in Mars atmosphere. It consists of a mass spectrometer coupled with a gas preparation line for separation of reactive and noble gas species, and noble gas species (and reactive gases) from each other, by chemical and cryogenic trapping, and possibly permeation techniques. This instrument, ranked among the most important four types of measurement recommended by the US Committee on Planetary and Lu- nar Exploration (COMPLEX), will be proposed as a part of the payload of the 07 NASA smart landers. The general objectives of PALOMA are to provide instanta- neous and time-varying patterns of noble gas isotopic spectra, and stable isotopes. Such measurements will allow to improve our general understanding of volatile cy- cles on Mars, and to better decipher the history of the atmosphere and climate. Past escape processes, exchanges between solid planet and atmosphere, post-accretional addition of volatil-rich matter from comets, are expected to have imprinted specific isotopic signatures. Although these signatures are strongly interlocked, a compara- tive Earth-Mars approach may allow to discriminate between them, and therefore to reconstruct the history of Martian volatiles. The evolution of atmospheric mass and composition may have had a major impact on climate evolution, e.g. through massive escape of carbon dioxide and water. In addition, precise measurements of isotopes in the present Mars atmosphere are the most promising way on the short term to confirm that SNC meteorites are from Martian origin. PALOMA also includes a small separate device for measuring ambient natural radioactivity, which might provide information about the presence of a near subsurface permafrost, possible residual volcanic activity, vertical mixing rate in the boundary layer.

Is it really organic?--multi-isotopic analysis as a tool to discriminate between organic and conventional plants.

PubMed

Laursen, K H; Mihailova, A; Kelly, S D; Epov, V N; Bérail, S; Schjoerring, J K; Donard, O F X; Larsen, E H; Pedentchouk, N; Marca-Bell, A D; Halekoh, U; Olesen, J E; Husted, S

2013-12-01

Novel procedures for analytical authentication of organic plant products are urgently needed. Here we present the first study encompassing stable isotopes of hydrogen, carbon, nitrogen, oxygen, magnesium and sulphur as well as compound-specific nitrogen and oxygen isotope analysis of nitrate for discrimination of organically and conventionally grown plants. The study was based on wheat, barley, faba bean and potato produced in rigorously controlled long-term field trials comprising 144 experimental plots. Nitrogen isotope analysis revealed the use of animal manure, but was unable to discriminate between plants that were fertilised with synthetic nitrogen fertilisers or green manures from atmospheric nitrogen fixing legumes. This limitation was bypassed using oxygen isotope analysis of nitrate in potato tubers, while hydrogen isotope analysis allowed complete discrimination of organic and conventional wheat and barley grains. It is concluded, that multi-isotopic analysis has the potential to disclose fraudulent substitutions of organic with conventionally cultivated plants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Post-rift magmatic evolution of the eastern North American “passive-aggressive” margin

USGS Publications Warehouse

Mazza, Sarah E.; Gazel, Esteban; Johnson, Elizabeth A.; Bizmis, Michael; McAleer, Ryan J.; Biryol, C. Berk

2017-01-01

Understanding the evolution of passive margins requires knowledge of temporal and chemical constraints on magmatism following the transition from supercontinent to rifting, to post-rifting evolution. The Eastern North American Margin (ENAM) is an ideal study location as several magmatic pulses occurred in the 200 My following rifting. In particular, the Virginia-West Virginia region of the ENAM has experienced two postrift magmatic pulses at ∼152 Ma and 47 Ma, and thus provides a unique opportunity to study the long-term magmatic evolution of passive margins. Here we present a comprehensive set of geochemical data that includes new 40Ar/39Ar ages, major and trace-element compositions, and analysis of radiogenic isotopes to further constrain their magmatic history. The Late Jurassic volcanics are bimodal, from basanites to phonolites, while the Eocene volcanics range from picrobasalt to rhyolite. Modeling suggests that the felsic volcanics from both the Late Jurassic and Eocene events are consistent with fractional crystallization. Sr-Nd-Pb systematics for the Late Jurassic event suggests HIMU and EMII components in the magma source that we interpret as upper mantle components rather than crustal interaction. Lithospheric delamination is the best hypothesis for magmatism in Virginia/West Virginia, due to tectonic instabilities that are remnant from the long-term evolution of this margin, resulting in a “passive-aggressive” margin that records multiple magmatic events long after rifting ended.

Variation in the terrestrial isotopic composition and atomic weight of argon

USGS Publications Warehouse

Böhlke, John Karl

2014-01-01

The isotopic composition and atomic weight of argon (Ar) are variable in terrestrial materials. Those variations are a source of uncertainty in the assignment of standard properties for Ar, but they provide useful information in many areas of science. Variations in the stable isotopic composition and atomic weight of Ar are caused by several different processes, including (1) isotope production from other elements by radioactive decay (radiogenic isotopes) or other nuclear transformations (e.g., nucleogenic isotopes), and (2) isotopic fractionation by physical-chemical processes such as diffusion or phase equilibria. Physical-chemical processes cause correlated mass-dependent variations in the Ar isotope-amount ratios (40Ar/36Ar, 38Ar/36Ar), whereas nuclear transformation processes cause non-mass-dependent variations. While atmospheric Ar can serve as an abundant and homogeneous isotopic reference, deviations from the atmospheric isotopic ratios in other Ar occurrences limit the precision with which a standard atomic weight can be given for Ar. Published data indicate variation of Ar atomic weights in normal terrestrial materials between about 39.7931 and 39.9624. The upper bound of this interval is given by the atomic mass of 40Ar, as some samples contain almost pure radiogenic 40Ar. The lower bound is derived from analyses of pitchblende (uranium mineral) containing large amounts of nucleogenic 36Ar and 38Ar. Within this interval, measurements of different isotope ratios (40Ar/36Ar or 38Ar/36Ar) at various levels of precision are widely used for studies in geochronology, water–rock interaction, atmospheric evolution, and other fields.

Stable Isotope Anatomy of Tropical Cyclone Ita, North-Eastern Australia, April 2014

PubMed Central

Munksgaard, Niels C.; Zwart, Costijn; Kurita, Naoyuki; Bass, Adrian; Nott, Jon; Bird, Michael I.

2015-01-01

The isotope signatures registered in speleothems during tropical cyclones (TC) provides information about the frequency and intensity of past TCs but the precise relationship between isotopic composition and the meteorology of TCs remain uncertain. Here we present continuous δ18O and δ2H data in rainfall and water vapour, as well as in discrete rainfall samples, during the passage of TC Ita and relate the evolution in isotopic compositions to local and synoptic scale meteorological observations. High-resolution data revealed a close relationship between isotopic compositions and cyclonic features such as spiral rainbands, periods of stratiform rainfall and the arrival of subtropical and tropical air masses with changing oceanic and continental moisture sources. The isotopic compositions in discrete rainfall samples were remarkably constant along the ~450 km overland path of the cyclone when taking into account the direction and distance to the eye of the cyclone at each sampling time. Near simultaneous variations in δ18O and δ2H values in rainfall and vapour and a near-equilibrium rainfall-vapour isotope fractionation indicates strong isotopic exchange between rainfall and surface inflow of vapour during the approach of the cyclone. In contrast, after the passage of spiral rainbands close to the eye of the cyclone, different moisture sources for rainfall and vapour are reflected in diverging d-excess values. High-resolution isotope studies of modern TCs refine the interpretation of stable isotope signatures found in speleothems and other paleo archives and should aim to further investigate the influence of cyclone intensity and longevity on the isotopic composition of associated rainfall. PMID:25742628

Understanding Copper Isotope Behavior in the High Temperature Magmatic-Hydrothermal Porphyry Environment

NASA Astrophysics Data System (ADS)

Gregory, Melissa J.; Mathur, Ryan

2017-11-01

Copper stable isotope geochemistry has the potential to constrain aspects of ore deposit formation once variations in the isotopic data can be related to the physiochemical conditions during metal deposition. This study presents Cu isotope ratios for samples from the Pebble porphyry Cu-Au-Mo deposit in Alaska. The δ65Cu values for hypogene copper sulfides range from -2.09‰ to 1.11‰ and show linear correlations with the δ18O isotope ratios calculated for the fluid in equilibrium with the hydrothermal alteration minerals in each sample. Samples with sodic-potassic, potassic, and illite alteration display a negative linear correlation between the Cu and O isotope results. This suggests that fractionation of Cu isotopes between the fluid and precipitating chalcopyrite is positive as the hydrothermal fluid is evolving from magmatic to mixed magmatic-meteoric compositions. Samples with advanced argillic alteration display a weak positive linear correlation between Cu and O isotope results consistent with small negative fluid-chalcopyrite Cu isotope fractionation during fluid evolution. The hydrothermal fluids that formed sodic-potassic, potassic, and illite alteration likely transported Cu as CuHS0. Hydrothermal fluids that resulted in advanced argillic alteration likely transport Cu as CuCl2-. The pH conditions also control Cu isotope fractionation, consistent with previous experimental work. Larger fractionation factors were found between fluids and chalcopyrite precipitating under neutral conditions contrasting with small fractionation factors calculated between fluids and chalcopyrite precipitating under acidic conditions. Therefore, this study proposes that hydrothermal fluid compositions and pH conditions are related to Cu isotope variations in high temperature magmatic-hydrothermal deposits.

Model for origin and evolution of water at volcanoes in São Miguel, Azores (Portugal), based on geochemical and isotopic data set

NASA Astrophysics Data System (ADS)

Woitischek, Julia; Dietzel, Martin; Virgílio Cruz, J.; Inguaggiato, Salvatore; Leis, Albrecht; Böttcher, Michael E.

2016-04-01

A conceptual model is presented to better constrain the origin and evolution of discharges at Sete Cidades, Fogo and Furnas Volcano, using geochemical and isotopic analyses of rock and water as well as recalculated gas composition. The evolution of thermal water clearly reveals that Na-HCO3 and Na-SO4 type of springs have their origin in meteoric water as isotope data are close to the local meteoric water line (δ 18OH2O =-3 ± 1 ‰ V-SMOW; δ DH2O= -13 ± 7 ‰ V-SMOW) with exception of a Na-Cl spring named Ferraria, Sete Cidades area (δ 18OH2O = 0.45 ‰ V-SMOW ; δ DH2O= 4.18 ‰ V-SMOW). Analysed solutions are chemical evolved by evaporation, uptake of volcanic gas, leaching of local basaltic rocks, precipitation of solids, partly admixture of sea water and/or biological activity. Following the individual concentrations supports this model e.g.: HCO3 concentration and the recalculated isotopic composition of gaseous CO2 (δ 13CCO_2 = -4 ± 2.5 ‰ V-PDB) reflect evolved magmatic CO2 uptake and the subsequent leaching progress; High SO42- concentration of up to 16.5 mmol L-1 with δ 34SSO4 = 0.35 ± 0.3 ‰ (V-CDT) reflects magmatic origin which mainly control water chemistry of boiling pools of both Fogo and Furnas lake; δ 18OSO4 = 10.5 ‰ (V-SMOW) suggests organic origin and fits together with the observation of stromatolitic structures in the related precipitates; Molar Mg/Caratio (≈ 0.77) of all thermal discharges reflects leaching of analysed local basalt (Mg/Ca≈ 0.78). Furthermore, shallow and evolved outgassing effects can be distinguished. Equilibrium temperatures for various minerals given in SI vs. T plots and further geothermometers (e.g. Na-K, Na-K-Ca geothermometers) were discussed to estimate temperatures of reservoirs.

Importance of the Lu-Hf isotopic system in studies of planetary chronology and chemical evolution

USGS Publications Warehouse

Patchett, P.J.

1983-01-01

The 176Lu-176Hf isotope method and its applications in earth sciences are discussed. Greater fractionation of Lu/Hf than Sm/Nd in planetary magmatic processes makes 176Hf 177Hf a powerful geochemical tracer. In general, proportional variations of 176Hf 177Hf exceed those of 143Nd l44Nd by factors of 1.5-3 in terrestrial and lunar materials. Lu-Hf studies therefore have a major contribution to make in understanding of terrestrial and other planetary evolution through time, and this is the principal importance of Lu-Hf. New data on basalts from oceanic islands show unequivocally that whereas considerable divergences occur in 176Hf 177Hf- 87Sr 86Sr and 143Nd l44Nd- 87Sr 86Sr diagrams, 176Hf 177Hf and 143Nd 144Nd display a single, linear isotopic variation in the suboceanic mantle. These discordant 87Sr 86Sr relationships may allow, with the acquisition of further Hf-Nd-Sr isotopic data, a distinction between processes such as mantle metasomatism, influence of seawater-altered material in the magma source, or recycling of sediments into the mantle. In order to evaluate the Hf-Nd isotopic correlation in terms of mantle fractionation history, there is a need for measurements of Hf distribution coefficients between silicate minerals and liquids, and specifically for a knowledge of Hf behavior in relation to rareearth elements. For studying ancient terrestrial Hf isotopic variations, the best quality Hf isotope data are obtained from granitoid rocks or zircons. New data show that very U-Pb discordant zircons may have upwardly-biased 176Hf 177Hf, but that at least concordant to slightly discordant zircons appear to be reliable carriers of initial 176Hf 177Hf. Until the controls on addition of radiogenic Hf to zircon are understood, combined zircon-whole rock studies are recommended. Lu-Hf has been demonstrated as a viable tool for dating of ancient terrestrial and extraterrestrial samples, but because it offers little advantage over existing methods, is unlikely to find wide application in pure chronological studies. ?? 1983.

The peculiar geochemical signatures of São Miguel (Azores) lavas: Metasomatised or recycled mantle sources?

NASA Astrophysics Data System (ADS)

Beier, Christoph; Stracke, Andreas; Haase, Karsten M.

2007-07-01

The island of São Miguel, Azores consists of four large volcanic systems that exhibit a large systematic intra-island Sr-Nd-Pb-Hf isotope and trace element variability. The westernmost Sete Cidades volcano has moderately enriched Sr-Nd-Pb-Hf isotope ratios. In contrast, lavas from the easternmost Nordeste volcano have unusually high Sr and Pb and low Nd and Hf isotope ratios suggesting a long-term evolution with high Rb/Sr, U/Pb, Th/Pb, Th/U and low Sm/Nd and Lu/Hf parent-daughter ratios. They have trace element concentrations similar to those of the HIMU islands, with the exception of notably higher alkali element (Cs, Rb, K, Ba) and Th concentrations. The time-integrated parent-daughter element evolution of both the Sete Cidades and Nordeste source matches the incompatibility sequence commonly observed during mantle melting and consequently suggests that the mantle source enrichment is caused by a basaltic melt, either as a metasomatic agent or as recycled oceanic crust. Our calculations show that a metasomatic model involving a small degree basaltic melt is able to explain the isotopic enrichment but, invariably, produces far too enriched trace element signatures. We therefore favour a simple recycling model. The trace element and isotopic signatures of the Sete Cidades lavas are consistent with the presence of ancient recycled oceanic crust that has experienced some Pb loss during sub-arc alteration. The coherent correlation of the parent-daughter ratios (e.g. Rb/Sr, Th/U, U/Pb) and incompatible element ratios (e.g. Nb/Zr, Ba/Rb, La/Nb) with the isotope ratios in lavas from the entire island suggest that the Sete Cidades and Nordeste source share a similar genetic origin. The more enriched trace element and isotopic variations of Nordeste can be reproduced by recycled oceanic crust in the Nordeste source that contains small amounts of evolved lavas (˜ 1-2%), possibly from a subducted seamount. The rare occurrence of enriched source signatures comparable to Nordeste may be taken as circumstantial evidence that stirring processes in the Earth's mantle are not able to homogenise material within the size of seamounts over timescales of mantle recycling.

Unraveling the Environmental Record of the Early Solar System: High Precision Laser Ablation Al-Mg Isotopes of Igneous CAIs

NASA Astrophysics Data System (ADS)

Young, E. D.; Simon, J. I.; Russell, S. S.; Tonui, E.; Krot, A.

2004-12-01

Variations in intrinsic Mg isotope compositions provide a potentially rich record of the physiochemical evolution of CAIs. Moreover, Mg excesses from the short-lived 26Al chronometer can be used to constrain when these processes occurred; e.g., during the nebular phase and/or during the development of planetisimals (< 4 Myr). We obtained in situ UV (213 nm) laser ablation MC-ICPMS measurements of Al and Mg isotope ratios within core-to-rim traverses of igneous CAIs to place temporal constraints on when features of CAIs formed. Results provide tests of models for the chemical and isotopic evolution of CAIs involving volatilization and recondensation of elements in the solar nebula. We studied five CV3 CAIs, including Allende 3576-1 "b", Allende M5, Leoville 144A, Leoville MRS3, and Efremovka E44. Our sample-standard comparison approach affords a precision <0.2 \\permil per amu (2s) for intrinsic Mg isotope measurements and <0.3 \\permil (2s) for measured 26Mg excesses. Intra-object variation in \\delta25Mg exists with values ranging from as low as -2 \\permil and as high as +8 \\permil (compared to DSM3). The distinct Mg isotope patterns in the CAIs are difficult to explain by a single process or within a single nebular environment and likely require changing conditions or transfer of CAIs from one nebular environment to another. The ˜pristine Mg isotope profile of Leoville 144A is compared to results produced by implicit finite difference modeling. Model curves reflect isotopic fractionation at the moving surface of a shrinking molten sphere coupled with diffusion-limited transport within the sphere. We find that using mass-dependant diffusivities increases \\delta25Mg with evaporation, but does not produce the tight curvature in the edgeward increases in \\delta25Mg characteristic of Leoville 144A. Three CAIs that exhibit edgeward \\delta25Mg decreases are well described by diffusion in a Mg-rich chondritic environment suggestive of nebular temperatures and timescales on order of 100 yrs at 1300 K (temperatures <900 K require heating times >2 Myr, and are improbable for parent body thermal histories). We concluded that: (1) CAIs exhibit enriched \\delta25Mg interiors that require evaporation of molten spheres in low total pressures, and/or low Mg partial pressure environments and systematic edgeward mineral independent intrinsic Mg isotope variations (-2 to +8 \\permil per amu) that require multiple evolutionary steps, (2) Isotopic profile measurements are accompanied by excess 26Mg and thus support a nebular origin for their development, (3) After initial isotopic enrichment CAIs undergo at least two divergent thermal histories as demonstrated by the two distinctive groups of Mg isotope profiles and their Al-Mg chronologies, and (4) Wark-Lovering rims are condensates from a nebular gas of chondritic or subchondritic Mg isotope composition that grew while 26Al was still extant.

Biometrics from the carbon isotope ratio analysis of amino acids in human hair.

PubMed

Jackson, Glen P; An, Yan; Konstantynova, Kateryna I; Rashaid, Ayat H B

2015-01-01

This study compares and contrasts the ability to classify individuals into different grouping factors through either bulk isotope ratio analysis or amino-acid-specific isotope ratio analysis of human hair. Using LC-IRMS, we measured the isotope ratios of 14 amino acids in hair proteins independently, and leucine/isoleucine as a co-eluting pair, to provide 15 variables for classification. Multivariate analysis confirmed that the essential amino acids and non-essential amino acids were mostly independent variables in the classification rules, thereby enabling the separation of dietary factors of isotope intake from intrinsic or phenotypic factors of isotope fractionation. Multivariate analysis revealed at least two potential sources of non-dietary factors influencing the carbon isotope ratio values of the amino acids in human hair: body mass index (BMI) and age. These results provide evidence that compound-specific isotope ratio analysis has the potential to go beyond region-of-origin or geospatial movements of individuals-obtainable through bulk isotope measurements-to the provision of physical and characteristic traits about the individuals, such as age and BMI. Further development and refinement, for example to genetic, metabolic, disease and hormonal factors could ultimately be of great assistance in forensic and clinical casework. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Distinct Chlorine Isotopic Reservoirs on Mars: Implications for Character, Extent and Relative Timing of Crustal Interaction with Mantle-Derived Magmas, Evolution of the Martian Atmosphere, and the Building Blocks of an Early Mars

NASA Technical Reports Server (NTRS)

Shearer, C. K.; Messenger, S.; Sharp, Z. D.; Burger, P. V.; Nguyen, N.; McCubbin, F. M.

2017-01-01

The style, magnitude, timing, and mixing components involved in the interaction between mantle derived Martian magmas and Martian crust have long been a point of debate. Understanding this process is fundamental to deciphering the composition of the Martian crust and its interaction with the atmosphere, the compositional diversity and oxygen fugacity variations in the Martian mantle, the bulk composition of Mars and the materials from which it accreted, and the noble gas composition of Mars and the Sun. Recent studies of the chlorine isotopic composition of Martian meteorites imply that although the variation in delta (sup 37) Cl is limited (total range of approximately14 per mille), there appears to be distinct signatures for the Martian crust and mantle. However, there are potential issues with this interpretation. New Cl isotope data from the SAM (Sample Analysis at Mars) instrument on the Mars Science Lab indicate a very wide range of Cl isotopic compositions on the Martian surface. Recent measurements by [10] duplicated the results of [7,8], but placed them within the context of SAM surface data. In addition, Martian meteorite Chassigny contains trapped noble gases with isotopic ratios similar to solar abundance, and has long been considered a pristine, mantle derived sample. However, previous studies of apatite in Chassigny indicate that crustal fluids have interacted with regions interstitial to the cumulus olivine. The initial Cl isotope measurements of apatite in Chassigny suggest an addition of crustal component to this lithology, apparently contradicting the rare gas data. Here, we examine the Cl isotopic composition of multiple generations and textures of apatite in Chassigny to extricate the crustal and mantle components in this meteorite and to reveal the style and timing of the addition of crustal components to mantle-derived magmas. These data reveal distinct Martian Cl sources whose signatures have their origins linked to both the early Solar System and the evolving Martian atmosphere.

What Mantle Processes Determine Isotopic

NASA Astrophysics Data System (ADS)

Tackley, P. J.; Xie, S.

2003-12-01

Isotopic measurements on Mid Ocean Ridge Basalts and Ocean Island Basalts indicate effective `ages' (from e.g., U-Pb or Sm-Nd systems) in the range 1-2 billion years- much less than the age of the Earth, even though melting should have been much more vigorous early on and skewed the mean time since melting to older values. This relatively young `age' has generally been explained in terms of stretching of heterogeneities by mantle convection, which might reduce them to dimensions too small to be individually distinguishable in short timescales of less than 1 Gyr. On the other hand, published numerical models that use tracers to track differentiated material (Christensen and Hofmann, 1994, Davies, 2002) suggest that Earth-like `ages' can be obtained without taking stretching-induced erasure of tracer signatures into account, although this might effectively happen if the lengthscale for sampling the isotope systems was large enough. In those models, the only explicit mechanism for resetting isotope systems was re-melting, but for this to explain the isotopic ages observed for basalts, the global rate of melting in the recent past would have had to be very much higher than present-day values. To investigate stretching vs. re-melting we have conducted numerical experiments of a cooling mantle with plate tectonics, differentiation and evolution of important isotopic systems. The time of last melting and the total strain is tracked on each tracer (in addition to isotopic information). The results confirm that a model matching today's crustal production rate and with a reasonable secular cooling history generates `ages' that are substantially larger than those observed, with the extent of crustal settling above the CMB making some difference but not enough. The effect of sampling lengthscale on observed `age' is also tested and found to be insufficient to explain the data. Thus, these results reaffirm the importance of stretching as a key mechanism for effectively deleting older heterogeneities. From analysis of strain vs. age and matching of the observed ages, it is estimated that erasure of heterogeneities occurs at strains of 103-104, somewhat larger than has often been assumed.

Combining Small-Vertebrate, Marine and Stable-Isotope Data to Reconstruct Past Environments

PubMed Central

Rofes, Juan; Garcia-Ibaibarriaga, Naroa; Aguirre, Mikel; Martínez-García, Blanca; Ortega, Luis; Zuluaga, María Cruz; Bailon, Salvador; Alonso-Olazabal, Ainhoa; Castaños, Jone; Murelaga, Xabier

2015-01-01

Three very different records are combined here to reconstruct the evolution of environments in the Cantabrian Region during the Upper Pleistocene, covering ~35.000 years. Two of these records come from Antoliñako Koba (Bizkaia, Spain), an exceptional prehistoric deposit comprising 9 chrono-cultural units (Aurignacian to Epipaleolithic). The palaeoecological signal of small-vertebrate communities and red deer stable-isotope data (δ13C and δ15N) from this mainland site are contrasted to marine microfaunal evidence (planktonic and benthic foraminifers, ostracods and δ18O data) gathered at the southern Bay of Biscay. Many radiocarbon dates for the Antoliña’s sequence, made it possible to compare the different proxies among them and with other well-known North-Atlantic records. Cooling and warming events regionally recorded, mostly coincide with the climatic evolution of the Upper Pleistocene in the north hemisphere. PMID:26391668

Coupled extremely light Ca and Fe isotopes in peridotites

NASA Astrophysics Data System (ADS)

Zhao, Xinmiao; Zhang, Zhaofeng; Huang, Shichun; Liu, Yufei; Li, Xin; Zhang, Hongfu

2017-07-01

Large metal stable isotopic variations have been observed in both extraterrestrial and terrestrial samples. For example, Ca exhibits large mass-dependent isotopic variation in terrestrial igneous rocks and mantle minerals (on the order of ∼2‰ variation in 44Ca/40Ca). A thorough assessment and understanding of such isotopic variations in peridotites provides important constraints on the evolution and compositon of the Earth's mantle. In order to better understand the Ca and Fe isotopic variations in terrestrial silicate rocks, we report Ca isotopic compositions in a set of peridotitic xenoliths from North China Craton (NCC), which have been studied for Fe isotopes. These NCC peridotites have large Ca and Fe isotopic variations, with δ44/40Ca ranging from -0.08 to 0.92 (delta value relative to SRM915a) and δ57/54Fe (delta value relative to IRMM-014) ranging from -0.61 to 0.16, and these isotopic variations are correlated with large Mg# (100 × Mg/(Mg + Fe) molar ratio) variation, ranging from 80 to 90. Importantly, NCC Fe-rich peridotites have the lowest 44Ca/40Ca and 57Fe/54Fe ratios in all terrestrial silicate rocks. In contrast, although ureilites, mantle rocks from a now broken differentiated asteroid(s), have large Mg# variation, from 70 to 92, they have very limited δ57Fe/54Fe variation (0.03-0.21, delta value relative to IRMM-014). Our model calculations show that the coupled extremely light Ca-Fe isotopic signatures in NCC Fe-rich peridotites most likely reflect kinetic isotopic fractionation during melt-peridotite reaction on a timescale of several to 104 years. In addition, our new data and compiled literature data show a possible compositional effect on the inter-mineral Ca isotopic fractionation between co-existing clinopyroxene and orthopyroxene pairs.

Evaluation of Ages in the Lunar Highlands with Implications for the Evolution of the Moon

NASA Astrophysics Data System (ADS)

Borg, L. E.; Gaffney, A. M.; Carlson, R. W.

2012-12-01

The lunar highlands are composed of rocks from the ferroan anorthosite (FAN) and Mg-suites. These samples have been extensively studied because they record most of the major events associated with the formation and evolution of the Earth's Moon. Despite their potential to constrain the timing of these events, chronologic investigations are often ambiguous; in most cases because absolute ages and/or initial isotopic compositions are inconsistent with stratigraphic and petrologic relationships of various rock suites inferred from mineralogical and geochemical studies. The problem is exacerbated by the fact that most samples are difficult to date due to their small size and nearly monomineralic nature, as well as isotopic disturbances associated with impacts. Here several criteria are used to assess the reliability of lunar ages, including: (1) concordance between multiple chronometers, (2) linearity of individual isochrons, (3) resistance of the chronometers to disruption by impact or contamination, (4) consistency between initial isotopic compositions and the petrogenisis of samples, and (5) reasonableness of the elemental concentrations of mineral fractions. If only those samples that meet 4 out of 5 of these criteria are used to constrain lunar chronology many of the apparent conflicts between chronometry and petrology disappear. For example, this analysis demonstrates that the most ancient ages reported for lunar samples are some of the least reliable. The oldest ages determined on both FAN and Mg-suite highland rocks with confidence are in fact ~4.35 Ga. This age is concordant with 142Nd mare source formation ages and a peak in zircon ages, suggesting it represents a major event at ~4.35 Ga. In contrast, several apparently reliable KREEP model ages are older at ~4.48 Ga. If these older model ages are correct, they may represent the solidification age of the Moon, whereas the 4.35 Ga event could reflect secondary magmatism and cumulate re-equilibration associated with density overturn of primordial magma ocean cumulates.

Hydrogen isotopes in lunar volcanic glasses and melt inclusions reveal a carbonaceous chondrite heritage.

PubMed

Saal, Alberto E; Hauri, Erik H; Van Orman, James A; Rutherford, Malcolm J

2013-06-14

Water is perhaps the most important molecule in the solar system, and determining its origin and distribution in planetary interiors has important implications for understanding the evolution of planetary bodies. Here we report in situ measurements of the isotopic composition of hydrogen dissolved in primitive volcanic glass and olivine-hosted melt inclusions recovered from the Moon by the Apollo 15 and 17 missions. After consideration of cosmic-ray spallation and degassing processes, our results demonstrate that lunar magmatic water has an isotopic composition that is indistinguishable from that of the bulk water in carbonaceous chondrites and similar to that of terrestrial water, implying a common origin for the water contained in the interiors of Earth and the Moon.

Fractionation of nitrogen isotopic on Mars: The role of the regolith as a buffer

NASA Technical Reports Server (NTRS)

Zent, A. P.; Quinn, R. C.; Jakosky, B. M.

1994-01-01

We have measured the adsorption of molecular nitrogen (N2) on palagonite, and modeled the adsorbed nitrogen inventory on the martian regolith. We were motivated by the fact that models of isotopic evolution predict stronger N2 fractionation than reported by Viking. Possible scenarios for reconciling models with the observation include a heavy CO2 atmosphere early in the planet's history, continued outgassing of N2 throughout the history of Mars, or a substantial adsorbed inventory. In this paper we investigate the plausibility of the last explanation. We find that the regolith reservoir of adsorbed N2 is inadequate by itself to buffer the atmospheric isotopic composition, but may play a role depending on the total regolith surface area available.

Evolution of collectivity near mid-shell from excited-state lifetime measurements in rare earth nuclei

NASA Astrophysics Data System (ADS)

Werner, V.; Cooper, N.; Régis, J.-M.; Rudigier, M.; Williams, E.; Jolie, J.; Cakirli, R. B.; Casten, R. F.; Ahn, T.; Anagnostatou, V.; Berant, Z.; Bonett-Matiz, M.; Elvers, M.; Heinz, A.; Ilie, G.; Radeck, D.; Savran, D.; Smith, M. K.

2016-03-01

The B (E 2 ) excitation strength of the first excited 2+ state in even-even nuclei should directly correlate with the size of the valence space and maximize at mid-shell. A previously found saturation of B (E 2 ) strengths in well-deformed rotors at mid-shell is tested through high-precision measurements of the lifetimes of the lowest-lying 2+ states of the 168Hf and 174W rare earth isotopes. Measurements were performed using fast LaBr3 scintillation detectors. Combined with the recently remeasured B (E 2 ;21+→01+) values for Hf and W isotopes the new data remove discrepancies observed in the differentials of B (E 2 ) values for these isotopes.

CNO isotopes in red giant stars

NASA Technical Reports Server (NTRS)

Wannier, P. G.

1985-01-01

Observational data on CNO abundance ratios in red giants and the interstellar medium (ISM) are analyzed for the implications for the production and distribution of CNO nuclides. The data included isotope abundance measurements for the atmospheres and recent ejecta of cool giants, e.g., carbon stars, S-type stars, red supergiants and oxygen-rich giants beginning an ascent of the giant branch. The contribution of intermediate-mass stars to galactic nuclear evolution is discussed after comparing red giant abundances with ISM abundances, particularly the isotopes O-16, -17 and -18. The O-12/O-18 ratios of red giants are distinctly different from those in interstellar molecular clouds. The CNO values also vary widely from the values found in the solar system.

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.

Decadal time scale variability recorded in the Quelccaya summit ice core δ18O isotopic ratio series and its relation with the sea surface temperature

NASA Astrophysics Data System (ADS)

Mélice, J. L.; Roucou, P.

The spectral characteristics of the δ18O isotopic ratio time series of the Quelccaya ice cap summit core are investigated with the multi taper method (MTM), the singular spectrum analysis (SSA) and the wavelet transform (WT) techniques for the 500 y long 1485-1984 period. The most significant (at the 99.8% level) cycle according to the MTM F-test has a period centered at 14.4 y while the largest variance explaining oscillation according to the SSA technique has a period centered at 12.9 y. The stability over time of these periods is investigated by performing evolutive MTM and SSA on the 500 y long δ18O series with a 100 y wide moving window. It is shown that the cycles with largest amplitude and that the oscillations with largest extracting variance have corresponding periods aggregated around 13.5 y that are very stable over the period between 1485 and 1984. The WT of the same isotopic time series reveals the existence of a main oscillation around 12 y which are also very stable in time. The relation between the isotopic data at Quelccaya and the annual sea surface temperature (SST) field anomalies is then evaluated for the overlapping 1919-1984 period. Significant global correlation and significant coherency at 12.1 y are found between the isotopic series and the annual global sea surface temperature (GSST) series. Moreover, the correlation between the low (over 8 y) frequency component of the isotopic time series and the annual SST field point out significant values in the tropical North Atlantic. This region is characterized by a main SST variability at 12.8 y. The Quelccaya δ18O isotopic ratio series may therefore be considered as a good recorder of the tropical North Atlantic SSTs. This may be explained by the following mechanism: the water vapor amount evaporated by the tropical North Atlantic is function of the SST. So is the water vapor δ18O isotopic ratio. This water vapor is advected during the rainy season by northeast winds and precipitates at the Quelccaya summit with its tropical North Atlantic isotopic signature. It is also suggested from this described stability of the decadal time scale variability observed in the Quelccaya isotopic series, that the decadal time scale GSST variability was also stable during the last five centuries.

Fragmentary Solar System History

NASA Technical Reports Server (NTRS)

Marti, Kurt

1997-01-01

The objective of this research is an improved understanding of the early solar system environment and of the processes involved in the nebula and in the evolution of solid bodies. We present results of our studies on the isotopic signatures in selected primitive solar system objects and on the evaluation of the cosmic ray records and of inferred collisional events. Furthermore, we report data of trapped martian atmospheric gases in meteorites and the inferred early evolution of Mars' atmosphere.

Fe isotopes and the contrasting petrogenesis of A-, I- and S-type granite

NASA Astrophysics Data System (ADS)

Foden, John; Sossi, Paolo A.; Wawryk, Christine M.

2015-01-01

We present new Fe isotope data of 42 S-, I- and A-type (ferroan) granites from the Cambrian Delamerian orogen in South Australia, the Palaeozoic Lachlan Fold Belt and Western USA. Interpretation of these data, together with modelling suggests that magmatic processes do result in quite complex Fe-isotopic differentiation trends and can lead to granites with isotopically heavy iron with δ57Fe > 0.35‰. By comparison Mid-Ocean Ridge Basalts (MORBs) have δ57Fe = 0.15‰ (Teng et al., 2013). These variations are similar to those previously reported (Poitrasson and Freydier, 2005; Heimann et al., 2008; Telus et al., 2012), but, contrary to some interpretations (Beard and Johnson, 2006; Heimann et al., 2008), heavy values are not necessarily the product of late-stage hydrothermal fluid loss, though this process is undoubtedly also an important factor in some circumstances. A-type (ferroan) granites reach very heavy δ57Fe values (0.4-0.5‰) whereas I-types are systematically lighter (δ57Fe = 0.2‰). S-type granites show a range of intermediate values, but also tend to be isotopically heavy (δ57Fe ≈ 0.2-0.4‰). Our results show that the iron isotopic values and trends are signatures that reflect granite generation processes. A modelling using the Rhyolite-MELTS software suggests that contrasting trajectories and end-points in Fe isotope evolution towards granite depend on: oxidation state of the evolving magma and, whether or not the system is oxygen-buffered. Iron isotopic evolution supports an origin of ferroan A-type granite from protracted, closed magma chamber fractionation of moderately reduced mafic magmas. In these systems magnetite saturation is delayed and the ferric iron budget is finite. I-type systems originate with the supply of relatively oxidised, hydrous, subduction-related magmas from the mantle wedge to the upper plate crust. These then experience oxygen-buffered open-system AFC processes in lower crustal hot-zones. S-type magmas are crustal melts that crystallise under reduced conditions initially imposed at source by sulphidic or graphitic sedimentary protoliths. The composition of the resulting melts reflects the domination of partial melting where conditions are hence buffered (open system) followed by subsequent late-stage, closed system fractionation of these extracted, reduced magmas.

Hydrogen Isotopic Systematics of Nominally Anhydrous Phases in Martian Meteorites

NASA Astrophysics Data System (ADS)

Tucker, Kera

Hydrogen isotope compositions of the martian atmosphere and crustal materials can provide unique insights into the hydrological and geological evolution of Mars. While the present-day deuterium-to-hydrogen ratio (D/H) of the Mars atmosphere is well constrained (~6 times that of terrestrial ocean water), that of its deep silicate interior (specifically, the mantle) is less so. In fact, the hydrogen isotope composition of the primordial martian mantle is of great interest since it has implications for the origin and abundance of water on that planet. Martian meteorites could provide key constraints in this regard, since they crystallized from melts originating from the martian mantle and contain phases that potentially record the evolution of the H 2O content and isotopic composition of the interior of the planet over time. Examined here are the hydrogen isotopic compositions of Nominally Anhydrous Phases (NAPs) in eight martian meteorites (five shergottites and three nakhlites) using Secondary Ion Mass Spectrometry (SIMS). This study presents a total of 113 individual analyses of H2O contents and hydrogen isotopic compositions of NAPs in the shergottites Zagami, Los Angeles, QUE 94201, SaU 005, and Tissint, and the nakhlites Nakhla, Lafayette, and Yamato 000593. The hydrogen isotopic variation between and within meteorites may be due to one or more processes including: interaction with the martian atmosphere, magmatic degassing, subsolidus alteration (including shock), and/or terrestrial contamination. Taking into consideration the effects of these processes, the hydrogen isotope composition of the martian mantle may be similar to that of the Earth. Additionally, this study calculated upper limits on the H2O contents of the shergottite and nakhlite parent melts based on the measured minimum H2O abundances in their maskelynites and pyroxenes, respectively. These calculations, along with some petrogenetic assumptions based on previous studies, were subsequently used to infer the H2O contents of the mantle source reservoirs of the depleted shergottites (200-700 ppm) and the nakhlites (10-100 ppm). This suggests that mantle source of the nakhlites is systematically drier than that of the depleted shergottites, and the upper mantle of Mars may have preserved significant heterogeneity in its H2O content. Additionally, this range of H2O contents is not dissimilar to the range observed for the Earth's upper mantle.

Variable microstructural response of baddeleyite to shock metamorphism in young basaltic shergottite NWA 5298 and improved U-Pb dating of Solar System events

NASA Astrophysics Data System (ADS)

Darling, James R.; Moser, Desmond E.; Barker, Ivan R.; Tait, Kim T.; Chamberlain, Kevin R.; Schmitt, Axel K.; Hyde, Brendt C.

2016-06-01

The accurate dating of igneous and impact events is vital for the understanding of Solar System evolution, but has been hampered by limited knowledge of how shock metamorphism affects mineral and whole-rock isotopic systems used for geochronology. Baddeleyite (monoclinic ZrO2) is a refractory mineral chronometer of great potential to date these processes due to its widespread occurrence in achondrites and robust U-Pb isotopic systematics, but there is little understanding of shock-effects on this phase. Here we present new nano-structural measurements of baddeleyite grains in a thin-section of the highly-shocked basaltic shergottite Northwest Africa (NWA) 5298, using high-resolution electron backscattered diffraction (EBSD) and scanning transmission electron microscopy (STEM) techniques, to investigate shock-effects and their linkage with U-Pb isotopic disturbance that has previously been documented by in-situ U-Pb isotopic analyses. The shock-altered state of originally igneous baddeleyite grains is highly variable across the thin-section and often within single grains. Analyzed grains range from those that preserve primary (magmatic) twinning and trace-element zonation (baddeleyite shock Group 1), to quasi-amorphous ZrO2 (Group 2) and to recrystallized micro-granular domains of baddeleyite (Group 3). These groups correlate closely with measured U-Pb isotope compositions. Primary igneous features in Group 1 baddeleyites (n = 5) are retained in high shock impedance grain environments, and an average of these grains yields a revised late-Amazonian magmatic crystallization age of 175 ± 30 Ma for this shergottite. The youngest U-Pb dates occur from Group 3 recrystallized nano- to micro-granular baddeleyite grains, indicating that it is post-shock heating and new mineral growth that drives much of the isotopic disturbance, rather than just shock deformation and phase transitions. Our data demonstrate that a systematic multi-stage microstructural evolution in baddeleyite results from a single cycle of shock-loading, heating and cooling during transit to space, and that this leads to variable disturbance of the U-Pb isotope system. Furthermore, by linking in-situ U-Pb isotopic measurements with detailed micro- to nano-structural analyses, it is possible to resolve the timing of both endogenic crustal processes and impact events in highly-shocked planetary materials using baddeleyite. This opens up new opportunities to refine the timing of major events across the Solar System.

Key Largo Limestone revisited: Pleistocene shelf-edge facies, Florida Keys, USA

USGS Publications Warehouse

Gray, Multer H.; Gischler, E.; Lundberg, J.; Simmons, K.R.; Shinn, E.A.

2002-01-01

New dates and analysis of 12 deep and 57 shallow cores allow a more detailed interpretation of the Pleistocene shelf edge of the Florida Platform as found in various facies of the Key Largo Limestone beneath the Florida Keys. In this study a three-phase evolution of the Quaternary units (Q1-Q5) of the Key Largo is presented with new subdivision of the Q5. (1) In the first phase, the Q1 and Q2 (perhaps deposited during oxygen-isotope stage 11) deep-water quartz-rich environment evolved into a shallow carbonate phase. (2) Subsequently, a Q3 (presumably corresponding to oxygen-isotope stage 9) flourishing reef and productive high-platform sediment phase developed. (3) Finally, a Q4 and Q5 (corresponding to oxygen-isotope stages 7 and 5) stabilization phase occured with reefs and leeward productive lagoons, followed by lower sea levels presenting a sequence of younger (isotope substages 5c, 5a) shelf-margin wedges, sediment veneers and outlier reefs. The Key Largo Limestone provides an accessible model of a carbonate shelf edge with fluctuating water depth, bordering a deep seaward basin for a period of at least 300 ka. During this time, at least four onlaps/offlaps, often separated by periods of karst development with associated diagenetic alterations, took place. The story presented by this limestone not only allows a better understanding of the history of south Florida but also aids in the interpretation of similar persistent shelf-edge sites bordering deep basins in other areas.

Hydrological processes in glacierized high-altitude basins of the western Himalayas

NASA Astrophysics Data System (ADS)

Jeelani, Ghulam; Shah, Rouf A.; Fryar, Alan E.; Deshpande, Rajendrakumar D.; Mukherjee, Abhijit; Perrin, Jerome

2018-03-01

Western Himalaya is a strategically important region, where the water resources are shared by China, India and Pakistan. The economy of the region is largely dependent on the water resources delivered by snow and glacier melt. The presented study used stable isotopes of water to further understand the basin-scale hydro-meteorological, hydrological and recharge processes in three high-altitude mountainous basins of the western Himalayas. The study provided new insights in understanding the dominant factors affecting the isotopic composition of the precipitation, snowpack, glacier melt, streams and springs. It was observed that elevation-dependent post-depositional processes and snowpack evolution resulted in the higher isotopic altitude gradient in snowpacks. The similar temporal trends of isotopic signals in rivers and karst springs reflect the rapid flow transfer due to karstification of the carbonate aquifers. The attenuation of the extreme isotopic input signal in karst springs appears to be due to the mixing of source waters with the underground karst reservoirs. Basin-wise, the input-output response demonstrates the vital role of winter precipitation in maintaining the perennial flow in streams and karst springs in the region. Isotopic data were also used to estimate the mean recharge altitude of the springs.

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.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

The geologic evolution of the moon

NASA Technical Reports Server (NTRS)

Lowman, P. D., Jr.

1971-01-01

A synthesis of pre- and post-Apollo 11 studies is presented to produce an outline of the moon's geologic evolution from three lines of evidence: (1) relative ages of lunar landforms and rock types, (2) absolute ages of returned lunar samples, and (3) petrography, chemistry, and isotopic ratios of lunar rocks and soils. It is assumed that the ray craters, circular mare basins, and most intermediate circular landforms are primarily of impact origin, although many other landforms are volcanic or of hybrid origin. The moon's evolution is divided into four main stages, each including several distinct but overlapping events or processes.

The evolution of Gondwana: U-Pb, Sm-Nd, Pb-Pb and geochemical data from Neoproterozoic to Early Palaeozoic successions of the Kango Inlier (Saldania Belt, South Africa)

NASA Astrophysics Data System (ADS)

Naidoo, Thanusha; Zimmermann, Udo; Chemale, Farid

2013-08-01

The provenance of Neoproterozoic to Early Palaeozoic rocks at the southern margin of the Kalahari craton reveals a depositional setting and evolution with a significant position in the formation of Gondwana. The sedimentary record shows a progression from immature, moderately altered rocks in the Ediacaran Cango Caves Group; to mature, strongly altered rocks in the Early Palaeozoic Kansa Group and overlying formations; culminating below very immature quartzarenites of Ordovician age. Petrographic and geochemical observations suggest the evolution of a small restricted basin with little recycling space towards a larger continental margin where substantial turbidite deposition is observed. For the southern Kalahari craton, a tectonic evolution comparable to supracrustal rocks in southern South America, Patagonia and Antarctica is supported by similarities in U-Pb ages of detrital zircons (Mesoproterozoic, Ediacaran and Ordovician grain populations); Sm-Nd isotopes (TDM: 1.2-1.8 Ga); and Pb-Pb isotopes. The maximum depositional age of the Huis Rivier Formation (upper Cango Caves Group) is determined at 644 Ma, but a younger age is still possible due to the limited zircon yield. The Cango Caves Group developed in a retro-arc foreland basin syntectonically to the Terra Australis Orogeny, which fringed Gondwana. The Kansa Group and overlying Schoemanspoort Formation are related to an active continental margin developed after the Terra Australis Orogen, with Patagonia being the ‘missing link’ between the Central South American arc and Antarctica during the Ordovician. This explains the occurrence of Ordovician detritus in these rocks, as a source rock of this age has not been discovered in South Africa. The absence of arc characteristics defines a position distal to the active continental margin, in a retro-arc foreland basin. The similarity of isotope proxies to major tectonic provinces in Antarctica and Patagonia, with those on the margins of the Kalahari craton, also points to a common geological evolution during the Mesoproterozoic and highlights the global relevance of this study.

Evolution of chemical and isotopic composition of inorganic carbon in a complex semi-arid zone environment: Consequences for groundwater dating using radiocarbon

NASA Astrophysics Data System (ADS)

Meredith, K. T.; Han, L. F.; Hollins, S. E.; Cendón, D. I.; Jacobsen, G. E.; Baker, A.

2016-09-01

Estimating groundwater age is important for any groundwater resource assessment and radiocarbon (14C) dating of dissolved inorganic carbon (DIC) can provide this information. In semi-arid zone (i.e. water-limited environments), there are a multitude of reasons why 14C dating of groundwater and traditional correction models may not be directly transferable. Some include; (1) the complex hydrological responses of these systems that lead to a mixture of different ages in the aquifer(s), (2) the varied sources, origins and ages of organic matter in the unsaturated zone and (3) high evaporation rates. These all influence the evolution of DIC and are not easily accounted for in traditional correction models. In this study, we determined carbon isotope data for; DIC in water, carbonate minerals in the sediments, sediment organic matter, soil gas CO2 from the unsaturated zone, and vegetation samples. The samples were collected after an extended drought, and again after a flood event, to capture the evolution of DIC after varying hydrological regimes. A graphical method (Han et al., 2012) was applied for interpretation of the carbon geochemical and isotopic data. Simple forward mass-balance modelling was carried out on key geochemical processes involving carbon and agreed well with observed data. High values of DIC and δ13CDIC, and low 14CDIC could not be explained by a simple carbonate mineral-CO2 gas dissolution process. Instead it is suggested that during extended drought, water-sediment interaction leads to ion exchange processes within the top ∼10-20 m of the aquifer which promotes greater calcite dissolution in saline groundwater. This process was found to contribute more than half of the DIC, which is from a mostly 'dead' carbon source. DIC is also influenced by carbon exchange between DIC in water and carbonate minerals found in the top 2 m of the unsaturated zone. This process occurs because of repeated dissolution/precipitation of carbonate that is dependent on the water salinity driven by drought and periodic flooding conditions. This study shows that although 14C cannot be directly applied as a dating tool in some circumstances, carbon geochemical/isotopic data can be useful in hydrological investigations related to identifying groundwater sources, mixing relations, recharge processes, geochemical evolution, and interaction with surface water.

Repeated kimberlite magmatism beneath Yakutia and its relationship to Siberian flood volcanism: Insights from in situ U-Pb and Sr-Nd perovskite isotope analysis

NASA Astrophysics Data System (ADS)

Sun, Jing; Liu, Chuan-Zhou; Tappe, Sebastian; Kostrovitsky, Sergey I.; Wu, Fu-Yuan; Yakovlev, Dmitry; Yang, Yue-Heng; Yang, Jin-Hui

2014-10-01

We report combined U-Pb ages and Sr-Nd isotope compositions of perovskites from 50 kimberlite occurrences, sampled from 9 fields across the Yakutian kimberlite province on the Siberian craton. The new U-Pb ages, together with previously reported geochronological constraints, suggest that kimberlite magmas formed repeatedly during at least 4 episodes: Late Silurian-Early Devonian (419-410 Ma), Late Devonian-Early Carboniferous (376-347 Ma), Late Triassic (231-215 Ma), and Middle/Late Jurassic (171-156 Ma). Recurrent kimberlite melt production beneath the Siberian craton - before and after flood basalt volcanism at 250 Ma - provides a unique opportunity to test existing models for the origin of global kimberlite magmatism. The internally consistent Sr and Nd isotope dataset for perovskites reveals that the Paleozoic and Mesozoic kimberlites of Yakutia have distinctly different initial radiogenic isotope compositions. There exists a notable increase in the initial 143Nd/144Nd ratios through time, with an apparent isotopic evolution that is intermediate between that of Bulk Earth and Depleted MORB Mantle. While the Paleozoic samples range between initial 87Sr/86Sr of 0.7028-0.7034 and 143Nd/144Nd of 0.51229-0.51241, the Mesozoic samples show values between 0.7032-0.7038 and 0.51245-0.51271, respectively. Importantly, perovskites from all studied Yakutian kimberlite fields and age groups have moderately depleted initial εNd values that fall within a relatively narrow range between +1.8 and +5.5. The perovskite isotope systematics of the Yakutian kimberlites are interpreted to reflect magma derivation from the convecting upper mantle, which appears to have a record of continuous melt depletion and crustal recycling throughout the Phanerozoic. The analyzed perovskites neither record highly depleted nor highly enriched isotopic components, which had been previously identified in likely plume-related Siberian Trap basalts. The Siberian craton has frequently been suggested to represent a type example of an association between kimberlite eruptions and flood basaltic volcanism within a single large igneous province (LIP), but our new extensive age and isotopic tracer constraints do not support a genetic link between these contrasting types of mantle-derived magmatism.

Decoding mass-independent fractionation of sulfur isotopes in modern atmosphere using cosmogenic 35S: A five-isotope approach and possible implications for Archean sulfur isotope records

NASA Astrophysics Data System (ADS)

Lin, M.; Thiemens, M. H.; Shen, Y.; Zhang, X.; Huang, X.; Chen, K.; Zhang, Z.; Tao, J.

2017-12-01

The signature of sulfur isotopic mass-independent fractionation (S-MIF) observed in Archean sediments have been interpreted as a proxy of the origins and evolution of atmospheric oxygen and early life on Earth [1]. Photochemistry of SOx in the short (< 290 nm) wavelength region accounts for much of the Archean record, but the S-MIF widely observed in modern tropospheric sulfate aerosols remains unexplained, indicating embedded uncertainties in interpreting Archean S-MIF records [2]. Here we present combined measurements of cosmogenic 35S (a stratospheric tracer) [3] and all four stable sulfur isotopes in the same modern atmospheric sulfate samples to define the mechanisms. The five-sulfur-isotope approach reveals that an altitude-dependent process (probably SOx photochemistry) mainly contributes to a positive Δ33S and a combustion-related process mainly leads to a negative Δ36S. After eliminating combustion impacts, the obtained Δ36S/Δ33S slope of -4.0 in the modern atmosphere is close to the Δ36S/Δ33S slope (-3.6) in some records from Paleoarchean [4], an era probably with active volcanism [5]. The significant role of volcanic OCS in the Archean atmosphere has been called for in terms of its ability to provide a continual SO2 high altitude source for photolysis [2]. The strong but previously underappreciated stratospheric signature of S-MIF in tropospheric sulfates suggests that a more careful investigation of wavelength-dependent sulfur isotopic fractionation at different altitudes are required. The combustion-induced negative Δ36S may be linked to recombination reactions of elemental sulfur [6], and relevant experiments are being conducted to test the isotope effect. Although combustion is unlikely in Archean, recombination reactions may occur in other previously unappreciated processes such as volcanism and may contribute in part to the heavily depleted 36S in some Paleoarchean records [5,7]. The roles of both photochemical and non-photochemical reactions in the variability of Archean S-MIF records require further analysis in the future. Refs: [1] Farquhar et al., Science 2000; [2] Shaheen et al., PNAS 2014; [3] Lin et al., PNAS 2016; [4] Wacey et al., Precambrian Res 2015; [5] Muller et al., PNAS 2016; [6] Babikov, PNAS 2017; [7] Shen et al., EPSL, 2009.

Sr isotopic composition of Afar volcanics and its implication for mantle evolution

NASA Astrophysics Data System (ADS)

Barberi, F.; Civetta, L.; Varet, J.

1980-10-01

Investigations of Rb-Sr systematics of basalts from the Afar depression (Ethiopia) indicate the presence of a heterogeneous mantle source region. The Sr isotopic compositions of the basalts from the Afar axial and transverse ranges identify source regions which are enriched in LIL elements and radiogenic Sr (axial ranges) and others which are relatively depleted (transverse ranges). Sr isotopic composition of basalts from the Red Sea, Gulf of Aden and Gulf of Tadjoura, which range from 0.70300 to 0.70340 are also reported and compared with the more radiogenic Afar region, which is characterized by 87Sr/ 86Sr ranging from 0.70328 to 0.70410. Available geochemical and isotopic data suggest that a relation exists between magma composition and the advancement of the rifting process through progressive lithosphere attenuation leading to continental break-up. However, the petrogenetic process is not simple and probably implies a vertically zoned mantle beneath the Afar region. Sr isotopic evidence suggests that the vertically zoned mantle is more radiogenic and enriched in LIL elements in its upper part.

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

Piper, Stephen C; Keeling, Ralph F

The main objective of this project was to continue research to develop carbon cycle relationships related to the land biosphere based on remote measurements of atmospheric CO2 concentration and its isotopic ratios 13C/12C, 18O/16O, and 14C/12C. The project continued time-series observations of atmospheric carbon dioxide and isotopic composition begun by Charles D. Keeling at remote sites, including Mauna Loa, the South Pole, and eight other sites. Using models of varying complexity, the concentration and isotopic measurements were used to study long-term change in the interhemispheric gradients in CO2 and 13C/12C to assess the magnitude and evolution of the northern terrestrialmore » carbon sink, to study the increase in amplitude of the seasonal cycle of CO2, to use isotopic data to refine constraints on large scale changes in isotopic fractionation which may be related to changes in stomatal conductance, and to motivate improvements in terrestrial carbon cycle models. The original proposal called for a continuation of the new time series of 14C measurements but subsequent descoping to meet budgetary constraints required termination of measurements in 2007.« less

Collaborative Project: Development of an Isotope-Enabled CESM for Testing Abrupt Climate Changes

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

Liu, Zhengyu

One of the most important validations for a state-of-art Earth System Model (ESM) with respect to climate changes is the simulation of the climate evolution and abrupt climate change events in the Earth’s history of the last 21,000 years. However, one great challenge for model validation is that ESMs usually do not directly simulate geochemical variables that can be compared directly with past proxy records. In this proposal, we have met this challenge by developing the simulation capability of major isotopes in a state-of-art ESM, the Community Earth System Model (CESM), enabling us to make direct model-data comparison by comparingmore » the model directly against proxy climate records. Our isotope-enabled ESM incorporates the capability of simulating key isotopes and geotracers, notably δ 18O, δD, δ 14C, and δ 13C, Nd and Pa/Th. The isotope-enabled ESM have been used to perform some simulations for the last 21000 years. The direct comparison of these simulations with proxy records has shed light on the mechanisms of important climate change events.« less

Workshop on Evolution of Martian Volatiles. Part 1

NASA Technical Reports Server (NTRS)

Jakosky, B. (Editor); Treiman, A. (Editor)

1996-01-01

This volume contains papers that were presented on February 12-14, 1996 at the Evolution for Martian Volatiles Workshop. Topics in this volume include: returned Martian samples; acidic volatiles and the Mars soil; solar EUV Radiation; the ancient Mars Thermosphere; primitive methane atmospheres on Earth and Mars; the evolution of Martian water; the role of SO2 for the climate history of Mars; impact crater morphology; the formation of the Martian drainage system; atmospheric dust-water ice Interactions; volatiles and volcanos; accretion of interplanetary dust particles; Mars' ionosphere; simulations with the NASA Ames Mars General Circulation Model; modeling the Martian water cycle; the evolution of Martian atmosphere; isotopic composition; solar occultation; magnetic fields; photochemical weathering; NASA's Mars Surveyor Program; iron formations; measurements of Martian atmospheric water vapor; and the thermal evolution Models of Mars.

Asian dust input in the western Philippine Sea: Evidence from radiogenic Sr and Nd isotopes

NASA Astrophysics Data System (ADS)

Jiang, Fuqing; Frank, Martin; Li, Tiegang; Chen, Tian-Yu; Xu, Zhaokai; Li, Anchun

2013-05-01

The radiogenic strontium (Sr) and neodymium (Nd) isotope compositions of the detrital fraction of surface and subsurface sediments have been determined to trace sediment provenance and contributions from Asian dust off the east coast of Luzon Islands in the western Philippine Sea. The Sr and Nd isotope compositions have been very homogenous near the east coast of the Luzon Islands during the latest Quaternary yielding relatively least radiogenic Sr (87Sr/86Sr = 0.70453 to 0.70491) and more radiogenic Nd isotope compositions (ɛNd(0) = +5.3 to +5.5). These isotope compositions are similar to Luzon rocks and show that these sediments were mainly derived from the Luzon Islands. In contrast, the Sr and Nd isotope compositions of sediments on the Benham Rise and in the Philippine Basin are markedly different in that they are characterized by overall more variable and more radiogenic Sr isotope compositions (87Sr/86Sr = 0.70452 to 0.70723) and less radiogenic Nd isotope compositions (ɛNd(0) = -5.3 to +2.4). The Sr isotope composition in the Huatung Basin is intermediate between those of the east coast of Luzon and Benham Rise, but shows the least radiogenic Nd isotope compositions. The data are consistent with a two end-member mixing relationship between Luzon volcanic rocks and eolian dust from the Asian continent, which is characterized by highly radiogenic Sr and unradiogenic Nd isotope compositions. The results show that Asian continental dust contributes about 10-50% of the detrital fraction of the sediments on Benham Rise in the western Philippine Sea, which offers the potentials to reconstruct the climatic evolution of eastern Asia from these sediments and compare this information to the records from the central and northern Pacific.

H, O, Sr, Nd, and Pb isotope geochemistry of the Latir volcanic field and cogenetic intrusions, New Mexico, and relations between evolution of a continental magmatic center and modifications of the lithosphere

USGS Publications Warehouse

Johnson, C.M.; Lipman, P.W.; Czamanske, G.K.

1990-01-01

Over 200 H, O, Sr, Nd, and Pb isotope analyses, in addition to geologic and petrologic constraints, document the magmatic evolution of the 28.5-19 Ma Latir volcanic field and associated intrusive rocks, which includes multiple stages of crustal assimilation, magma mixing, protracted crystallization, and open- and closed-system evolution in the upper crust. In contrast to data from younger volcanic centers in northern New Mexico, relatively low and restricted primary ??18O values (+6.4 to +7.4) rule out assimilation of supracrustal rocks enriched in 18O. Initial 87Sr/86Sr ratios (0.705 to 0.708), ??18O values (-2 to-7), and 206Pb/204Pb ratios (17.5 to 18.4) of metaluminous precaldera volcanic rocks and postcaldera plutonic rocks suggest that most Latir rocks were generated by fractional crystallization of substantial volumes of mantle-derived basaltic magma that had near-chondritic Nd isotope ratios, accompanied by assimilation of crustal material in two main stages: 1) assimilation of non-radiogenic lower crust, followed by 2) assimilation of middle and upper crust by inter-mediate-composition magmas that had been contaminated during the first stage. Magmatic evolution in the upper crust peaked with eruption of the peralkaline Amalia Tuff (???26 Ma), which evolved from metaluminous parental magmas. A third stage of late, roofward assimilation of Proterozoic rocks in the Amalia Tuff magma is indicated by trends in initial 87Sr/86Sr and 206Pb/204Pb ratios from 0.7057 to 0.7098 and 19.5 to 18.8, respectively, toward the top of the pre-eruptive magma chamber. Highly evolved postcaldera plutons are generally fine grained and are zoned in initial 87Sr/86Sr and 206Pb/204Pb ratios, varying from 0.705 to 0.709 and 17.8 to 18.6, respectively. In contrast, the coarser-grained Cabresto Lake (???25 Ma) and Rio Hondo (???21 Ma) plutons have relatively homogeneous initial 87Sr/86Sr and 206Pb/204Pb ratios of approximately 0.7053 and 17.94 and 17.55, respectively. ??18O values for all the postcaldera plutons overlap those of the precaldera rocks and Amalia Tuff, except for those for two late-stage rhyolite dikes associated with the Rio Hondo pluton that have ??18O values of-8.6 and-9.5; these dikes are the only Latir rocks which may be largely crustal melts. Chemical and isotopic data from the Latir field suggest that large fluxes of mantle-derived basaltic magma are necessary for developing and sustaining large-volume volcanic centers. Development of a detailed model suggests that 6-15 km of new crust may have been added beneath the volcanic center; such an addition may result in significant changes in the chemical and Sr and Nd isotopic compositions of the crust, although Pb isotope ratios will remain relatively unchanged. If accompanied by assimilation, crystallization of pooled basaltic magma near the MOHO may produce substantial cumulates beneath the MOHO that generate large changes in the isotopic composition of the upper mantle. The Latir field may be similar to other large-volume, long-lived intracratonal volcanic fields that fundamentally owe their origins to extensive injection of basaltic magma into the lower parts of their magmatic systems. Such fields may overlie areas of significant crustal growth and hybridization. ?? 1990 Springer-Verlag.

Applications of stable isotope analysis in mammalian ecology.

PubMed

Walter, W David; Kurle, Carolyn M; Hopkins, John B

2014-01-01

In this editorial, we provide a brief introduction and summarize the 10 research articles included in this Special Issue on Applications of stable isotope analysis in mammalian ecology. The first three articles report correction and discrimination factors that can be used to more accurately estimate the diets of extinct and extant mammals using stable isotope analysis. The remaining seven applied research articles use stable isotope analysis to address a variety of wildlife conservation and management questions from the oceans to the mountains.

Evolution of the Reactor Antineutrino Flux and Spectrum at Daya Bay

DOE PAGES

An, F. P.; Balantekin, A. B.; Band, H. R.; ...

2017-06-19

Here, the Daya Bay experiment has observed correlations between reactor core fuel evolution and changes in the reactor antineutrino flux and energy spectrum. Four antineutrino detectors in two experimental halls were used to identify 2.2 million inverse beta decays (IBDs) over 1230 days spanning multiple fuel cycles for each of six 2.9 GW th reactor cores at the Daya Bay and Ling Ao nuclear power plants. Using detector data spanning effective 239Pu fission fractions F 239 from 0.25 to 0.35, Daya Bay measures an average IBD yield ¯σf of (5.90±0.13)×10 –43 cm 2/fission and a fuel-dependent variation in the IBDmore » yield, dσ f/dF 239, of (–1.86±0.18)×10 –43 cm 2/fission. This observation rejects the hypothesis of a constant antineutrino flux as a function of the 239Pu fission fraction at 10 standard deviations. The variation in IBD yield is found to be energy dependent, rejecting the hypothesis of a constant antineutrino energy spectrum at 5.1 standard deviations. While measurements of the evolution in the IBD spectrum show general agreement with predictions from recent reactor models, the measured evolution in total IBD yield disagrees with recent predictions at 3.1σ. This discrepancy indicates that an overall deficit in the measured flux with respect to predictions does not result from equal fractional deficits from the primary fission isotopes 235U, 239Pu, 238U, and 241Pu. Based on measured IBD yield variations, yields of (6.17±0.17) and (4.27±0.26)×10 –43 cm 2/fission have been determined for the two dominant fission parent isotopes 235U and 239Pu. A 7.8% discrepancy between the observed and predicted 235U yields suggests that this isotope may be the primary contributor to the reactor antineutrino anomaly.« less

Evolution of the Reactor Antineutrino Flux and Spectrum at Daya Bay.

PubMed

An, F P; Balantekin, A B; Band, H R; Bishai, M; Blyth, S; Cao, D; Cao, G F; Cao, J; Chan, Y L; Chang, J F; Chang, Y; Chen, H S; Chen, Q Y; Chen, S M; Chen, Y X; Chen, Y; Cheng, J; Cheng, Z K; Cherwinka, J J; Chu, M C; Chukanov, A; Cummings, J P; Ding, Y Y; Diwan, M V; Dolgareva, M; Dove, J; Dwyer, D A; Edwards, W R; Gill, R; Gonchar, M; Gong, G H; Gong, H; Grassi, M; Gu, W Q; Guo, L; Guo, X H; Guo, Y H; Guo, Z; Hackenburg, R W; Hans, S; He, M; Heeger, K M; Heng, Y K; Higuera, A; Hsiung, Y B; Hu, B Z; Hu, T; Huang, E C; Huang, H X; Huang, X T; Huang, Y B; Huber, P; Huo, W; Hussain, G; Jaffe, D E; Jen, K L; Ji, X P; Ji, X L; Jiao, J B; Johnson, R A; Jones, D; Kang, L; Kettell, S H; Khan, A; Kohn, S; Kramer, M; Kwan, K K; Kwok, M W; Langford, T J; Lau, K; Lebanowski, L; Lee, J; Lee, J H C; Lei, R T; Leitner, R; Leung, J K C; Li, C; Li, D J; Li, F; Li, G S; Li, Q J; Li, S; Li, S C; Li, W D; Li, X N; Li, X Q; Li, Y F; Li, Z B; Liang, H; Lin, C J; Lin, G L; Lin, S; Lin, S K; Lin, Y-C; Ling, J J; Link, J M; Littenberg, L; Littlejohn, B R; Liu, J L; Liu, J C; Loh, C W; Lu, C; Lu, H Q; Lu, J S; Luk, K B; Ma, X Y; Ma, X B; Ma, Y Q; Malyshkin, Y; Martinez Caicedo, D A; McDonald, K T; McKeown, R D; Mitchell, I; Nakajima, Y; Napolitano, J; Naumov, D; Naumova, E; Ngai, H Y; Ochoa-Ricoux, J P; Olshevskiy, A; Pan, H-R; Park, J; Patton, S; Pec, V; Peng, J C; Pinsky, L; Pun, C S J; Qi, F Z; Qi, M; Qian, X; Qiu, R M; Raper, N; Ren, J; Rosero, R; Roskovec, B; Ruan, X C; Steiner, H; Stoler, P; Sun, J L; Tang, W; Taychenachev, D; Treskov, K; Tsang, K V; Tull, C E; Viaux, N; Viren, B; Vorobel, V; Wang, C H; Wang, M; Wang, N Y; Wang, R G; Wang, W; Wang, X; Wang, Y F; Wang, Z; Wang, Z; Wang, Z M; Wei, H Y; Wen, L J; Whisnant, K; White, C G; Whitehead, L; Wise, T; Wong, H L H; Wong, S C F; Worcester, E; Wu, C-H; Wu, Q; Wu, W J; Xia, D M; Xia, J K; Xing, Z Z; Xu, J L; Xu, Y; Xue, T; Yang, C G; Yang, H; Yang, L; Yang, M S; Yang, M T; Yang, Y Z; Ye, M; Ye, Z; Yeh, M; Young, B L; Yu, Z Y; Zeng, S; Zhan, L; Zhang, C; Zhang, C C; Zhang, H H; Zhang, J W; Zhang, Q M; Zhang, R; Zhang, X T; Zhang, Y M; Zhang, Y X; Zhang, Y M; Zhang, Z J; Zhang, Z Y; Zhang, Z P; Zhao, J; Zhou, L; Zhuang, H L; Zou, J H

2017-06-23

The Daya Bay experiment has observed correlations between reactor core fuel evolution and changes in the reactor antineutrino flux and energy spectrum. Four antineutrino detectors in two experimental halls were used to identify 2.2 million inverse beta decays (IBDs) over 1230 days spanning multiple fuel cycles for each of six 2.9 GW_{th} reactor cores at the Daya Bay and Ling Ao nuclear power plants. Using detector data spanning effective ^{239}Pu fission fractions F_{239} from 0.25 to 0.35, Daya Bay measures an average IBD yield σ[over ¯]_{f} of (5.90±0.13)×10^{-43}  cm^{2}/fission and a fuel-dependent variation in the IBD yield, dσ_{f}/dF_{239}, of (-1.86±0.18)×10^{-43}  cm^{2}/fission. This observation rejects the hypothesis of a constant antineutrino flux as a function of the ^{239}Pu fission fraction at 10 standard deviations. The variation in IBD yield is found to be energy dependent, rejecting the hypothesis of a constant antineutrino energy spectrum at 5.1 standard deviations. While measurements of the evolution in the IBD spectrum show general agreement with predictions from recent reactor models, the measured evolution in total IBD yield disagrees with recent predictions at 3.1σ. This discrepancy indicates that an overall deficit in the measured flux with respect to predictions does not result from equal fractional deficits from the primary fission isotopes ^{235}U, ^{239}Pu, ^{238}U, and ^{241}Pu. Based on measured IBD yield variations, yields of (6.17±0.17) and (4.27±0.26)×10^{-43}  cm^{2}/fission have been determined for the two dominant fission parent isotopes ^{235}U and ^{239}Pu. A 7.8% discrepancy between the observed and predicted ^{235}U yields suggests that this isotope may be the primary contributor to the reactor antineutrino anomaly.

Evolution of the Reactor Antineutrino Flux and Spectrum at Daya Bay

NASA Astrophysics Data System (ADS)

An, F. P.; Balantekin, A. B.; Band, H. R.; Bishai, M.; Blyth, S.; Cao, D.; Cao, G. F.; Cao, J.; Chan, Y. L.; Chang, J. F.; Chang, Y.; Chen, H. S.; Chen, Q. Y.; Chen, S. M.; Chen, Y. X.; Chen, Y.; Cheng, J.; Cheng, Z. K.; Cherwinka, J. J.; Chu, M. C.; Chukanov, A.; Cummings, J. P.; Ding, Y. Y.; Diwan, M. V.; Dolgareva, M.; Dove, J.; Dwyer, D. A.; Edwards, W. R.; Gill, R.; Gonchar, M.; Gong, G. H.; Gong, H.; Grassi, M.; Gu, W. Q.; Guo, L.; Guo, X. H.; Guo, Y. H.; Guo, Z.; Hackenburg, R. W.; Hans, S.; He, M.; Heeger, K. M.; Heng, Y. K.; Higuera, A.; Hsiung, Y. B.; Hu, B. Z.; Hu, T.; Huang, E. C.; Huang, H. X.; Huang, X. T.; Huang, Y. B.; Huber, P.; Huo, W.; Hussain, G.; Jaffe, D. E.; Jen, K. L.; Ji, X. P.; Ji, X. L.; Jiao, J. B.; Johnson, R. A.; Jones, D.; Kang, L.; Kettell, S. H.; Khan, A.; Kohn, S.; Kramer, M.; Kwan, K. K.; Kwok, M. W.; Langford, T. J.; Lau, K.; Lebanowski, L.; Lee, J.; Lee, J. H. C.; Lei, R. T.; Leitner, R.; Leung, J. K. C.; Li, C.; Li, D. J.; Li, F.; Li, G. S.; Li, Q. J.; Li, S.; Li, S. C.; Li, W. D.; Li, X. N.; Li, X. Q.; Li, Y. F.; Li, Z. B.; Liang, H.; Lin, C. J.; Lin, G. L.; Lin, S.; Lin, S. K.; Lin, Y.-C.; Ling, J. J.; Link, J. M.; Littenberg, L.; Littlejohn, B. R.; Liu, J. L.; Liu, J. C.; Loh, C. W.; Lu, C.; Lu, H. Q.; Lu, J. S.; Luk, K. B.; Ma, X. Y.; Ma, X. B.; Ma, Y. Q.; Malyshkin, Y.; Martinez Caicedo, D. A.; McDonald, K. T.; McKeown, R. D.; Mitchell, I.; Nakajima, Y.; Napolitano, J.; Naumov, D.; Naumova, E.; Ngai, H. Y.; Ochoa-Ricoux, J. P.; Olshevskiy, A.; Pan, H.-R.; Park, J.; Patton, S.; Pec, V.; Peng, J. C.; Pinsky, L.; Pun, C. S. J.; Qi, F. Z.; Qi, M.; Qian, X.; Qiu, R. M.; Raper, N.; Ren, J.; Rosero, R.; Roskovec, B.; Ruan, X. C.; Steiner, H.; Stoler, P.; Sun, J. L.; Tang, W.; Taychenachev, D.; Treskov, K.; Tsang, K. V.; Tull, C. E.; Viaux, N.; Viren, B.; Vorobel, V.; Wang, C. H.; Wang, M.; Wang, N. Y.; Wang, R. G.; Wang, W.; Wang, X.; Wang, Y. F.; Wang, Z.; Wang, Z.; Wang, Z. M.; Wei, H. Y.; Wen, L. J.; Whisnant, K.; White, C. G.; Whitehead, L.; Wise, T.; Wong, H. L. H.; Wong, S. C. F.; Worcester, E.; Wu, C.-H.; Wu, Q.; Wu, W. J.; Xia, D. M.; Xia, J. K.; Xing, Z. Z.; Xu, J. L.; Xu, Y.; Xue, T.; Yang, C. G.; Yang, H.; Yang, L.; Yang, M. S.; Yang, M. T.; Yang, Y. Z.; Ye, M.; Ye, Z.; Yeh, M.; Young, B. L.; Yu, Z. Y.; Zeng, S.; Zhan, L.; Zhang, C.; Zhang, C. C.; Zhang, H. H.; Zhang, J. W.; Zhang, Q. M.; Zhang, R.; Zhang, X. T.; Zhang, Y. M.; Zhang, Y. X.; Zhang, Y. M.; Zhang, Z. J.; Zhang, Z. Y.; Zhang, Z. P.; Zhao, J.; Zhou, L.; Zhuang, H. L.; Zou, J. H.; Daya Bay Collaboration

2017-06-01

The Daya Bay experiment has observed correlations between reactor core fuel evolution and changes in the reactor antineutrino flux and energy spectrum. Four antineutrino detectors in two experimental halls were used to identify 2.2 million inverse beta decays (IBDs) over 1230 days spanning multiple fuel cycles for each of six 2.9 G Wth reactor cores at the Daya Bay and Ling Ao nuclear power plants. Using detector data spanning effective 239Pu fission fractions F239 from 0.25 to 0.35, Daya Bay measures an average IBD yield σ¯f of (5.90 ±0.13 )×10-43 cm2/fission and a fuel-dependent variation in the IBD yield, d σf/d F239, of (-1.86 ±0.18 )×10-43 cm2/fission . This observation rejects the hypothesis of a constant antineutrino flux as a function of the 239Pu fission fraction at 10 standard deviations. The variation in IBD yield is found to be energy dependent, rejecting the hypothesis of a constant antineutrino energy spectrum at 5.1 standard deviations. While measurements of the evolution in the IBD spectrum show general agreement with predictions from recent reactor models, the measured evolution in total IBD yield disagrees with recent predictions at 3.1 σ . This discrepancy indicates that an overall deficit in the measured flux with respect to predictions does not result from equal fractional deficits from the primary fission isotopes 235U, 239Pu, 238U, and 241Pu. Based on measured IBD yield variations, yields of (6.17 ±0.17 ) and (4.27 ±0.26 )×10-43 cm2 /fission have been determined for the two dominant fission parent isotopes 235U and 239Pu. A 7.8% discrepancy between the observed and predicted 235U yields suggests that this isotope may be the primary contributor to the reactor antineutrino anomaly.

Evolution of the Reactor Antineutrino Flux and Spectrum at Daya Bay

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

An, F. P.; Balantekin, A. B.; Band, H. R.

Here, the Daya Bay experiment has observed correlations between reactor core fuel evolution and changes in the reactor antineutrino flux and energy spectrum. Four antineutrino detectors in two experimental halls were used to identify 2.2 million inverse beta decays (IBDs) over 1230 days spanning multiple fuel cycles for each of six 2.9 GW th reactor cores at the Daya Bay and Ling Ao nuclear power plants. Using detector data spanning effective 239Pu fission fractions F 239 from 0.25 to 0.35, Daya Bay measures an average IBD yield ¯σf of (5.90±0.13)×10 –43 cm 2/fission and a fuel-dependent variation in the IBDmore » yield, dσ f/dF 239, of (–1.86±0.18)×10 –43 cm 2/fission. This observation rejects the hypothesis of a constant antineutrino flux as a function of the 239Pu fission fraction at 10 standard deviations. The variation in IBD yield is found to be energy dependent, rejecting the hypothesis of a constant antineutrino energy spectrum at 5.1 standard deviations. While measurements of the evolution in the IBD spectrum show general agreement with predictions from recent reactor models, the measured evolution in total IBD yield disagrees with recent predictions at 3.1σ. This discrepancy indicates that an overall deficit in the measured flux with respect to predictions does not result from equal fractional deficits from the primary fission isotopes 235U, 239Pu, 238U, and 241Pu. Based on measured IBD yield variations, yields of (6.17±0.17) and (4.27±0.26)×10 –43 cm 2/fission have been determined for the two dominant fission parent isotopes 235U and 239Pu. A 7.8% discrepancy between the observed and predicted 235U yields suggests that this isotope may be the primary contributor to the reactor antineutrino anomaly.« less

The need for New In Situ Measurements to Understand the Climate, Geology and Evolution of Venus.

NASA Astrophysics Data System (ADS)

Grinspoon, D. H.

2017-12-01

Many measurements needed to address outstanding questions about current processes and evolution of Venus can only be made from in situ platforms such as entry probes, balloons or landers. Among these are precise determination of the value and altitude dependence of the deuterium-to-hydrogen ratio, an important tracer of water history which, while clearly greatly elevated compared to the terrestrial ratio, is still unknown within a large range of uncertainty and appears, based on Venus Express results, to display an enigmatic altitude dependence. Rare gas abundances and isotopes provide clues to volatile sources and histories of outgassing and exospheric escape. Modern mass spectrometry at Venus would yield abundances of the eight stable xenon isotopes, bulk abundances of krypton, and isotopes of neon. Altitude profiles of sulfur-containing chemical species would illuminate global geochemical cycles, including cloud formation, outgassing rates and surface-atmosphere interactions. The altitude profile of wind speeds and radiation fluxes, interpreted in light of the Venus Express and Akatsuki data, would enrich understanding of the global circulation and climate dynamics of Venus. Descent and surface images of carefully chosen locations would lend ground truth to interpretations of the near-global Magellan data sets and provide context for global remote sensing data obtained by future orbiter missions. Landed instruments would provide refinement and calibration for chemical abundance measurements by historical missions as well as direct mineralogical measurements of Venusian surface and subsurface rocks. In concert with atmospheric measurements these would greatly constrain geologic history as well as the nature of surface-atmosphere interactions. Such a suite of measurements will deepen our understanding of the origin and evolution of Venus in the context of Solar System and extrasolar terrestrial planets, determine the level and style of current geological activity, characterize the divergent climate evolution of Venus and Earth and extend our knowledge of the limits of habitability on hot terrestrial planets.

Validation of GC-IRMS techniques for δ13C and δ2H CSIA of organophosphorus compounds and their potential for studying the mode of hydrolysis in the environment.

PubMed

Wu, Langping; Kümmel, Steffen; Richnow, Hans H

2017-04-01

Compound-specific stable isotope analysis (CSIA) is among the most promising tools for studying the fate of organic pollutants in the environment. However, the feasibility of multidimensional CSIA was limited by the availability of a robust method for precise isotope analysis of heteroatom-bearing organic compounds. We developed a method for δ 13 C and δ 2 H analysis of eight organophosphorus compounds (OPs) with different chemical properties. In particular, we aimed to compare high-temperature conversion (HTC) and chromium-based HTC (Cr/HTC) units to explore the limitations of hydrogen isotope analysis of heteroatom-bearing compounds. Analysis of the amount dependency of the isotope values (linearity analysis) of OPs indicated that the formation of HCl was a significant isotope fractionation process leading to inaccurate δ 2 H analysis in HTC. In the case of nonchlorinated OPs, by-product formation of HCN, H 2 S, or PH 3 in HTC was observed but did not affect the dynamic range of reproducible isotope values above the limit of detection. No hydrogen-containing by-products were found in the Cr/HTC process by use of ion trap mass spectrometry analysis. The accuracy of gas chromatography - isotope ratio mass spectrometry was validated in comparison with elemental analyzer - isotope ratio mass spectrometry. Dual-isotope fractionation yielded Λ values of 0 ± 0 at pH 7, 7 ± 1 at pH 9, and 30 ± 6 at pH 12, indicating the potential of 2D CSIA to characterize the hydrolysis mechanisms of OPs. This is the first report on the combination of δ 2 H and δ 13 C isotope analysis of OPs, and this is the first study providing a systematic evaluation of HTC and Cr/HTC for hydrogen isotope analysis using OPs as target compounds. Graphical Abstract Comparison of δ 2 H measurement of non-chlorinated and chlorinated OPs via GC-Cr/HTC-IRMS and GC-HTC-IRMS system.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

Fekete, Szandra; Weis, Philipp; Scott, Samuel; Driesner, Thomas

2018-02-01

Stable isotope signatures of oxygen, hydrogen and other elements in minerals from hydrothermal veins and metasomatized host rocks are widely used to investigate fluid sources and paths. Previous theoretical studies mostly focused on analyzing stable isotope fronts developing during single-phase, isothermal fluid flow. In this study, numerical simulations were performed to assess how temperature changes, transport phenomena, kinetic vs. equilibrium isotope exchange, and isotopic source signals determine mineral oxygen isotopic compositions during fluid-rock interaction. The simulations focus on one-dimensional scenarios, with non-isothermal single- and two-phase fluid flow, and include the effects of quartz precipitation and dissolution. If isotope exchange between fluid and mineral is fast, a previously unrecognized, significant enrichment in heavy oxygen isotopes of fluids and minerals occurs at the thermal front. The maximum enrichment depends on the initial isotopic composition of fluid and mineral, the fluid-rock ratio and the maximum change in temperature, but is independent of the isotopic composition of the incoming fluid. This thermally induced isotope front propagates faster than the signal related to the initial isotopic composition of the incoming fluid, which forms a trailing front behind the zone of transient heavy oxygen isotope enrichment. Temperature-dependent kinetic rates of isotope exchange between fluid and rock strongly influence the degree of enrichment at the thermal front. In systems where initial isotope values of fluids and rocks are far from equilibrium and isotope fractionation is controlled by kinetics, the temperature increase accelerates the approach of the fluid to equilibrium conditions with the host rock. Consequently, the increase at the thermal front can be less dominant and can even generate fluid values below the initial isotopic composition of the input fluid. As kinetics limit the degree of isotope exchange, a third front may develop in kinetically limited systems, which propagates with the advection speed of the incoming fluid and is, therefore, traveling fastest. The results show that oxygen isotope signatures at thermal fronts recorded in rocks and veins that experienced isotope exchange with fluids can easily be misinterpreted, namely if bulk analytical techniques are applied. However, stable isotope microanalysis on precipitated minerals may - if later isotope exchange is kinetically limited - provide a valuable archive of the transient thermal and hydrological evolution of a system.

A Neutral Particle Analyser Proposed On Board Bepicolombo Planetary Orbiter: Serena (searching For Exospheric Refilling and Emitted Neutral Abundances)

NASA Astrophysics Data System (ADS)

Orsini, S.; Npa-Serena Team

The Neutral Particle Analyser SERENA, proposed on board the BepiColombo Mer- cury Planetary Orbiter (MPO), has the purpose of investigating the Hermean exo- spheric and energetic neutral populations. Local and detailed analysis of the exo- spheric composition will be performed by a ram-pointing sensor (MAIA), while en- ergetic neutrals produced through sputtering and charge-exchange processes will be collected by two nadir-pointing sensors (L-ENA, MH-ENA). A central problem in the understanding of the evolution of solar system bodies is the role played by the so- lar wind, solar radiation and micro-meteorite bombardment in controlling mass losses. The direct in situ detection of the Hermean exosphere, the gas evolving from the planet as a product of the different physical processes acting onto the surface, is of crucial importance to understand the past and present evolution of the crust. Current knowl- edge of the origin and evolution of the solar system is based on detailed measurement of chemical, elemental, and isotopic composition of matter. The proposed instrument suite is unique in its capability to perform quantitative analysis and resolve exospheric gas composition under all these three aspects. The value of neutral particles mea- surements for getting a comprehensive picture of the solar wind-planets interaction has been appreciated since the late eighties. Comparison of the measurements in the Mercury environment with those achieved by neutral particle imagers already flying around Earth (IMAGE), Mars (Mars Express), Jupiter and Saturn (Cassini) will allow comparative investigations of evolution and dynamics of planetary magnetospheres.

Mars atmospheric escape and evolution; interaction with the solar wind

NASA Astrophysics Data System (ADS)

Chassefière, Eric; Leblanc, François

2004-09-01

This tutorial deals with the question of atmospheric escape on Mars. After a brief introduction describing the general context of Mars escape studies, we will present in Section 2 a simplified theory of thermal escape, of both Jeans and hydrodynamic types. The phenomenon of hydrodynamic escape, still hypothetical and not proved to have ever existed on terrestrial planets, will be treated with the help of two well known examples: (i) the isotopic fractionation of xenon in Mars and Earth atmospheres, (ii) the paradox of missing oxygen in Venus atmosphere. In Section 3, a simplified approach of non-thermal escape will be developed, treating in a specific way the different kinds of escape (photochemical escape, ion sputtering, ion escape and ionospheric outflow). As a matter of illustration, some calculations of the relative contributions of these mechanisms, and of their time evolutions, will be given, and the magnitude of the total amount of atmosphere lost by non-thermal escape will be estimated. Section 4 will present the state of knowledge concerning the constraints derived from Mars isotopic geochemistry in terms of past escape and evolution. Finally, a few conclusions, which are more interrogations, will be proposed.

Red-giant evolution, metallicity, and new bounds on hadronic axions

NASA Technical Reports Server (NTRS)

Haxton, W. C.; Lee, K. Y.

1991-01-01

Stellar cooling by nuclear axion emission is explored, identifying those special isotopes that dominate this process for temperatures from 10 to the 7th to 10 to the 9th K. It is argued that such nuclear energy-loss mechanisms are distinctive because the effects track metallicity. Three observables associated with evolution of stars along the red-giant and horizontal branches are shown to impose new and restrictive constraints on axions in the hadronic window.

Basalt Pb isotope analysis and the prehistoric settlement of Polynesia.

PubMed Central

Weisler, M I; Woodhead, J D

1995-01-01

The prehistoric settlement of the Pacific Ocean has intrigued scholars and stimulated anthropological debate for the past two centuries. Colonized over a few millennia during the mid to late Holocene, the islands of the Pacific--displaying a wide diversity of geological and biotic variability--provided the stage for endless "natural experiments" in human adaptation. Crucial to understanding the evolution and transformation of island societies is documenting the relative degree of interisland contacts after island colonization. In the western Pacific, ideal materials for archaeologically documenting interisland contact--obsidian, pottery, and shell ornaments--are absent or of limited geographic distribution in Polynesia. Consequently, archaeologists have relied increasingly on fine-grained basalt artifacts as a means for documenting colonization routes and subsequent interisland contacts. Routinely used x-ray fluorescence characterization of oceanic island basalt has some problems for discriminating source rocks and artifacts in provenance studies. The variation in trace and major element abundances is largely controlled by near-surface magma-chamber processes and is broadly similar between most oceanic islands. We demonstrate that Pb isotope analysis accurately discriminates rock source and is an excellent technique for charting the scale, frequency, and temporal span of imported fine-grained basalt artifacts found throughout Polynesia. The technique adds another tool for addressing evolutionary models of interaction, isolation, and cultural divergence in the eastern Pacific. PMID:7892194

13C-METHYL Formate in Orion-Kl Alma Observations and Spectroscopic Characterization

NASA Astrophysics Data System (ADS)

Favre, Cécile; Carvajal, Miguel; Field, David; Bergin, Edwin; Neill, Justin; Crockett, Nathan; Jørgensen, Jes; Bisschop, Suzanne; Brouillet, Nathalie; Despois, Didier; Baudry, Alain; Kleiner, Isabelle; Margulès, L.; Huet, T. R.; Demaison, Jean

2014-06-01

Determination of elemental isotopic ratios is valuable for understanding the chemical evolution of interstellar material. Until now the 12C/13C ratio has predominantly been measured in simple species such as CO, CN and H2CO and, becomes larger with increasing distance from the Galactic Center. We have investigated the carbon isotopic ratio for methyl formate HCOOCH3, and its isotopologues H13COOCH3 and HCOO13CH3 addressing the issue whether the 12C/13C ratio is the same for both simple and large molecules. Using ALMA science verification observations of Orion-KL and the spectroscopic characterization of the complex H13COOCH3 and HCOO13CH3 species that we have performed, we have 1) confirmed the detection of the 13C-methyl formate species in Orion-KL and, 2) image for the first time their spatial distribution. I will present some of these results. In particular, our analysis shows that the 12C/13C isotope ratio in methyl formate toward the Compact Ridge and Hot Core-SW components that are associated with Orion-KL are, for both the 13C-methyl formate isotopologues, commensurate with the well-known 12C/13C ratio of the simple species CO. Our findings suggest that grain surface chemistry very likely prevails in the formation of methyl formate main and 13C isotopologues.

A non-zircon Hf isotope record in Archean black shales from the Pilbara craton confirms changing crustal dynamics ca. 3 Ga ago.

PubMed

Nebel-Jacobsen, Yona; Nebel, Oliver; Wille, Martin; Cawood, Peter A

2018-01-17

Plate tectonics and associated subduction are unique to the Earth. Studies of Archean rocks show significant changes in composition and structural style around 3.0 to 2.5 Ga that are related to changing tectonic regime, possibly associated with the onset of subduction. Whole rock Hf isotope systematics of black shales from the Australian Pilbara craton, selected to exclude detrital zircon components, are employed to evaluate the evolution of the Archean crust. This approach avoids limitations of Hf-in-zircon analyses, which only provide input from rocks of sufficient Zr-concentration, and therefore usually represent domains that already underwent a degree of differentiation. In this study, we demonstrate the applicability of this method through analysis of shales that range in age from 3.5 to 2.8 Ga, and serve as representatives of their crustal sources through time. Their Hf isotopic compositions show a trend from strongly positive εHf initial values for the oldest samples, to strongly negative values for the younger samples, indicating a shift from juvenile to differentiated material. These results confirm a significant change in the character of the source region of the black shales by 3 Ga, consistent with models invoking a change in global dynamics from crustal growth towards crustal reworking around this time.

Parsing parallel evolution: ecological divergence and differential gene expression in the adaptive radiations of thick-lipped Midas cichlid fishes from Nicaragua.

PubMed

Manousaki, Tereza; Hull, Pincelli M; Kusche, Henrik; Machado-Schiaffino, Gonzalo; Franchini, Paolo; Harrod, Chris; Elmer, Kathryn R; Meyer, Axel

2013-02-01

The study of parallel evolution facilitates the discovery of common rules of diversification. Here, we examine the repeated evolution of thick lips in Midas cichlid fishes (the Amphilophus citrinellus species complex)-from two Great Lakes and two crater lakes in Nicaragua-to assess whether similar changes in ecology, phenotypic trophic traits and gene expression accompany parallel trait evolution. Using next-generation sequencing technology, we characterize transcriptome-wide differential gene expression in the lips of wild-caught sympatric thick- and thin-lipped cichlids from all four instances of repeated thick-lip evolution. Six genes (apolipoprotein D, myelin-associated glycoprotein precursor, four-and-a-half LIM domain protein 2, calpain-9, GTPase IMAP family member 8-like and one hypothetical protein) are significantly underexpressed in the thick-lipped morph across all four lakes. However, other aspects of lips' gene expression in sympatric morphs differ in a lake-specific pattern, including the magnitude of differentially expressed genes (97-510). Generally, fewer genes are differentially expressed among morphs in the younger crater lakes than in those from the older Great Lakes. Body shape, lower pharyngeal jaw size and shape, and stable isotopes (δ(13)C and δ(15)N) differ between all sympatric morphs, with the greatest differentiation in the Great Lake Nicaragua. Some ecological traits evolve in parallel (those related to foraging ecology; e.g. lip size, body and head shape) but others, somewhat surprisingly, do not (those related to diet and food processing; e.g. jaw size and shape, stable isotopes). Taken together, this case of parallelism among thick- and thin-lipped cichlids shows a mosaic pattern of parallel and nonparallel evolution. © 2012 Blackwell Publishing Ltd.

Leaf wax biomarker reconstruction of Early Pleistocene hydrological variation during hominin evolution in West Turkana, Kenya

NASA Astrophysics Data System (ADS)

Lupien, R.; Russell, J. M.; Cohen, A. S.; Feibel, C. S.; Beck, C.; Castañeda, I. S.

2016-12-01

Climate change is thought to play a critical role in human evolution; however, this hypothesis is difficult to test due to a lack of long, high-quality paleoclimate records from key hominin fossil locales. To address this issue, we examine Plio-Pleistocene lake sediment drill cores from East Africa that were recovered by the Hominin Sites and Paleolakes Drilling Project, an international effort to study the environment in which our hominin ancestors evolved and dispersed. With new data we test various evolutionary hypotheses, such as the "variability selection" hypothesis, which posits that high-frequency environmental variations selected for generalist traits that allowed hominins to expand into variable environments. We analyzed organic geochemical signals of climate in lake cores from West Turkana, Kenya, which span 1.87-1.38 Ma and contain the first fossils from Homo erectus. In particular, we present a compound-specific hydrogen isotopic analysis of terrestrial plant waxes (δDwax) that records regional hydrology. The amount effect dominates water isotope fractionation in the tropics; therefore, these data are interpreted to reflect mean annual rainfall, which affects vegetation structure and thus, hominin habitats. The canonical view of East Africa is that climate became drier and increasingly felt high-latitude glacial-interglacial cycles during the Plio-Pleistocene. However, the drying trend seen in some records is not evident in Turkana δDwax, signifying instead a climate with a steady mean state. Spectral and moving variance analyses indicate paleohydrological variations related to both high-latitude glaciation (41 ky cycle) and local insolation-forced monsoons (21 ky cycle). An interval of particularly high-amplitude rainfall variation occurs at 1.7 Ma, which coincides with the intensification of the Walker Circulation. These results identify high- and low-latitude controls on East African paleohydrology during Homo erectus evolution. In particular, the interval of high-amplitude variability coincides with hominin evolution changes and lends support for the "variability selection" hypothesis. Similar analyses of a drill core from Northern Awash, Ethiopia ( 3.3-2.9 Ma) will be presented to compare Pliocene and Pleistocene climate variations.

A combined chemical, isotopic and microstructural study of pyrite from roll-front uranium deposits, Lake Eyre Basin, South Australia

NASA Astrophysics Data System (ADS)

Ingham, Edwina S.; Cook, Nigel J.; Cliff, John; Ciobanu, Cristiana L.; Huddleston, Adam

2014-01-01

The common sulfide mineral pyrite is abundant throughout sedimentary uranium systems at Pepegoona, Pepegoona West and Pannikan, Lake Eyre Basin, South Australia. Combined chemical, isotopic and microstructural analysis of pyrite indicates variation in fluid composition, sulfur source and precipitation conditions during a protracted mineralization event. The results show the significant role played by pyrite as a metal scavenger and monitor of fluid changes in low-temperature hydrothermal systems. In-situ micrometer-scale sulfur isotope analyses of pyrite demonstrated broad-scale isotopic heterogeneity (δ34S = -43.9 to +32.4‰VCDT), indicative of complex, multi-faceted pyrite evolution, and sulfur derived from more than a single source. Preserved textures support this assertion and indicate a genetic model involving more than one phase of pyrite formation. Authigenic pyrite underwent prolonged evolution and recrystallization, evidenced by a genetic relationship between archetypal framboidal aggregates and pyrite euhedra. Secondary hydrothermal pyrite commonly displays hyper-enrichment of several trace elements (Mn, Co, Ni, As, Se, Mo, Sb, W and Tl) in ore-bearing horizons. Hydrothermal fluids of magmatic and meteoric origins supplied metals to the system but the geochemical signature of pyrite suggests a dominantly granitic source and also the influence of mafic rock types. Irregular variation in δ34S, coupled with oscillatory trace element zonation in secondary pyrite, is interpreted in terms of continuous variations in fluid composition and cycles of diagenetic recrystallization. A late-stage oxidizing fluid may have mobilized selenium from pre-existing pyrite. Subsequent restoration of reduced conditions within the aquifer caused ongoing pyrite re-crystallization and precipitation of selenium as native selenium. These results provide the first qualitative constraints on the formation mechanisms of the uranium deposits at Beverley North. Insights into depositional conditions and sources of both sulfide and uranium mineralization and an improved understanding of pyrite geochemistry can also underpin an effective vector for uranium exploration at Beverley North and other sedimentary systems of the Lake Eyre Basin, as well as in comparable geological environments elsewhere. Average intensity of 32S signal in counts per second × 108.Drift corrected 34S/32S prior to IMF calibration.Two-sigma propagated uncertainty on individual measurements.

The {sup 12}C/{sup 13}C Ratio in Sgr B2(N): Constraints for Galactic Chemical Evolution and Isotopic Chemistry

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

Halfen, D. T.; Ziurys, L. M.; Woolf, N. J., E-mail: halfend@email.arizona.edu

A study has been conducted of {sup 12}C/{sup 13}C ratios in five complex molecules in the Galactic center. H{sub 2}CS, CH{sub 3}CCH, NH{sub 2}CHO, CH{sub 2}CHCN, and CH{sub 3}CH{sub 2}CN and their {sup 13}C-substituted species have been observed in numerous transitions at 1, 2, and 3 mm, acquired in a spectral-line survey of Sgr B2(N), conducted with the telescopes of the Arizona Radio Observatory (ARO). Between 22 and 54 individual, unblended lines for the {sup 12}C species and 2–54 for {sup 13}C-substituted analogs were modeled in a global radiative transfer analysis. All five molecules were found to consistently exhibit twomore » velocity components near V {sub LSR} ∼ 64 and 73 km s{sup −1}, with column densities ranging from N {sub tot} ∼ 3 × 10{sup 14} − 4 × 10{sup 17} cm{sup −2} and ∼2 × 10{sup 13} − 1 × 10{sup 17} cm{sup −2} for the {sup 12}C and {sup 13}C species, respectively. Based on 14 different isotopic combinations, ratios were obtained in the range {sup 12}C/{sup 13}C = 15 ± 5 to 33 ± 13, with an average value of 24 ± 7, based on comparison of column densities. These measurements better anchor the {sup 12}C/{sup 13}C ratio at the Galactic center, and suggest a slightly revised isotope gradient of {sup 12}C/{sup 13}C = 5.21(0.52) D {sub GC} + 22.6(3.3). As indicated by the column densities, no preferential {sup 13}C enrichment was found on the differing carbon sites of CH{sub 3}CCH, CH{sub 2}CHCN, and CH{sub 3}CH{sub 2}CN. Because of the elevated temperatures in Sgr B2(N), {sup 13}C isotopic substitution is effectively “scrambled,” diminishing chemical fractionation effects. The resulting ratios thus reflect stellar nucleosynthesis and Galactic chemical evolution, as is likely the case for most warm clouds.« less

The organic analysis and carbon chemistry of lunar samples: Their significance for exobiology; Proceedings of the Conference, University of Maryland, College Park, Md., October 26-28, 1971.

NASA Technical Reports Server (NTRS)

1972-01-01

Various methods used in the organic analysis of lunar samples are reviewed. The scope, advantages, and limitations of these methods are discussed, with particular emphasis on possible sources of contamination and experimental artifacts inherent in their use. A broad survey of the organogenic elements and compounds found in lunar samples covers the search for biogenic structures and viable organisms; the abundance and isotopic composition of various elements and compounds; the search for porphyrins, amino acids, or amino acid precursors; and the presence of heterocylics, aromatic hydrocarbons, and other organic compounds. The sources of the organogenic elements and compounds detected in lunar samples are discussed. The significance of the lunar organic analysis for exobiology is discussed in terms of its relevance to and implications for the studies of chemical evolution and terrestrial organic geochemistry. Individual items are announced in this issue.

Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).

PubMed

Chew, Gina; Walczyk, Thomas

2013-04-02

Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored.

Development and validation of an universal interface for compound-specific stable isotope analysis of chlorine (37Cl/35Cl) by GC-high-temperature conversion (HTC)-MS/IRMS.

PubMed

Renpenning, Julian; Hitzfeld, Kristina L; Gilevska, Tetyana; Nijenhuis, Ivonne; Gehre, Matthias; Richnow, Hans-Hermann

2015-03-03

A universal application of compound-specific isotope analysis of chlorine was thus far limited by the availability of suitable analysis techniques. In this study, gas chromatography in combination with a high-temperature conversion interface (GC-HTC), converting organic chlorine in the presence of H2 to gaseous HCl, was coupled to a dual-detection system, combining an ion trap mass spectrometer (MS) and isotope-ratio mass spectrometer (IRMS). The combination of the MS/IRMS detection enabled a detailed characterization, optimization, and online monitoring of the high-temperature conversion process via ion trap MS as well as a simultaneous chlorine isotope analysis by the IRMS. Using GC-HTC-MS/IRMS, chlorine isotope analysis at optimized conversion conditions resulted in very accurate isotope values (δ(37)Cl(SMOC)) for measured reference material with known isotope composition, including chlorinated ethylene, chloromethane, hexachlorocyclohexane, and trichloroacetic acids methyl ester. Respective detection limits were determined to be <15 nmol Cl on column with achieved precision of <0.3‰.

Environmental Survey of the B-3 and Ford’s Farm Ranges,

DTIC Science & Technology

1983-08-01

reported have an estimated analytical error of *35% unless noted otherwise. 14 Isotopic Analysis The isotopic uranium analysis procedure used by UST...sulfate buffer and elec- trodeposited on a stainless steel disc, and isotopes of uranium (234U, 23 5U, and 2 38U) were determined by pulse height analysis ...measurements and some environmental sampling. Several special studies were also conducted, including analyses of the isotopic composition of uranium in

In-situ Isotopic Analysis at Nanoscale using Parallel Ion Electron Spectrometry: A Powerful New Paradigm for Correlative Microscopy

NASA Astrophysics Data System (ADS)

Yedra, Lluís; Eswara, Santhana; Dowsett, David; Wirtz, Tom

2016-06-01

Isotopic analysis is of paramount importance across the entire gamut of scientific research. To advance the frontiers of knowledge, a technique for nanoscale isotopic analysis is indispensable. Secondary Ion Mass Spectrometry (SIMS) is a well-established technique for analyzing isotopes, but its spatial-resolution is fundamentally limited. Transmission Electron Microscopy (TEM) is a well-known method for high-resolution imaging down to the atomic scale. However, isotopic analysis in TEM is not possible. Here, we introduce a powerful new paradigm for in-situ correlative microscopy called the Parallel Ion Electron Spectrometry by synergizing SIMS with TEM. We demonstrate this technique by distinguishing lithium carbonate nanoparticles according to the isotopic label of lithium, viz. 6Li and 7Li and imaging them at high-resolution by TEM, adding a new dimension to correlative microscopy.

Stable isotope probing in the metagenomics era: a bridge towards improved bioremediation

PubMed Central

Uhlik, Ondrej; Leewis, Mary-Cathrine; Strejcek, Michal; Musilova, Lucie; Mackova, Martina; Leigh, Mary Beth; Macek, Tomas

2012-01-01

Microbial biodegradation and biotransformation reactions are essential to most bioremediation processes, yet the specific organisms, genes, and mechanisms involved are often not well understood. Stable isotope probing (SIP) enables researchers to directly link microbial metabolic capability to phylogenetic and metagenomic information within a community context by tracking isotopically labeled substances into phylogenetically and functionally informative biomarkers. SIP is thus applicable as a tool for the identification of active members of the microbial community and associated genes integral to the community functional potential, such as biodegradative processes. The rapid evolution of SIP over the last decade and integration with metagenomics provides researchers with a much deeper insight into potential biodegradative genes, processes, and applications, thereby enabling an improved mechanistic understanding that can facilitate advances in the field of bioremediation. PMID:23022353

Genome evolution and nitrogen fixation in bacterial ectosymbionts of a protist inhabiting wood-feeding cockroaches

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

Tai, Vera; Carpenter, Kevin J.; Weber, Peter K.

By combining genomics and isotope imaging analysis using high-resolution secondary ion mass spectrometry (NanoSIMS), we examined the function and evolution of Bacteroidales ectosymbionts of the protistBarbulanymphafrom the hindguts of the wood-eating cockroachCryptocercus punctulatus. In particular, we investigated the structure of ectosymbiont genomes, which, in contrast to those of endosymbionts, has been little studied to date, and tested the hypothesis that these ectosymbionts fix nitrogen. Unlike with most obligate endosymbionts, genome reduction has not played a major role in the evolution of the Barbulanympha ectosymbionts. Instead, interaction with the external environment has remained important for this symbiont as genes for synthesismore » of transporters, outer membrane proteins, lipopolysaccharides, and lipoproteins have been retained. The ectosymbiont genome carried two complete operons for nitrogen fixation, a urea transporter, and a urease, indicating the availability of nitrogen as a driving force behind the symbiosis. NanoSIMS analysis ofC. punctulatushindgut symbionts exposedin vivoto 15N 2 supports the hypothesis thatBarbulanymphaectosymbionts are capable of nitrogen fixation. This genomic andin vivofunctional investigation of protist ectosymbionts highlights the diversity of evolutionary forces and trajectories that shape symbiotic interactions. The ecological and evolutionary importance of symbioses is increasingly clear, but the overall diversity of symbiotic interactions remains poorly explored. Here in this study, we investigated the evolution and nitrogen fixation capabilities of ectosymbionts attached to the protist Barbulanympha from the hindgut of the wood-eating cockroach Cryptocercus punctulatus. In addressing genome evolution of protist ectosymbionts, our data suggest that the ecological pressures influencing the evolution of extracellular symbionts clearly differ from intracellular symbionts and organelles. Using NanoSIMS analysis, we also obtained direct imaging evidence of a specific hindgut microbe playing a role in nitrogen fixation. These results demonstrate the power of combining NanoSIMS and genomics tools for investigating the biology of uncultivable microbes. This investigation paves the way for a more precise understanding of microbial interactions in the hindguts of wood-eating insects and further exploration of the diversity and ecological significance of symbiosis between microbes.« less

Genome evolution and nitrogen fixation in bacterial ectosymbionts of a protist inhabiting wood-feeding cockroaches

DOE PAGES

Tai, Vera; Carpenter, Kevin J.; Weber, Peter K.; ...

2016-05-27

By combining genomics and isotope imaging analysis using high-resolution secondary ion mass spectrometry (NanoSIMS), we examined the function and evolution of Bacteroidales ectosymbionts of the protistBarbulanymphafrom the hindguts of the wood-eating cockroachCryptocercus punctulatus. In particular, we investigated the structure of ectosymbiont genomes, which, in contrast to those of endosymbionts, has been little studied to date, and tested the hypothesis that these ectosymbionts fix nitrogen. Unlike with most obligate endosymbionts, genome reduction has not played a major role in the evolution of the Barbulanympha ectosymbionts. Instead, interaction with the external environment has remained important for this symbiont as genes for synthesismore » of transporters, outer membrane proteins, lipopolysaccharides, and lipoproteins have been retained. The ectosymbiont genome carried two complete operons for nitrogen fixation, a urea transporter, and a urease, indicating the availability of nitrogen as a driving force behind the symbiosis. NanoSIMS analysis ofC. punctulatushindgut symbionts exposedin vivoto 15N 2 supports the hypothesis thatBarbulanymphaectosymbionts are capable of nitrogen fixation. This genomic andin vivofunctional investigation of protist ectosymbionts highlights the diversity of evolutionary forces and trajectories that shape symbiotic interactions. The ecological and evolutionary importance of symbioses is increasingly clear, but the overall diversity of symbiotic interactions remains poorly explored. Here in this study, we investigated the evolution and nitrogen fixation capabilities of ectosymbionts attached to the protist Barbulanympha from the hindgut of the wood-eating cockroach Cryptocercus punctulatus. In addressing genome evolution of protist ectosymbionts, our data suggest that the ecological pressures influencing the evolution of extracellular symbionts clearly differ from intracellular symbionts and organelles. Using NanoSIMS analysis, we also obtained direct imaging evidence of a specific hindgut microbe playing a role in nitrogen fixation. These results demonstrate the power of combining NanoSIMS and genomics tools for investigating the biology of uncultivable microbes. This investigation paves the way for a more precise understanding of microbial interactions in the hindguts of wood-eating insects and further exploration of the diversity and ecological significance of symbiosis between microbes.« less

Groundwater hydrochemistry evolution in cyclone driven hydrological regimes, NW Australia

NASA Astrophysics Data System (ADS)

Skrzypek, G.; Dogramaci, S.; Grierson, P.

2013-12-01

Groundwater reserves supply the water needs of many arid regions around the world. Aquifer recharge in these regions is primarily depended on the amount and distribution of rainfall, coupled with exceedingly high rates of evaporation and interactions with both local and regional geomorphology and geology. In semi-arid northwest Australia, the majority of rainfall is delivered by large but infrequent cyclonic events and relatively more frequent but low intensity frontal systems. Changes to rainfall patterns due to global climate change may impact hydrological regimes, recharge rates and groundwater hydrochemistry. These changes may significantly restrict freshwater resources in the future. Between 2008 and 2012, we analysed >400 groundwater, surface and rainwater samples for stable isotope composition (δ2H and δ18O) and major ion chemistry. We then developed conceptual geochemical models of groundwater evolution for the Hamersley Basin (>100,000 km2) and a salt inventory for the Fortescue Marsh (the largest wetland in NW Australia) [1,2]. Fresh groundwater from the alluvium (-8.02 × 0.83‰) and fractured aquifers (-8.22 × 0.70‰) were hydrochemically similar and characterised by a very narrow range of δ18O [1]. In contrast, δ18O of saline and brine groundwater (TDS >10 g L-1) varies in wide range from +2.5 to -7.2‰ [2]. Most of the fresh and brackish groundwater reflects modern recharge and is evaporated by <20% prior to recharge. In contrast, highly saline and brine groundwater reflects mixing between modern rainfall, brackish water and older deep groundwater. The Fortescue Marsh primarily acts as a terminal basin for surface water from the upper Fortescue River catchment [2]. The stable isotope composition of the deep brine groundwater under the Marsh suggests a complex evolution, which cannot be explained by evaporation under current climatic conditions. The observed salinity and δ18O values may result from progressive evaporation from highly saline lake that existed in the past, as the dynamic fractionation from brine is much different compared to that in fresh and brackish waters. Therefore, deeper brine groundwater under the Marsh developed under a different climatic regime and that the current salt in the Marsh has accumulated over at least 40,000 years but could have been as long as 700,000 years [2]. Our combined chemical and stable isotope analyses confirm the general dominance of vertical over horizontal flow in the region and decoupling of processes that control water evolution from those that control salt evolution in groundwater. [1] Dogramaci S., Skrzypek G., Dodson W., Grierson P.F., 2012, Stable isotope and hydrochemical evolution of groundwater in the semi-arid Hamersley Basin of sub-tropical northwest Australia. Journal of Hydrology 475: 281-293. [2] Skrzypek G., Dogramaci S., Grierson P.F., 2013, Geochemical and hydrological processes controlling groundwater salinity of a large inland wetland of northwest Australia. Chemical Geology (in press).

Continental igneous rock composition: A major control of past global chemical weathering

PubMed Central

Bataille, Clément P.; Willis, Amy; Yang, Xiao; Liu, Xiao-Ming

2017-01-01

The composition of igneous rocks in the continental crust has changed throughout Earth’s history. However, the impact of these compositional variations on chemical weathering, and by extension on seawater and atmosphere evolution, is largely unknown. We use the strontium isotope ratio in seawater [(87Sr/86Sr)seawater] as a proxy for chemical weathering, and we test the sensitivity of (87Sr/86Sr)seawater variations to the strontium isotopic composition (87Sr/86Sr) in igneous rocks generated through time. We demonstrate that the 87Sr/86Sr ratio in igneous rocks is correlated to the epsilon hafnium (εHf) of their hosted zircon grains, and we use the detrital zircon record to reconstruct the evolution of the 87Sr/86Sr ratio in zircon-bearing igneous rocks. The reconstructed 87Sr/86Sr variations in igneous rocks are strongly correlated with the (87Sr/86Sr)seawater variations over the last 1000 million years, suggesting a direct control of the isotopic composition of silicic magmatism on (87Sr/86Sr)seawater variations. The correlation decreases during several time periods, likely reflecting changes in the chemical weathering rate associated with paleogeographic, climatic, or tectonic events. We argue that for most of the last 1000 million years, the (87Sr/86Sr)seawater variations are responding to changes in the isotopic composition of silicic magmatism rather than to changes in the global chemical weathering rate. We conclude that the (87Sr/86Sr)seawater variations are of limited utility to reconstruct changes in the global chemical weathering rate in deep times. PMID:28345044

The isotopic and chemical evolution of planets: Mars as a missing link

NASA Technical Reports Server (NTRS)

Depaolo, D. J.

1988-01-01

The study of planetary bodies has advanced to a stage where it is possible to contemplate general models for the chemical and physical evolution of planetary interiors, which might be referred to as UMPES (Unified Models of Planetary Evolution and Structure). UMPES would be able to predict the internal evolution and structure of a planet given certain input parameters such as mass, distance from the sun, and a time scale for accretion. Such models are highly dependent on natural observations because the basic material properties of planetary interiors, and the processes that take place during the evolution of planets are imperfectly understood. The idea of UMPES was particularly unrealistic when the only information available was from the earth. However, advances have been made in the understanding of the general aspects of planetary evolution now that there is geochemical and petrological data available for the moon and for meteorites.

Lunar initial Nd-143/Nd-144 - Differential evolution of the lunar crust and mantle

NASA Technical Reports Server (NTRS)

Lugmair, G. W.; Marti, K.

1978-01-01

The Sm-Nd evolution of Apollo 15 green glass is discussed. The ICE age (intercept with chondritic evolution) of 3.8 + or - 0.4 eons overlaps the range of reported (Ar-39)-(Ar-40) ages and implies a distinct source region for green glass, characterized by very low and unfractionated REE abundances. Evidence is presented that LINd (lunar initial Nd) is compatible with a 'chondritic'-type Nd isotopic evolution as observed in the Juvinas meteorite. This normalization is used to study the Sm-Nd system of various lunar rock types. The results obtained from a limited number of rocks clearly indicate differential Sm-Nd evolution for the lunar crust and mantle. High-Ti basalts returned by the Apollo 11 and 17 missions were derived from distinct source regions. The Nd-143 evolution in KREEP requires a source region which is clearly distinct from any mantle reservoir.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

NASA Astrophysics Data System (ADS)

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; Nittler, Larry R.; Meyer, Bradley S.; O’D. Alexander, Conel M.; Davis, Andrew M.; Trappitsch, Reto; Pellin, Michael J.

2018-03-01

We report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB (14N/15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains (14N/15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likely originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars’ pre-SN evolution rather than from an explosive neutron-capture process. In addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

DOE PAGES

Liu, Nan; Stephan, Thomas; Boehnke, Patrick; ...

2018-03-16

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Common Occurrence of Explosive Hydrogen Burning in Type II Supernovae

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

Liu, Nan; Stephan, Thomas; Boehnke, Patrick

In this paper, we report Mo isotopic data for 16 15N-rich presolar SiC grains of type AB ( 14N/ 15N < solar, AB1) and their correlated Sr and Ba isotope ratios when available. Of the 16 AB1 grains, 8 show s-process Mo isotopic compositions, together with s-process Ba and/or Sr isotopic compositions. We found that a higher percentage of AB1 grains show anomalous isotopic compositions than that of AB2 grains ( 14N/ 15N > solar), thus providing further support to the division of the two AB subgroups recently proposed by Liu et al., who showed that AB1 grains most likelymore » originated from Type II supernovae (SNe) with explosive H burning. Comparison of the Sr, Mo, and Ba isotopic compositions of the AB1 grains with SN model predictions indicates that the s-process isotopic compositions of AB1 grains resulted from neutron-capture processes occurring during the progenitor massive stars' pre-SN evolution rather than from an explosive neutron-capture process. Finally, in addition, the observations of (1) explosive H burning occurring in the C-rich regions of the progenitor SNe of X grains as suggested by the isotopic compositions of X grains, and (2) explosive H burning occurring both at the bottom of the He/C zone and at the top of the He/N zone as suggested by model simulations, imply that explosive H burning is a common phenomenon in outer SN zones.« less

Copper and tin isotopic analysis of ancient bronzes for archaeological investigation: development and validation of a suitable analytical methodology.

PubMed

Balliana, Eleonora; Aramendía, Maite; Resano, Martin; Barbante, Carlo; Vanhaecke, Frank

2013-03-01

Although in many cases Pb isotopic analysis can be relied on for provenance determination of ancient bronzes, sometimes the use of "non-traditional" isotopic systems, such as those of Cu and Sn, is required. The work reported on in this paper aimed at revising the methodology for Cu and Sn isotope ratio measurements in archaeological bronzes via optimization of the analytical procedures in terms of sample pre-treatment, measurement protocol, precision, and analytical uncertainty. For Cu isotopic analysis, both Zn and Ni were investigated for their merit as internal standard (IS) relied on for mass bias correction. The use of Ni as IS seems to be the most robust approach as Ni is less prone to contamination, has a lower abundance in bronzes and an ionization potential similar to that of Cu, and provides slightly better reproducibility values when applied to NIST SRM 976 Cu isotopic reference material. The possibility of carrying out direct isotopic analysis without prior Cu isolation (with AG-MP-1 anion exchange resin) was investigated by analysis of CRM IARM 91D bronze reference material, synthetic solutions, and archaeological bronzes. Both procedures (Cu isolation/no Cu isolation) provide similar δ (65)Cu results with similar uncertainty budgets in all cases (±0.02-0.04 per mil in delta units, k = 2, n = 4). Direct isotopic analysis of Cu therefore seems feasible, without evidence of spectral interference or matrix-induced effect on the extent of mass bias. For Sn, a separation protocol relying on TRU-Spec anion exchange resin was optimized, providing a recovery close to 100 % without on-column fractionation. Cu was recovered quantitatively together with the bronze matrix with this isolation protocol. Isotopic analysis of this Cu fraction provides δ (65)Cu results similar to those obtained upon isolation using AG-MP-1 resin. This means that Cu and Sn isotopic analysis of bronze alloys can therefore be carried out after a single chromatographic separation using TRU-Spec resin. Tin isotopic analysis was performed relying on Sb as an internal standard used for mass bias correction. The reproducibility over a period of 1 month (n = 42) for the mass bias-corrected Sn isotope ratios is in the range of 0.06-0.16 per mil (2 s), for all the ratios monitored.

Uranium Isotope Ratios in Modern and Precambrian Soils

NASA Astrophysics Data System (ADS)

DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

2015-12-01

Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

The initial Hf isotopic composition of the Earth

NASA Astrophysics Data System (ADS)

Bouvier, A.; Boyet, M. M.; Vervoort, J. D.; Patchett, P. J.

2011-12-01

One area of considerable activity in trying to understand the formation and evolution of Earth's crust is the isotopic analysis of Hf in parallel with Sm-Nd and U-Pb zircon studies, either to constrain early crustal growth and evolution [1], or as a complement to detrital zircon studies [2]. The 176Lu decay constant deduced from early planetary and Earth materials have different values. It has been suggested that a period of irradiation in the early Solar System affected the 176Hf production rate in meteoritic and planetary materials [3,4]. In this scenario, the initial Hf isotopic composition of the Solar System and the Earth would be ~4 ∈Hf units lower, affecting tremendously the interpretation of the differentiation history of the early Earth. We investigated Lu-Hf compositions of calcium-aluminum-rich inclusions, the oldest known objects of the Solar System dated at 4568 Ma [5], to assess the possibility of neutrino irradiation in the solar nebula. Here we report high-precision 176Lu-176Hf systematics of leached and unleached, and spiked and unspiked, bulk fractions and mineral separates of 6 individual CAIs from 2 CV3 chondrites. Isotopic analyses were carried out by Neptune MC-ICPMS at ASU. Analytical details are in [6,7]. The unspiked Hf fractions reveal stable isotope anomalies of μ178Hf= 20 ± 6 and μ180Hf= 31 ± 9 (2SD) for the CAI B4 fractions (n=3) and μ178Hf= -4 ± 10 and μ180Hf= 2 ± 10 (n=2) for BCR-2 relative to the JMC 475 Hf standard. Further high-precision analysis of unspiked Sm and Nd fractions of the samples will be made to correct from nucleosynthetic or neutron capture anomalies [8]. Such Hf stable isotopic anomalies predict no more than 50ppm correction on 176Hf/177Hf. At this stage, we have thus regressed together the spiked and unspiked Hf compositions of CAI fractions (n=13) for isochron calculations. The slope of the Lu-Hf isochron is 0.0882 ± 0.0026 (2SD) which corresponds to a 176Lu decay constant value of 1.852 (± 0.052) ×10-11×y-1 consistent with the "terrestrial" determination [9,10]. We do not find evidence of 176Hf excesses in the CAI Lu-Hf systematics which excludes the possibility of neutrino irradiation to explain the anomalous Lu-Hf isochron ages of eucrite and angrite meteorites [3]. The initial 176Hf/177Hf of the CAIs and thus of the Solar System is 0.28286 ± 0.00011 which is consistent with the estimates of 0.28279 ± 0.00002 obtained using the modern CHUR composition [6] and the terrestrial decay constant [9,10]. This last composition remains the best estimate for the initial 176Hf/177Hf of the Earth. [1] Harrison. AREP Sci. 2009 37, 479. [2] Sun et al. Prec. Res. 2009 172, 99. [3] Albarède et al. GCA 2006 70, 1261. [4] Thrane et al. Astrophys. J. 2010 717, 861-867. [5] Bouvier & Wadhwa. Nat. Geosci. 2010 3, 637. [6] Bouvier et al. EPSL 2008 273, 48. [7] Münker et al. G3 2001 2. [8] Sprung et al. EPSL 2010 295, 1. [9] Scherer et al. Science 2001 293, 683. [10] Söderlund et al. EPSL 2004 219, 311.

Converting isotope ratios to diet composition - the use of mixing models - June 2010

EPA Science Inventory

One application of stable isotope analysis is to reconstruct diet composition based on isotopic mass balance. The isotopic value of a consumer’s tissue reflects the isotopic values of its food sources proportional to their dietary contributions. Isotopic mixing models are used ...

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.

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

NASA Technical Reports Server (NTRS)

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

2010-01-01

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

Origin of heavy Fe isotope compositions in high-silica igneous rocks: A rhyolite perspective

NASA Astrophysics Data System (ADS)

Du, De-Hong; Wang, Xiao-Lei; Yang, Tao; Chen, Xin; Li, Jun-Yong; Li, Weiqiang

2017-12-01

The origin of heavy Fe isotope compositions in high-silica (>70 wt% SiO2) igneous rocks remains a highly controversial topic. Considering that fluid exsolution in eruptive rocks is more straight-forward to constrain than in plutonic rocks, this study addresses the problem of Fe isotope fractionation in high-silica igneous rocks by measuring Fe isotope compositions of representative rhyolitic samples from the Neoproterozoic volcanic-sedimentary basins in southern China and the Triassic Tu Le Basin in northern Vietnam. The samples show remarkably varied δ56FeIRMM014 values ranging from 0.05 ± 0.05‰ to 0.55 ± 0.05‰, which is among the highest values reported from felsic rocks. The extensional tectonic setting and short melt residence time in magma chambers for the studied rhyolites rule out Soret diffusion and thermal migration processes as causes of the high δ56Fe values. Effects of volcanic degassing and fluid exsolution on bulk rock δ56Fe values for the rhyolites are also assessed using bulk rock geochemical indicators and Rayleigh fractionation models, and these processes are found to be insufficient to produce resolvable changes in Fe isotope compositions of the residual melt. The most probable mechanism accounting for heavy Fe isotope compositions in the high-silica rhyolites is narrowed down to fractional crystallization processes in the magma before rhyolite eruption. Removal of isotopically light Fe-bearing minerals (i.e. ulvöspinel-rich titanomagnetite, ilmenite and biotite) is proposed as the main cause of Fe isotope variation in silicic melts during magmatic evolution. This study implies that crystal fractionation is the dominant mechanism that controls Fe isotope fractionation in eruptive rocks and Fe isotopes could be used to study magmatic differentiation of high-silica magmas.

Generation and Reworking of Archaean and Hadean Crust

NASA Astrophysics Data System (ADS)

Hawkesworth, C.; Kemp, T.; Storey, C.; Dhuime, B.

2008-12-01

Combined Hf and O isotopes in well-dated zircons are increasingly used to investigate the age of the crustal source rocks of detrital and inherited zircons. O isotopes are used to screen out samples that may have a sediment contribution in the parental magma, since sediments yield hybrid model ages that are difficult to interpret. Mafic and granitic rocks also have different Lu/Hf ratios, and so in principle the Hf isotope ratios of zircons can be used to investigate the broad composition of the average crust. The unradiogenic Hf isotope compositions of the Jack Hills zircons from Western Australia indicate the existence of enriched (crustal) reservoirs by at least 4.3 Ga (Y. Amelin et al., 1998, Nature v. 399, p. 252- 255; T. M. Harrison et al., 2005, Science, v. 310, p. 1947-1950). We report in situ Hf isotope analyses of the Jack Hills zircons in which the Pb isotope age information is measured concurrently with the Hf isotope data. The simple data arrays provide clear evidence for Earth differentiation at 4.5 Ga, with the production of both continental crust-like material and a mafic crustal reservoir with higher Lu/Hf. The continued resampling of this reservoir over at least 1.5 Ga argues for a substantial stabilised volume of mafic crust, and, in tandem with oxygen isotope data, the existence of Hadean continents. Zircons remain poor windows into the upper mantle. We therefore investigate Nd isotopes in well-dated titanites; they have closure temperatures for Pb in the range 600-750oC and they can retain cores with distinct age and REE chemistry to subsequent rim overgrowths. Nd isotopes offer a complementary approach to Hf in zircon that can be used to construct the both depleted mantle evolution and crustal growth curves.

Cenozoic intra-plate magmatism in the Darfur volcanic province: mantle source, phonolite-trachyte genesis and relation to other volcanic provinces in NE Africa

NASA Astrophysics Data System (ADS)

Lucassen, Friedrich; Pudlo, Dieter; Franz, Gerhard; Romer, Rolf L.; Dulski, Peter

2013-01-01

Chemical and Sr, Nd and Pb isotopic compositions of Late Cenozoic to Quaternary small-volume phonolite, trachyte and related mafic rocks from the Darfur volcanic province/NW-Sudan have been investigated. Isotope signatures indicate variable but minor crustal contributions. Some phonolitic and trachytic rocks show the same isotopic composition as their primitive mantle-derived parents, and no crustal contributions are visible in the trace element patterns of these samples. The magmatic evolution of the evolved rocks is dominated by crystal fractionation. The Si-undersaturated strongly alkaline phonolite and the Si-saturated mildly alkaline trachyte can be modelled by fractionation of basanite and basalt, respectively. The suite of basanite-basalt-phonolite-trachyte with characteristic isotope signatures from the Darfur volcanic province fits the compositional features of other Cenozoic intra-plate magmatism scattered in North and Central Africa (e.g., Tibesti, Maghreb, Cameroon line), which evolved on a lithosphere that was reworked or formed during the Neoproterozoic.

Stable Isotope Measurements of Martian Atmospheric CO2 at the Phoenix Landing Site

NASA Astrophysics Data System (ADS)

Niles, Paul B.; Boynton, William V.; Hoffman, John H.; Ming, Douglas W.; Hamara, Dave

2010-09-01

Carbon dioxide is a primary component of the martian atmosphere and reacts readily with water and silicate rocks. Thus, the stable isotopic composition of CO2 can reveal much about the history of volatiles on the planet. The Mars Phoenix spacecraft measurements of carbon isotopes [referenced to the Vienna Pee Dee belemnite (VPDB)] [δ13CVPDB = -2.5 ± 4.3 per mil (‰)] and oxygen isotopes [referenced to the Vienna standard mean ocean water (VSMOW)] (δ18OVSMOW = 31.0 ± 5.7‰), reported here, indicate that CO2 is heavily influenced by modern volcanic degassing and equilibration with liquid water. When combined with data from the martian meteorites, a general model can be constructed that constrains the history of water, volcanism, atmospheric evolution, and weathering on Mars. This suggests that low-temperature water-rock interaction has been dominant throughout martian history, carbonate formation is active and ongoing, and recent volcanic degassing has played a substantial role in the composition of the modern atmosphere.

Using stable isotopes and major ions to identify hydrological processes and geochemical characteristics in a typical karstic basin, Guizhou, Southwest China.

PubMed

Han, Zhiwei; Tang, Changyuan; Wu, Pan; Zhang, Ruixue; Zhang, Chipeng

2014-01-01

The investigation of hydrological processes is very important for water resource development in karst basins. In order to understand these processes associated with complex hydrogeochemical evolution, a typical basin was chosen in Houzai, southwest China. The basin was hydrogeologically classified into three zones based on hydrogen and oxygen isotopes as well as the field surveys. Isotopic values were found to be enriched in zone 2 where paddy fields were prevailing with well-developed underground flow systems, and heavier than those in zone 1. Zone 3 was considered as the mixture of zones 1 and 2 with isotopic values falling in the range between the two zones. A conceptual hydrological model was thus proposed to reveal the probable hydrological cycle in the basin. In addition, major processes of long-term chemical weathering in the karstic basin were discussed, and reactions between water and carbonate rocks proved to be the main geochemical processes in karst aquifers.

[High-precision in situ analysis of the lead isotopic composition in copper using femtosecond laser ablation MC-ICP-MS and the application in ancient coins].

PubMed

Chen, Kai-Yun; Fan, Chao; Yuan, Hong-Lin; Bao, Zhi-An; Zong, Chun-Lei; Dai, Meng-Ning; Ling, Xue; Yang, Ying

2013-05-01

In the present study we set up a femtosecond laser ablation MC-ICP-MS method for lead isotopic analysis. Pb isotopic composition of fifteen copper (brass, bronze) standard samples from the National Institute of Standards Material were analyzed using the solution method (MC-ICP-MS) and laser method (fLA-MC-ICPMS) respectively, the results showed that the Pb isotopic composition in CuPb12 (GBW02137) is very homogeneous, and can be used as external reference material for Pb isotopic in situ analysis. On CuPb12 112 fLA-MC-ICPMS Pb isotope analysis, the weighted average values of the Pb isotopic ratio are in good agreement with the results analyzed by bulk solution method within 2sigma error, the internal precision RSEs of the 208 Pb/204 Pb ratio and 207 Pb/206 Pb ratio are less than 90 and 40 ppm respectively, and the external precision RSDs of them are less than 60 and 30 ppm respectively. Pb isotope of thirteen ancient bronze coins was analyzed via fLA-MC-ICPMS, the results showed that the Pb isotopic composition of ancient coins of different dynasties is significantly different, and not all the Pb isotopic compositions in the coins even from the same dynasty are in agreement with each other.

Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

NASA Technical Reports Server (NTRS)

Williford, Kenneth H.; Ushikubo, Takayuki; Lepot, Kevin; Hallmann, Christian; Spicuzza, Michael J.; Eigenbrode, Jennifer L.; Summons, Roger E.; Valley, John W.

2011-01-01

Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

Laser Ablation Molecular Isotopic Spectrometry for Molecules Formation Chemistry in Femtosecond-Laser Ablated Plasmas.

PubMed

Hou, Huaming; Mao, Xianglei; Zorba, Vassilia; Russo, Richard E

2017-07-18

Recently, laser ablated molecular isotopic spectrometry (LAMIS) has expanded its capability to explore molecules formation mechanism in laser-induced plasma in addition to isotope analysis. LAMIS is a powerful tool for tracking the origination of atoms that is involved in formation of investigated molecules by labeling atoms with their isotopic substitution. The evolutionary formation pathways of organic molecules, especially of C 2 dimers and CN radicals, were frequently reported. However, very little is known about the formation pathways for metallic radicals and heterodimers in laser ablated plasma. This research focuses on elucidating the formation pathways of AlO radicals in femtosecond laser ablated plasma from 18 O-labeled Al 2 O 3 pellet. Plasmas expanding with strong forward bias in the direction normal to the sample surface were generated in the wake of a weakly ionized channel created by a femtosecond laser. The formation mechanism of AlO and influence of air were investigated with multiple plasma diagnostic methods such as monochromatic fast gating imaging, spatiotemporal resolved optical emission spectroscopy, and LAMIS. An advanced LAMIS fitting procedure was used to deduce the spatiotemporal distributions of Al 18 O and Al 16 O number densities and also their ratios. We found that the Al 16 O/Al 18 O number density ratio is higher for plasma portion closer to the sample surface, which suggests that chemical reactions between the plasma plume and ambient air are more intense at the tail of the plasma. The results also reveals that direct association of free Al and O atoms is the main mechanism for the formation of AlO at the early stage of the plasma. To the contrast, chemical reactions between plasma materials and ambient oxygen molecules and the isotope exchange effect are the dominant mechanisms of the formation of AlO and evolution of Al 16 O/Al 18 O number density ratio at the late stage of the plasma.

Life sciences and space research 24 (4): Planetary biology and origins of life; Topical Meeting of the COSPAR Interdisciplinary Scientific Commission F (Meeting F3) of the COSPAR Plenary Meeting, 29th, Washington, DC, Aug. 28-Sep. 5, 1992

NASA Technical Reports Server (NTRS)

Greenberg, J. M. (Editor); Oro, J. (Editor); Brack, A. (Editor); Devincenzi, D. L. (Editor); Banin, A. (Editor); Friedmann, E. I. (Editor); Rummel, J. D. (Editor); Raulin, F. (Editor); Mckay, C. P. (Editor); Baltscheffsky, H. (Editor)

1995-01-01

The proceedings include sessions on extraterrestrial organic chemistry and the origins of life; life on Mars: past, present and future; planetary protection of Mars missions; chemical evolution on Titan; origins and early evolution of biological (a) energy transduction and membranes (b) information and catalysis; and carbon chemistry and isotopic fractionations in astrophysical environments.

Correlated silicon and titanium isotopic compositions of presolar SiC grains from the Murchison CM2 chondrite

NASA Astrophysics Data System (ADS)

Gyngard, Frank; Amari, Sachiko; Zinner, Ernst; Marhas, Kuljeet Kaur

2018-01-01

We report correlated Si, and Ti isotopic compositions and elemental concentrations of 238 presolar SiC grains from the Murchison CM2 meteorite. Combined with measurements of the C and N isotopic compositions of these 238 grains, 220 were determined to be of type mainstream, 10 type AB, 4 type Y and 4 type Z. SiC grains of diameter ≳2.5 μm, to ensure enough material to attempt Ti measurements, were randomly chosen without any other prejudice. The Ti isotopic compositions of the majority of the grains are characterized by enrichments in 46Ti, 47Ti, 49Ti, and 50Ti relative to 48Ti, and show linear isotopic correlations indicative of galactic chemical evolution and neutron capture of the grains parent stars. The variability in the observed Ti signal as a function of depth in most of the grains indicates the presence of distinct subgrains, likely TiC that have been previously observed in TEM studies. Vandium-51 concentrations correlate with those of Ti, indicating V substitutes for Ti in the TiC matrix in many of the grains. No isotopic anomalies in 52Cr/53Cr ratios were observed, and Cr concentrations did not correlate with those of either Ti or V.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event.

PubMed

Planavsky, Noah J; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D; Lyons, Timothy W

2012-11-06

Carbonates from approximately 2.3-2.1 billion years ago show markedly positive δ(13)C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ(13)C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth's most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ(34)S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ(34)S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ(34)S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion.

Contribution of collagen stable isotope biogeochemistry to the paleobiology of extinct endemic vertebrates from Tenerife (Canary Islands, Spain).

PubMed

Bocherens, H; Michaux, J; Billiou, D; Castanet, J; Garcìa-Talavera, F

2003-09-01

The paleodiet and paleoenvironmental context of two extinct species from Tenerife island, one giant rat Canariomys bravoi and one giant lizard Gallotia goliath, have been investigated using carbon and nitrogen isotopic compositions of fossil bone collagen. Preliminary to this study, a calibration of the isotopic variations of bone collagen from modern Rat Rattus rattus, Rabbit Oryctolagus cuniculus and Lizard Gallotia galotti relative to environmental conditions on Tenerife Islands has been attempted. No clear relationship could be found between collagen delta13C and delta15N values and aridity; the only relevant factors seem to be seashore proximity for rat, and the relative amount of C3 and CAM plants. It seems that anthropic activities have interfered with the expected relationships between collagen isotopic compositions and environmental conditions. Most fossil specimens yielded well preserved collagen. The isotopic composition of giant rat and giant lizard collagen suggest a purely C3 environment, possibly more humid than today on Tenerife. Large ranges of nitrogen isotopic compositions, especially within giant rats, may be due to local environmental conditions. Further work is needed in order to provide more valuable paleobiological information in order to better understand the role of environmental factors in the evolution and extinction of insular endemic species on Tenerife.

Seasonal C-13 variations of methane from an anoxic marine sediment

NASA Technical Reports Server (NTRS)

Blair, Neal; Desmarais, David S.; Martens, Christopher S.

1985-01-01

Recent analyses of glacial ice suggest that the atmospheric concentration of methane has doubled in the last several hundred years, presumably due to anthropogenic perturbations of the relevant biogeochemical cycles. In principal, carbon isotopic measurements of atmospheric methane would provide information concerning changes in the sources and sinks of methane. The isotopic composition of methane is dependent on the source of the methane carbon, the mechanism of methane synthesis, and the degree and mode of oxidation which the methane has experienced. Unfortunately, few carbon isotopic measurements of atmospheric variations have been reported, so conclusions about temporal isotopic variations cannot be made. Also, before isotopic measurements of atmospheric methane can be used to identify changes in methane isotopic composition from different sources must be obtained. Methane bubbles from the anoxic sediments of Cape Lookout Bight, NC exhibit seasonal C-13 variations. The C-13 values ranged from -58 in August to -64 in the winter months with the evolution of the C-13 enriched gas occurring during periods of peak methane production. Even though a few intramolecular C-13 measurements of the pore water acetate have been made (methyl group, -26 per mil; carbonyl, -6 per mil), it is not clear how the acetate fermentation pathway affects the methane C-13/C-12 composition.

Emplacement ages, geochemical and Sr-Nd-Hf isotopic characterization of Mesozoic to early Cenozoic granitoids of the Sikhote-Alin Orogenic Belt, Russian Far East: Crustal growth and regional tectonic evolution

NASA Astrophysics Data System (ADS)

Jahn, Bor-ming; Valui, Galina; Kruk, Nikolai; Gonevchuk, V.; Usuki, Masako; Wu, Jeremy T. J.

2015-11-01

The Sikhote-Alin Range of the Russian Far East is an important accretionary orogen of the Western Pacific Orogenic Belt. In order to study the formation and tectonic evolution of the orogen, we performed zircon U-Pb dating, as well as geochemical and Sr-Nd-Hf isotopic analyses on 24 granitoid samples from various massifs in the Primorye and Khabarovsk regions. The zircon dating revealed that the granitoids were emplaced from 131 to 56 Ma (Cretaceous to Paleogene). In the Primorye Region, granitoids in the coastal Sikhote-Alin intruded the Cretaceous Taukha Accretionary Terrane from ca. 90 to 56 Ma, whereas those along the Central Sikhote-Alin Fault zone intruded the Jurassic Samarka Accretionary Terrane during ca. 110-75 Ma. The "oldest" monzogranite (131 Ma) was emplaced in the Lermontovka area of the NW Primorye Region. Granitoid massifs along the Central Sikhote-Alin Fault zone in the Khabarovsk Region formed from 109 to 58 Ma. Thus, the most important tectonothermal events in the Sikhote-Alin orogen took place in the Cretaceous. Geochemical analysis indicates that most samples are I-type granitoids. They have initial 87Sr/86Sr ratios ranging from 0.7040 to 0.7083, and initial Nd isotopic ratios, expressed as εNd(t) values, from +3.0 to -5.0 (mostly 0 to -5). The data suggest that the granitoid magmas were generated by partial melting of sources with mixed lithologies, including the subducted accretionary complex ± hidden Paleozoic-Proterozoic basement rocks. Based on whole-rock Nd isotopic data, we estimated variable proportions (36-77%) of juvenile component (=mantle-derived basaltic rocks) in the generation of the granitic magmas. Furthermore, zircon Hf isotopic data (εHf(t) = 0 to +15) indicate that the zircon grains crystallized from melts of mixed sources and that crustal assimilation occurred during magmatic differentiation. The quasi-continuous magmatism in the Sikhote-Alin orogen suggests that the Paleo-Pacific plate subduction was very active in the Late Cretaceous. The apparently regular progression of granitic intrusion ages from 80 to 56 Ma in the Taukha Terrane may reflect oblique underflow of the Paleo-Pacific plate beneath the Eurasian continental margin. Subduction was not only manifested by granitic intrusion, but also by abundant silicic volcanism. The Late Cretaceous Paleo-Pacific plate motion probably changed from parallel or sub-parallel to oblique relative to the continental margin of the Sikhote-Alin, leading to the change of magmatic source region and geochemical characteristics of the derived igneous rocks. Late Cretaceous rapid sea-floor spreading at ca. 100 Ma induced highly active subduction and led to voluminous magmatism in the entire Circum-Pacific realm. Finally, the present age and isotopic study lends support to the hypothesis of geologic and tectonic correlation between Sikhote-Alin and SW Japan.

The case for a deep-atmospheric in situ mission to address the highest priority Decadal Survey questions for Venus (Invited)

NASA Astrophysics Data System (ADS)

Atreya, S. K.; Garvin, J. B.; Glaze, L. S.; Campbell, B. A.; Fisher, M. E.; Flores, A.; Gilmore, M. S.; Johnson, N.; Kiefer, W. S.; Lorenz, R. D.; Mahaffy, P. R.; Ravine, M. A.; Webster, C. R.; Zolotov, M. Y.

2013-12-01

Current understanding of Venus lags behind that for Mars, with a major disparity of information concerning noble and trace gases and the small scale surface processes needed for comparative studies of terrestrial planet evolution. Despite global surface mapping by Magellan, discoveries by Venera landers, and ongoing atmospheric observations by the Venus Express (VEx) orbiter, significant questions about Venus remain unanswered. To place Venus into its proper context with respect to Mars and Earth, it is necessary to obtain new measurements that address top issues identified in the National Research Council (NRC) Solar System Decadal Survey: (1) evolution of the atmosphere, history of climate, and evidence of past hydrologic cycles; (2) history of volatiles and sedimentary cycles; and (3) planetary surface evolution. To answer these questions, new measurements are needed. First and foremost, in situ noble gas measurements are needed to constrain solar system formation and Venus evolution. In particular, the isotopic ratios of Xe and Kr can provide unique insights into planetary accretion. Isotopic measurements of nitrogen (15N/14N) will place important constraints on atmospheric loss processes. Current knowledge of this ratio has a substantial uncertainty of ×20%. VEx observations of hydrogen isotopes indicate the D/H ratio above the clouds is substantially greater than measured by Pioneer Venus, and varies with height. High precision measurements of the vertical distribution of the D/H isotopic ratio below the cloud layers will provide constraints on models of the climate history of water on Venus. The majority of atmospheric mass is located below the clouds. Current data suggest intense interaction among atmospheric gases down to the surface. The haze within the cloud region of unknown composition plays a central role in the radiative balance. Photochemically-derived species (H2SO4, OCS, CO, Sn) are subjected to thermochemical reactions below the clouds, especially within 30 km of the surface. Competing temperature-pressure dependent reactions and atmospheric circulation may cause vertical and latitudinal gradients of chemically-active trace gases (e.g., SO2, H2S, OCS, CO). Measurements of the chemical composition of the near-surface atmosphere can be used to evaluate the stability of primary and secondary minerals and can help to understand chemistry of atmosphere-surface interactions. However, concentrations of many trace species have never been measured below ~30 km, and multiple in situ measurements are required to evaluate chemical processes and cycles of volatiles, which can only be accomplished with deep entry probes. Current lack of understanding about Venus not only limits our understanding of evolutionary pathways Earth could experience, but also suggests that we are ill-equipped to understand the evolution of star systems with similar-sized planets.

What can one sample tell us? Stable isotopes can assess complex processes in national assessments of lakes, rivers and streams.

EPA Science Inventory

Stable isotopes can be very useful in large-scale monitoring programs because samples for isotopic analysis are easy to collect, and isotopes integrate information about complex processes such as evaporation from water isotopes and denitrification from nitrogen isotopes. Traditi...

Stable nitrogen isotope analysis of dentine serial sections elucidate sex differences in weaning patterns of wild chimpanzees (Pan troglodytes).

PubMed

Fahy, Geraldine E; Richards, Michael P; Fuller, Benjamin T; Deschner, Tobias; Hublin, Jean-Jacques; Boesch, Christophe

2014-04-01

Offspring provisioning is one of the most energetically demanding aspects of reproduction for female mammals. Variation in lactation length and weaning strategies between chimpanzees (Pan troglodytes), our closest living relative, and modern human societies have been reported. When and why these changes occurred is frequently debated. Our study used stable nitrogen isotope data of tooth root dentine from wild Western chimpanzees (Pan troglodytes verus) in Taï National Park, Côte d'Ivoire, to quantify weaning in these chimpanzees and explore if infant sex plays a role in maternal investment. We analyzed serial sections of deciduous lateral incisor root dentine from four Taï chimpanzees to establish the δ(15) N signal of nursing infants; we then analyzed serial sections of first permanent mandibular molar root dentine from 12 Taï chimpanzees to provide quantitative δ(15) N data on weaning in this population. Up to 2 years of age both sexes exhibited dentine δ(15) N values ≈2-3‰ higher than adult female Taï chimpanzees, consistent with a nursing signal. Thereafter a steady decrease in δ(15) N values consistent with the onset, and progression, of weaning, was visible. Sex differences were also evident, where male δ(15) N values decreased at a significantly slower rate compared to females. Confirmation of sex differences in maternal investment among Taï chimpanzees, demonstrates the viability of using isotope analysis to investigate weaning in non-human primates. Additionally, assuming that behaviors observed in the Taï chimpanzees are illustrative of the ancestral pattern, our results provide a platform to enable the trajectory of weaning in human evolution to be further explored. Copyright © 2013 Wiley Periodicals, Inc.

An in situ accelerator-based diagnostic for plasma-material interactions science on magnetic fusion devices.

PubMed

Hartwig, Zachary S; Barnard, Harold S; Lanza, Richard C; Sorbom, Brandon N; Stahle, Peter W; Whyte, Dennis G

2013-12-01

This paper presents a novel particle accelerator-based diagnostic that nondestructively measures the evolution of material surface compositions inside magnetic fusion devices. The diagnostic's purpose is to contribute to an integrated understanding of plasma-material interactions in magnetic fusion, which is severely hindered by a dearth of in situ material surface diagnosis. The diagnostic aims to remotely generate isotopic concentration maps on a plasma shot-to-shot timescale that cover a large fraction of the plasma-facing surface inside of a magnetic fusion device without the need for vacuum breaks or physical access to the material surfaces. Our instrument uses a compact (~1 m), high-current (~1 milliamp) radio-frequency quadrupole accelerator to inject 0.9 MeV deuterons into the Alcator C-Mod tokamak at MIT. We control the tokamak magnetic fields--in between plasma shots--to steer the deuterons to material surfaces where the deuterons cause high-Q nuclear reactions with low-Z isotopes ~5 μm into the material. The induced neutrons and gamma rays are measured with scintillation detectors; energy spectra analysis provides quantitative reconstruction of surface compositions. An overview of the diagnostic technique, known as accelerator-based in situ materials surveillance (AIMS), and the first AIMS diagnostic on the Alcator C-Mod tokamak is given. Experimental validation is shown to demonstrate that an optimized deuteron beam is injected into the tokamak, that low-Z isotopes such as deuterium and boron can be quantified on the material surfaces, and that magnetic steering provides access to different measurement locations. The first AIMS analysis, which measures the relative change in deuterium at a single surface location at the end of the Alcator C-Mod FY2012 plasma campaign, is also presented.

Constraints on the composition of the ancient terrestrial atmosphere and hydrosphere from fluid inclusion analysis

NASA Astrophysics Data System (ADS)

Marty, B.; Avice, G.; Burgess, R.

2016-12-01

The evolution of the hydrosphere and atmosphere during the first half of Earth's history is still largely unknown. We are currently investigating the compositions of these reservoirs from the analysis of fluid inclusions trapped in 3.5-2.7 Ga-old hydrothermal quartz. We specifically analyze noble gases and nitrogen which are conservative enough to have survived the long history of their host phases. The samples come from Archean terranes situated in North Pole, the Pilbara, NW Australia, and in the Barberton greenstone belt, South Africa. Their morphologies suggest that the quartz deposition was contemporary with terrane formation. They were selected on the basis of their ages determined by the Ar-Ar method. The results published by our group show that the noble gas isotopic composition of the Archean atmosphere was similar to the modern one, with the outstanding exception of xenon. This heavy noble gas experienced gradual isotopic fractionation through time, as a result of its preferential escape to space, which mechanism remains to be elucidated. In contrast, the isotope composition of atmospheric N was similar to the modern one, suggesting little, if any, loss of this element from the terrestrial atmosphere from 3.5 Ga to Present. The atmospheric partial pressure of N2 was likely to be comparable to, or lower than, the modern one, casting doubt on the possibility of enhanced pN2 as a mean to counterbalance the faint Sun energy flux. Here we shall newly report data on chlorine and potassium in fluid inclusions with, together with noble gases, suggest that the salinity of the Archean oceans was not very different from that of the modern seawater.

Laboratory Analysis of Silicate Stardust Grains of Diverse Stellar Origins

NASA Technical Reports Server (NTRS)

Nguyen, Ann N.; Keller, Lindsay P.; Nakamura-Messenger, Keiko

2016-01-01

Silicate dust is ubiquitous in a multitude of environments across the cosmos, including evolved oxygen-rich stars, interstellar space, protoplanetary disks, comets, and asteroids. The identification of bona fide silicate stardust grains in meteorites, interplanetary dust particles, micrometeorites, and dust returned from comet Wild 2 by the Stardust spacecraft has revolutionized the study of stars, interstellar space, and the history of dust in the Galaxy. These stardust grains have exotic isotopic compositions that are records of nucleosynthetic processes that occurred in the depths of their now extinct parent stars. Moreover, the chemical compositions and mineralogies of silicate stardust are consequences of the physical and chemical nature of the stellar condensation environment, as well as secondary alteration processes that can occur in interstellar space, the solar nebula, and on the asteroid or comet parent body in which they were incorporated. In this talk I will discuss our use of advanced nano-scale instrumentation in the laboratory to conduct coordinated isotopic, chemical, and mineralogical analyses of silicate stardust grains from AGB stars, supernovae, and novae. By analyzing the isotopic compositions of multiple elements in individual grains, we have been able to constrain their stellar sources, explore stellar nucleosynthetic and mixing processes, and Galactic chemical evolution. Through our mineralogical studies, we have found these presolar silicate grains to have wide-ranging chemical and mineral characteristics. This diversity is the result of primary condensation characteristics and in some cases secondary features imparted by alteration in space and in our Solar System. The laboratory analysis of actual samples of stars directly complements astronomical observations and astrophysical models and offers an unprecedented level of detail into the lifecycles of dust in the Galaxy.

Experimental evidence for the microscopic mechanism of the unusual spin-induced electric polarization in GdMn2O5

NASA Astrophysics Data System (ADS)

Yahia, G.; Damay, F.; Chattopadhyay, S.; Balédent, V.; Peng, W.; Kim, S. W.; Greenblatt, M.; Lepetit, M.-B.; Foury-Leylekian, P.

2018-02-01

We report in this paper the temperature evolution of the magnetic structure of GdMn2O5 , in the range 2-40 K, studied by neutron diffraction on an isotope-enriched powder. We detail a thorough analysis of the microscopic mechanisms needed to release the different magnetic frustrations that are at the origin of the polarization. In addition to the usual exchange-striction term, known to be at the origin of the polarization in this family, an additional exchange-striction effect between the Gd3 + and Mn3 + spins is found to be responsible for the very large polarization in the Gd compound.

Iron isotope biogeochemistry of Neoproterozoic marine shales

NASA Astrophysics Data System (ADS)

Kunzmann, Marcus; Gibson, Timothy M.; Halverson, Galen P.; Hodgskiss, Malcolm S. W.; Bui, Thi Hao; Carozza, David A.; Sperling, Erik A.; Poirier, André; Cox, Grant M.; Wing, Boswell A.

2017-07-01

Iron isotopes have been widely applied to investigate the redox evolution of Earth's surface environments. However, it is still unclear whether iron cycling in the water column or during diagenesis represents the major control on the iron isotope composition of sediments and sedimentary rocks. Interpretation of isotopic data in terms of oceanic redox conditions is only possible if water column processes dominate the isotopic composition, whereas redox interpretations are less straightforward if diagenetic iron cycling controls the isotopic composition. In the latter scenario, iron isotope data is more directly related to microbial processes such as dissimilatory iron reduction. Here we present bulk rock iron isotope data from late Proterozoic marine shales from Svalbard, northwestern Canada, and Siberia, to better understand the controls on iron isotope fractionation in late Proterozoic marine environments. Bulk shales span a δ 56Fe range from -0.45 ‰ to +1.04 ‰ . Although δ 56Fe values show significant variation within individual stratigraphic units, their mean value is closer to that of bulk crust and hydrothermal iron in samples post-dating the ca. 717-660 Ma Sturtian glaciation compared to older samples. After correcting for the highly reactive iron content in our samples based on iron speciation data, more than 90% of the calculated δ 56Fe compositions of highly reactive iron falls in the range from ca. -0.8 ‰ to +3 ‰ . An isotope mass-balance model indicates that diagenetic iron cycling can only change the isotopic composition of highly reactive iron by < 1 ‰ , suggesting that water column processes, namely the degree of oxidation of the ferrous seawater iron reservoir, control the isotopic composition of highly reactive iron. Considering a long-term decrease in the isotopic composition of the iron source to the dissolved seawater Fe(II) reservoir to be unlikely, we offer two possible explanations for the Neoproterozoic δ 56Fe trend. First, a decreasing supply of Fe(II) to the ferrous seawater iron reservoir could have caused the reservoir to decrease in size, allowing a higher degree of partial oxidation, irrespective of increasing environmental oxygen levels. Alternatively, increasing oxygen levels would have led to a higher proportion of Fe(II) being oxidized, without decreasing the initial size of the ferrous seawater iron pool. We consider the latter explanation as the most likely. According to this hypothesis, the δ 56Fe record reflects the redox evolution of Earth's surface environments. δ 56Fe values in pre-Sturtian samples significantly heavier than bulk crust and hydrothermal iron imply partial oxidation of a ferrous seawater iron reservoir. In contrast, mean δ 56Fe values closer to that of hydrothermal iron in post-Sturtian shales reflects oxidation of a larger proportion of the ferrous seawater iron reservoir, and by inference, higher environmental oxygen levels. Nevertheless, significant iron isotopic variation in post-Sturtian shales suggest redox heterogeneity and possibly a dominantly anoxic deep ocean, consistent with results from recent studies using iron speciation and redox sensitive trace metals. However, the interpretation of generally increasing environmental oxygen levels after the Sturtian glaciation highlights the need to better understand the sensitivity of different redox proxies to incremental changes in oxygen levels to enable us to reconcile results from different paleoredox proxies.

A synthesis of Plio-Pleistocene leaf wax biomarker records of hydrological variation in East Africa and their relationship with hominin evolution

NASA Astrophysics Data System (ADS)

Lupien, R.; Russell, J. M.; Campisano, C. J.; Feibel, C. S.; Deino, A. L.; Kingston, J.; Potts, R.; Cohen, A. S.

2017-12-01

Climate change is thought to play a critical role in human evolution. However, the mechanisms behind this relationship are difficult to test due to a lack of long, high-quality paleoclimate records from hominin fossil locales. We improve the understanding of this relationship by examining Plio-Pleistocene lake sediment cores from East Africa that were drilled by the Hominin Sites and Paleolakes Drilling Project, an international effort to study the environment in which our hominin ancestors evolved and dispersed. We have analyzed organic geochemical signals of climate from drill cores from Ethiopia and Kenya spanning the Pliocene to recent time (from north to south: paleolake Hadar, Lake Turkana, Lake Baringo, and paleolake Koora). Specifically, we analyzed the hydrogen isotopic composition of terrestrial leaf waxes, which records changes in regional atmospheric circulation and hydrology. We reconstructed quantitative records of rainfall amount at each of the study sites, which host sediment spanning different geologic times and regions. By compiling these records, we test hominin evolutionary hypotheses as well as crucial questions about climate trend and variability. We find that there is a gradual or step-wise enrichment in δDwax, signifying a trend from a wet to dry climate, from the Pliocene to the Pleistocene, perhaps implying an influence of global temperature, ice sheet extent, and/or atmospheric greenhouse gas concentrations on East African climate. However, the shift is small relative to the amplitude of orbital-scale isotopic variations. The records indicate a strong influence of eccentricity-modulated orbital precession, and imply that local insolation effects are the likely cause of East African precipitation. Several of the intervals of high isotopic variability coincide with key hominin fossil or technological transitions, suggesting that climate variability plays a key role in hominin evolution.

Origins and ages of fracture fluids in the South African Crust

NASA Astrophysics Data System (ADS)

Heard, A. W.; Warr, O.; Borgonie, G.; Linage-Alvarez, B.; Kuloyo, O.; Magnabosco, C.; Lau, M.; Erasmus, M.; Cason, E. D.; van Heerden, E.; Kieft, T. L.; Mabry, J.; Onstott, T. C.; Sherwood Lollar, B.; Ballentine, C. J.

2017-12-01

Crustal fracture fluids can remain isolated for millions (Myr) to billions of years (Gyr), and contain information on paleohydrogeology, subsurface ecology, and conservative components that may elucidate the atmospheric evolution of the early Earth [1-3]. Stable isotope analyses of water combined with isotopic analyses of the dissolved noble gases provide insight into the history of aqueous fracture fluids. We report stable isotope and noble gas data for fracture fluids from 5 different sites in the Witwatersrand Basin and Bushveld Igneous Province, South Africa. We determine radiogenic noble gas residence times ranging from thousands of years to tens of millions of years. The oldest sample, from Masimong Mine, has a water stable isotopic composition close to the global meteoric water line (GMWL), indicating its preservation in the crust and making it one of the oldest recorded paleometeoric waters. The δ2H and δ18O of water in this sample and similar age samples from the same mining district [1,4] require isotopically depleted groundwater recharge compared to modern precipitation. This could reflect a recharge regime at a higher paleolatitude, elevation, or with higher rainfall, established up to tens of Myr ago, and perhaps similar to the recharge regime in the modern Lesotho Highlands [5]. These data suggest that groundwater isotopes may provide useful paleoclimatic information for many Myr. As hypothesized, such paleometeoric water samples lack 124-128Xe enrichments reported from Gyr age groundwaters discovered on the Canadian Shield [3] and in Archean fluid inclusions [6], providing an important control set and reaffirming that those samples record the evolution of ancient atmospheric Xe rather than subsurface alteration. [1] Lippmann, J. et al. (2003) GCA 67, 4597-4619. [2] Lin, L.-H. (2006) et al. Science 314, 479-482. [3] Holland, G. et al. (2013) Nature 497, 357-360. [4] Lippmann-Pipke, J. et al. (2011) Chem. Geol. 283, 287-296. [5] West, A. G. et al. (2014) J. Geochem. Explor. 145, 213-222. [6] Pujol, M. et al. (2011) EPSL 308,298-306.

Low-temperature aqueous alteration on the CR chondrite parent body: Implications from in situ oxygen-isotope analyses

NASA Astrophysics Data System (ADS)

Jilly-Rehak, Christine E.; Huss, Gary R.; Nagashima, Kazu; Schrader, Devin L.

2018-02-01

The presence of hydrated minerals in chondrites indicates that water played an important role in the geologic evolution of the early Solar System; however, the process of aqueous alteration is still poorly understood. Renazzo-like carbonaceous (CR) chondrites are particularly well-suited for the study of aqueous alteration. Samples range from being nearly anhydrous to fully altered, essentially representing snapshots of the alteration process through time. We studied oxygen isotopes in secondary-minerals from six CR chondrites of varying hydration states to determine how aqueous fluid conditions (including composition and temperature) evolved on the parent body. Secondary minerals analyzed included calcite, dolomite, and magnetite. The O-isotope composition of calcites ranged from δ18O ≈ 9 to 35‰, dolomites from δ18O ≈ 23 to 27‰, and magnetites from δ18O ≈ -18 to 5‰. Calcite in less-altered samples showed more evidence of fluid evolution compared to heavily altered samples, likely reflecting lower water/rock ratios. Most magnetite plotted on a single trend, with the exception of grains from the extensively hydrated chondrite MIL 090292. The MIL 090292 magnetite diverges from this trend, possibly indicating an anomalous origin for the meteorite. If magnetite and calcite formed in equilibrium, then the relative 18O fractionation between them can be used to extract the temperature of co-precipitation. Isotopic fractionation in Al Rais carbonate-magnetite assemblages revealed low precipitation temperatures (∼60 °C). Assuming that the CR parent body experienced closed-system alteration, a similar exercise for parallel calcite and magnetite O-isotope arrays yields "global" alteration temperatures of ∼55 to 88 °C. These secondary mineral arrays indicate that the O-isotopic composition of the altering fluid evolved upon progressive alteration, beginning near the Al Rais water composition of Δ17O ∼ 1‰ and δ18O ∼ 10‰, and becoming increasingly 16O-enriched toward a final fluid composition of Δ17O ∼ -1.2‰ and δ18O ∼ -15‰.

Living on the Edge? Clumped Isotope and Oxygen Isotope Record of Early Cascade Topography (Eocene Chumstick Basin, WA, USA)

NASA Astrophysics Data System (ADS)

Methner, K.; Mulch, A.; Fiebig, J.; Wacker, U.; Umhoefer, P. J.; Chamberlain, C. P.

2014-12-01

The topographic evolution of the world's major orogens exerts a strong impact on atmospheric circulation and precipitation patterns and is a key element in reconstructing the interactions among tectonics, climate, and Earth surface processes. Using carbonate stable and clumped isotope data together with low-temperature thermochronology information from the terrestrial Eocene Chumstick Basin (Central Washington; USA), today located to the East of the Washington Cascades, we investigate the E-W extent of the western North American plateau region and the evolution of Cascade topography. Oxygen isotope measurements of Eocene (51 to 37 Ma) pedogenic carbonate concretions and calcic horizons yield low δ18Ocarbonate values of +9 to +13 ‰ (SMOW) despite the proximity of the Eocene Chumstick Basin to the Pacific moisture source and paleofloral data that indicate moderate elevations and montane rain forest conditions during a warm and rather wet, seasonal climate. This either suggests that 51-37 Ma ago Cascade-like topography characterized the western edge of the North American-Pacific plate margin to the West of the Chumstick Basin or that the δ18Ocarbonate data were variably reset or only formed during burial and diagenesis. Clumped isotope (Δ47) thermometry of pedogenic carbonate and carbonate concretions (n=11 samples) indicates spatially variable burial temperatures of 80 to 120 °C that correlate with vitrinite reflectance data in these sediments. In concordance with changes in depositional environment the youngest (<40 Ma) Chumstick sediments experienced a lesser degree of post-depositional burial and heating (ca. 70 - 80 °C) compared to the older Chumstick series (80 - 120 °C). Calculated δ18O values of the circulating fluids in the Chumstick basin sediments range from -6 ‰ (T ~100 °C at ca. 40-30 Ma) to -9 ‰ (T ~75 °C at ca. 25-15 Ma). These values suggest a low-altitude meteoric fluid source and as a consequence only moderate Cascade topography during the Eo-/Oligocene. The combined stable isotope and clumped isotope data, therefore support models of late Miocene Cascade uplift and provide insight into the topographic configuration of the western North American plate margin prior to the late Miocene.

The Cadmium Isotope Record of the Great Oxidation Event from the Turee Creek Group, Hamersley Basin, Australia

NASA Astrophysics Data System (ADS)

Abouchami, W.; Busigny, V.; Philippot, P.; Galer, S. J. G.; Cheng, C.; Pecoits, E.

2016-12-01

The evolution of the ocean, atmosphere and biosphere throughout Earth's history has impacted on the biogeochemistry of some key trace metals that are of particular importance in regulating the exchange between Earth's reservoirs. Several geochemical proxies exhibit isotopic shifts that have been linked to major changes in the oxygenation levels of the ancient oceans during the Great Oxygenation Event (GOE) between 2.45 and 2.2 Ga and the Neoproterozoic Oxygenation Event at ca. 0.6 Ga. Studies of the modern marine biogeochemical cycle of the transition metal Cadmium have shown that stable Cd isotope fractionation is mainly driven by biological uptake of light Cd into marine phytoplankton in surface waters leaving behind the seawater enriched in the heavy Cd isotopes. Here we use of the potential of this novel proxy to trace ancient biological productivity which remains an enigma, particularly during the early stages of Earth history. The Turee Creek Group in the Hamersley Basin, Australia, provides a continuous stratigraphic sedimentary section covering the GOE and at least two glacial events, offering a unique opportunity to examine the changes that took place during these periods and possibly constrain the evolution, timing and onset of oxygenic photosynthesis. Stable Cd isotope data were obtained on samples from the Boolgeeda Iron Fm. (BIFs), the siliciclastic and carbonate successions of Kungara (including the Meteorite Bore Member) and the Kazputt Fm., using a double spike technique by TIMS (ThermoFisher Triton) and Cd concentrations were determined by isotope dilution. The Boolgeeda BIFs have generally low Cd concentrations varying between 8 and 50ppb, with two major excursions marked by an increase in Cd content, reaching similar levels to those in the overlying Kungarra Fm. (≥150 ppb). These variations are associated with a large range in ɛ112/110Cd values (-2 to +2), with the most negative values typically found in the organic and Cd-rich shales and siltstones of the Kungara and Kazput formations. This suggests that a significant portion of the Cd present is organically bound, as also supported by the relationship with δ13Corg and TOC. These data will serve to assess the size of the ancient biomass during the GOE in view of our understanding of the modern Cd isotope biogeochemical cycling in the oceans.

Amino acid stable isotope applications to deep-sea corals: A molecular geochemistry approach to reconstructing past ocean conditions

NASA Astrophysics Data System (ADS)

McMahon, K.; McCarthy, M. D.; Guilderson, T. P.; Sherwood, O.; Williams, B.; Larsen, T.; Glynn, D. S.

2017-12-01

Future climate change is predicted to alter ocean productivity, food web dynamics, biogeochemical cycling, and the efficacy of the biological pump. Proteinaceous deep-sea corals act as "living sediment traps," providing long-term, high-resolution records of exported surface ocean production and a window into past changes in ocean condition as a historical context for potential future changes. Here, we present recent work developing the application of compound-specific stable isotope analysis of individual amino acids to proteinaceous deep-sea corals to reconstruct past changes in phytoplankton community composition and biogeochemical cycling. We present new calibrations for molecular isotope comparisons between metabolically active coral polyp tissue and bioarchival proteinaceous skeleton. We then applied these techniques to deep-sea corals from the North Pacific Subtropical Gyre (NPSG) to reconstruct centennial to millennial time scale changes in phytoplankton community composition and biogeochemical cycling as a function of regional climate change. This work suggests that the NPSG has undergone multiple major phytoplankton regime shifts over the last millennium between prokaryotic and eukaryotic phytoplankton communities and associated sources of nitrogen fueling production. The most recent regime, which started around the end of the Little Ice Age and the onset of the Industrial era, is unprecedented in the last 1000 years and resulted in a 30-50% increase in diazotrophic cyanobacteria contribution to export production and an associated 17-27% increase in N2-fixation in the NPSG over last century. By offering the first direct phylogenetic context for long-term shifts in isotopic records of exported particulate organic matter, our data represent a major step forward in understanding the evolution of marine plankton community dynamics, food web architecture, biogeochemical cycling, and the climate feedback loops through the biological pump.

The isotopic and chemical evolution of Mount St. Helens

USGS Publications Warehouse

Halliday, A.N.; Fallick, A.E.; Dickin, A.P.; Mackenzie, A.B.; Stephens, W.E.; Hildreth, W.

1983-01-01

Isotopic and major and trace element analysis of nine samples of eruptive products spanning the history of the Mt. St. Helens volcano suggest three different episodes; (1) 40,000-2500 years ago: eruptions of dacite with ??{lunate}Nd = +5, ??{lunate}Sr = -10, variable ??18O, 206Pb/204Pb ??? 18.76, Ca/Sr ??? 60, Rb/Ba ??? 0.1, La/Yb ??? 18, (2) 2500-1000 years ago: eruptions of basalt, andesite and dacite with ??{lunate}Nd = +4 to +8, ??{lunate}Sr = -7 to -22, variable ??18O (thought to represent melting of differing mantle-crust reservoirs), 206Pb/204Pb = 18.81-18.87, variable Ca/Sr, Rb/Ba, La/Yb and high Zr, (3) 1000 years ago to present day: eruptions of andesite and dacite with ??{lunate}Nd = +6, ??{lunate}Sr = -13, ??18O ???6???, variable 206Pb/204Pb, Ca/Sr ??? 77, Rb/Ba = 0.1, La/Yb ??? 11. None of the products exhibit Eu anomalies and all are LREE enriched. There is a strong correlation between 87Sr/86Sr and differentiation indices. These data are interpreted in terms of a mantle heat source melting young crust bearing zircon and garnet, but not feldspar, followed by intrusion of this crustal reservoir by mantle-derived magma which caused further crustal melting and contaminated the crustal magma system with mafic components. Since 1000 years ago all the eruptions have been from the same reservoir which has displayed a much more gradual re-equilibration of Pb isotopic compositions than other components suggesting that Pb is being transported via a fluid phase. The Nd and Sr isotopic compositions lie along the mantle array and suggest that the mantle underneath Mt. St. Helens is not as depleted as MORB sources. There is no indication of seawater involvement in the source region. ?? 1983.

Measurement of picosecond lifetimes in neutron-rich Xe isotopes

NASA Astrophysics Data System (ADS)

Ilieva, S.; Kröll, Th.; Régis, J.-M.; Saed-Samii, N.; Blanc, A.; Bruce, A. M.; Fraile, L. M.; de France, G.; Hartig, A.-L.; Henrich, C.; Ignatov, A.; Jentschel, M.; Jolie, J.; Korten, W.; Köster, U.; Lalkovski, S.; Lozeva, R.; Mach, H.; Mǎrginean, N.; Mutti, P.; Paziy, V.; Regan, P. H.; Simpson, G. S.; Soldner, T.; Thürauf, M.; Ur, C. A.; Urban, W.; Warr, N.

2016-09-01

Background: Lifetimes of nuclear excited states in fission fragments have been studied in the past following isotope separation, thus giving access mainly to the fragments' daughters and only to long-lived isomeric states in the primary fragments. For the first time now, short-lived excited states in the primary fragments, produced in neutron-induced prompt fission of 235U and 241Pu, were studied within the EXILL&FATIMA campaign at the intense neutron-beam facility of the Institute Laue-Langevin in Grenoble. Purpose: We aim to investigate the quadrupole collective properties of neutron-rich even-even 138,140,142Xe isotopes lying between the double shell closure N =82 and Z =50 and a deformed region with octupole collectivity. Method: The γ rays emitted from the excited fragments were detected with a mixed array consisting of 8 HPGe EXOGAM Clover detectors (EXILL) and 16 LaBr3(Ce) fast scintillators (FATIMA). The detector system has the unique ability to select the interesting fragment making use of the high resolution of the HPGe detectors and determine subnanosecond lifetimes using the fast scintillators. For the analysis the generalized centroid difference method was used. Results: We show that quadrupole collectivity increases smoothly with increasing neutron number above the closed N =82 neutron shell. Our measurements are complemented by state-of-the-art theory calculations based on shell-model descriptions. Conclusions: The observed smooth increase in quadrupole collectivity is similar to the evolution seen in the measured masses of the xenon isotopic chain and is well reproduced by theory. This behavior is in contrast to higher Z even-even nuclei where abrupt change in deformation occurs around N =90 .

Geochemistry and origin of regional dolomites. Final report

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

Hanson, G.N.; Meyers, W.J.

1995-05-01

The main goal of our research on dolomites has been to better understand the composition of the fluids and processes of the fluid-rock interaction responsible for the formation of massive dolostones occurring over regional scales within sedimentary sequences. Understanding the timing of dolomitization, the fluids responsible for the dolomitization and the timing of the development of porosity has major economic ramifications in that dolomites are major oil reservoirs often having better reservoir properties than associated limestones. Our approach has been to apply trace element, major element, petrographic, crystallographic, stable isotope and radiogenic isotope systems to test models for the originsmore » of dolomites and to give information that may allow us to develop new models. Fluid compositions and processes are evaluated through the use of numerical models which we have developed showing the simultaneous evolution of the trace element and isotope systems during dolomitization. Our research has included the application of B, O, C, Sr, Nd and Pb isotope systematics and the trace elements Mn, Fe St, rare earth elements, Rb, Ba, U, Th, Pb, Zn, Na, Cl, F and SO{sub 4}{sup 2-}. Analyses are possible on individual cements or dolomite types using micro-sampling or microprobe techniques. The microprobe techniques used include synchrotron X-ray microprobe analysis at Brookhaven National Laboratory or electron microprobe at Stony Brook. Lack of a modern analogue for ancient massive dolostones has limited the application of the uniformitarian concept to developing models for the ancient regional dolostones. In addition it has not been possible to synthesize dolomite in the laboratory under conditions similar to the sedimentary or diagenetic possible environments in which the dolomites must have formed.« less

Textural and isotopic development of marble assemblages during the Barrovian-style M2 metamorphic event, Naxos, Greece

NASA Astrophysics Data System (ADS)

Baker, Judy; Matthews, Alan

1994-03-01

A detailed petrological analysis of the marble assemblages observed within the M2 metamorphic complex on Naxos is presented. Two distinct periods of mineral growth are documented; the first is associated with prograde M2 metamorphism and the second with retrograde M2 metamorphism occurring during ductile extensional thinning of the complex. The textural and miner-alogical characteristics and the carbon and oxygen isotope compositions of each generation are described, and the P-T-X CO 2 conditions at which these two mineral generations were stable, and the compositions of the fluids present during metamorphism are characterised. Whereas the low variance and stable isotope compositions of prograde siliceous dolomite assemblages are consistent with internally buffered fluid evolution, the retrograde mineral generation is shown to have grown as a result of the infiltration of a water-rich fluid phase that transported silica, Al2O3, Na2O and FeO into the host rocks. This observation, together with the stable isotope compositions of the retrograde calcite, and the fact that occurrences of veins of this type are limited to marbles in the highest grade areas ( T>600° C) of the metamorphic complex, suggests that the fluids responsible for vein formation were generated during the crystallisation of melts as the metamorphic complex cooled from peak temperatures. The existence of this second generation of minerals has significant implications for previous studies of heat transport by fluid flow on Naxos, because many of the unusually low δ18O compositions of pelites at high grades may be ascribable to the effects of interaction with retrograde M2 fluids, rather than with prograde fluids.

Calcium isotope analysis by mass spectrometry.

PubMed

Boulyga, Sergei F

2010-01-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Cupid's Arrow: An Innovative Nanosat to Sample Venus' Upper Atmosphere

NASA Technical Reports Server (NTRS)

Bienstock, Bernie; Darrach, Murray; Madzunkov, Stojan; Sotin, Christophe

2016-01-01

In NASA's Discovery 2014 AO, the opportunity to propose a Technology Demonstration Opportunity (TDO) to enhance the primary mission was specified. For the Venus Emissivity, Radio Science, InSAR, Topography, and Spectroscopy (VERITAS) mission, we elected to include the Cupid's Arrow nanosat TDO to sample and measure the abundances of noble gases and their isotopic ratios in Venus's upper atmosphere below the homopause. This paper will provide a basic overview of the VERITAS mission, with a focus on the Cupid's Arrow concept including a description of the mission, spacecraft design, and JPL's quadrupole ion trap mass spectrometer (QITMS) instrument specifications and design. In previous planetary entry probe mission designs, particularly at Venus, engineers w ere focused on entry and descent. A landed probe was also proposed for the New Frontiers SAGE mission. For Cupid's Arrow, the nanosat is designed to skim through the upper atmosphere, just below the homopause, in order to sample the atmosphere, perform the analysis, and then exit the atmosphere to transmit its data to the orbiting VERITAS spacecraft. Cupid's Arrow is a compelling addition to the VERITAS geology mission. A key missing link in our understanding of Venus' evolution is the noble gas abundances and their isotopic ratios. Not since Pioneer Venus have these measurements been made in the Venus atmosphere and never in the upper atmosphere, just below the homopause, to the degree of accuracy that will be accomplished by VERITAS' Cupid's Arrow nanosat.Such measurements were ranked as the number 1 investigation of the number 1 objective of the goal "Atmospheric Formation, Evolution, and Climate History ".

Evolution, Nucleosynthesis, and Yields of Low-mass Asymptotic Giant Branch Stars at Different Metallicities. II. The FRUITY Database

NASA Astrophysics Data System (ADS)

Cristallo, S.; Piersanti, L.; Straniero, O.; Gallino, R.; Domínguez, I.; Abia, C.; Di Rico, G.; Quintini, M.; Bisterzo, S.

2011-12-01

By using updated stellar low-mass stars models, we systematically investigate the nucleosynthesis processes occurring in asymptotic giant branch (AGB) stars. In this paper, we present a database dedicated to the nucleosynthesis of AGB stars: FRANEC Repository of Updated Isotopic Tables & Yields (FRUITY). An interactive Web-based interface allows users to freely download the full (from H to Bi) isotopic composition, as it changes after each third dredge-up (TDU) episode and the stellar yields the models produce. A first set of AGB models, having masses in the range 1.5 <=M/M ⊙ <= 3.0 and metallicities 1 × 10-3 <= Z <= 2 × 10-2, is discussed. For each model, a detailed description of the physical and the chemical evolution is provided. In particular, we illustrate the details of the s-process and we evaluate the theoretical uncertainties due to the parameterization adopted to model convection and mass loss. The resulting nucleosynthesis scenario is checked by comparing the theoretical [hs/ls] and [Pb/hs] ratios to those obtained from the available abundance analysis of s-enhanced stars. On the average, the variation with the metallicity of these spectroscopic indexes is well reproduced by theoretical models, although the predicted spread at a given metallicity is substantially smaller than the observed one. Possible explanations for such a difference are briefly discussed. An independent check of the TDU efficiency is provided by the C-stars luminosity function. Consequently, theoretical C-stars luminosity functions for the Galactic disk and the Magellanic Clouds have been derived. We generally find good agreement with observations.

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.

Formation waters from Mississippian-Pennsylvanian reservoirs, Illinois basin, USA: Chemical and isotopic constraints on evolution and migration

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

Stueber, A.M.; Walter, L.M.; Huston, T.J.

1993-02-01

We have analyzed a suite of seventy-four formation-water samples from Mississippian and Pennsylvanian carbonate and siliciclastic strata in the Illinois basin for major, minor, and trace element concentrations and for strontium isotopic composition. A subset of these samples was also analyzed for boron isotopic composition. Data are used to interpret origin of salinity and chemical and Sr isotopic evolution of the brines and in comparison with a similar data set from an earlier study of basin formation waters from Silurian-Devonian reservoirs. Systematics of Cl-Br-Na show that present Mississippian-Pennsylvanian brine salinity can be explained by a combination of subaerial seawater evaporationmore » short of halite saturation and subsurface dissolution of halite from an evaporite zone in the middle Mississippian St. Louis Limestone, along with extensive dilution by mixing with meteoric waters. Additional diagenetic modifications in the subsurface interpreted from cation/Br ratios include K depletion through interaction with clay minerals, Ca enrichment, and Mg depletion by dolomitization, and Sr enrichment through CaCO[sub 3] recrystallization and dolomitization. Ste. Genevieve Limestone (middle Mississippian) formation waters show [sup 87]Sr/[sup 86]Sr ratios in the range 0.70782-0.70900, whereas waters from the siliciclastic reservoirs are in the rante 0.70900-0.71052. Inverse correlations between [sup 87]Sr/[sup 86]Sr and B,Li, and Mg concentrations suggest that the brines acquired radiogenic [sup 87]Sr through interaction with siliciclastic minerals. Completely unsystematic relations between [sup 87]Fr/[sup 86]Sr and 1/Sr are observed; Sr concentrations in Ste. Genevieve and Aux Vases (middle Mississippian) waters appear to be buffered by equilibrium with respect to SrSo[sub 4]. These formation waters are distinguished from Silurian-Devonian brines in the basin by elevated Cl/Br and Na/Br ratios and by unsystematic Sr isotope relationships.« less

In situ U-Pb and Lu-Hf isotopic studies of zircons from the Sancheong-Hadong AMCG suite, Yeongnam Massif, Korea: Implications for the petrogenesis of ∼1.86 Ga massif-type anorthosite

NASA Astrophysics Data System (ADS)

Lee, Yuyoung; Cho, Moonsup; Yi, Keewook

2017-05-01

Isotopic and geochemical characteristics of Proterozoic anorthosite-mangerite-charnockite-granite (AMCG) suite have long been used for tracing the mantle-crustal source and magmatic evolution. We analyzed Lu-Hf isotopic compositions of zircon from the Sancheong-Hadong AMCG complex, Yeongnam Massif, Korea, in order to understand tectonomagmatic evolution of the Paleoproterozoic AMCG suite occurring at the southeastern margin of the North China Craton (NCC). The anorthositic rocks in this complex, associated with charnockitic and granitic gneisses, were recrystallized to eradicate magmatic features. In situ SHRIMP (sensitive high-resolution ion microprobe) U-Pb analyses of zircon from a leuconorite and an oxide-bearing gabbroic dyke yielded weighted mean 207Pb/206Pb ages of 1870 ± 2 Ma and 1861 ± 6 Ma, respectively. Charnockitic, granitic, and porphyroblastic gneisses yielded weighted mean 207Pb/206Pb zircon ages of 1861 ± 6 Ma, 1872 ± 6 Ma, and 1873 ± 4 Ma, respectively. These crystallization ages, together with our previous geochronological data for anorthosites (1862 ± 2 Ma), are indicative of episodic AMCG magmatism over an ∼10 Ma interval. Initial εHf(t) values of zircon analyzed from five anorthositic rocks and four felsic gneisses range from +2.1 to -6.1 and -0.3 to -5.4, respectively. Zircon Hf isotopic data in combination with available whole rock Sr-Nd isotopic data suggest that anorthositic parental magma was most likely derived from a mantle source and variably affected by crustal contamination. This crustal component is also reflected in charnockitic-granitic magmas produced primarily by the melting of lower crust. Taken together, the AMCG magmatism at 1.87-1.86 Ga in the Yeongnam Massif is most likely a late orogenic product of Paleoproterozoic NCC amalgamation tectonically linked to assembly of the Columbia supercontinent.

Photochemical fractionation of O-16 in the space medium modeled by resonance excitation of CO by H-Lyman alpha

NASA Technical Reports Server (NTRS)

Arrhenius, G.; Corrigan, M. J.; Fitzgerald, R. W.

1988-01-01

Analyses of meteorite matter, the present structure of the solar system, and the evolution of matter in stellar systems are used to provide inferences concerning the formation of primordial matter in the solar system. Results indicate that molecular excitation processes similar to those observed today in circumstellar regions and dark interstellar clouds were operating in the early solar nebula. It is suggested that resonance excitation of broad isotopic bands by strong UV line sources may have resulted in the anomalous isotopic compositions noted in meteorites.

Peering Through a Martian Veil: ALHA84001 Sm-Nd Age Revisited

NASA Technical Reports Server (NTRS)

Nyquist, Laurence E.; Shih, Chi-Yu

2013-01-01

The ancient Martian orthopyroxenite ALH84001experienced a complex history of impact and aqueous alteration events. Here we summarize Sm-147-Nd-143 and Sm-146-Nd-142 analyses performed at JSC. Further, using REE data, we model the REE abundance pattern of the basaltic magma parental to ALH84001 cumulus orthopyroxene. We find the Sm-146-Nd-142 isotopic data to be consistent with isotopic evolution in material having the modeled Sm/Nd ratio from a time very close to the planet's formation to igneous crystallization of ALH84001 as inferred from the Sm-Nd studies.

Pb, Sr, and Nd isotopic compositions of a suite of Large Archean, igneous rocks, eastern Beartooth Mountains - Implications for crust-mantle evolution

NASA Technical Reports Server (NTRS)

Wooden, J. L.; Mueller, P. A.

1988-01-01

Compositionally diverse Late Archean rocks (2.74-2.79 Ga old) from the eastern Beartooth Mountains (Montana and Wyoming) were studied and shown to have the same initial Pb, Sr, and Nd isotopic ratios. Lead and Sr initial ratios are higher and Nd initial values lower than predicted for rocks derived from model mantle sources and strongly indicate the involvement of an older crustal reservoir in the genesis of these rocks. A model involving subduction of continental detritus and contamination of the overlying mantle is suggested.

Supernova Neutrino-Process and Implication in Neutrino Oscillation

NASA Astrophysics Data System (ADS)

Kajino, T.; Aoki, W.; Fujiya, W.; Mathews, G. J.; Yoshida, T.; Shaku, K.; Nakamura, K.; Hayakawa, T.

2012-08-01

We studied the supernova nucleosynthesis induced by neutrino interactions and found that several isotopes of rare elements like 7Li, 11B, 138La, 180Ta and many others are predominantly produced by the neutrino-process in core-collapse supernovae. These isotopes are strongly affected by the neutrino flavor oscillation due to the MSW (Mikheyev-Smirnov-Wolfenstein) effect. We here propose a new novel method to determine the unknown neutrino oscillation parameters, θ13 and mass hierarchy simultaneously from the supernova neutrino-process, combined with the r-process for heavy-element synthsis and the Galactic chemical evolution on light nuclei.

Accretion timescales and style of asteroidal differentiation in an 26Al-poor protoplanetary disk

PubMed Central

Larsen, K.K.; Schiller, M.; Bizzarro, M.

2016-01-01

The decay of radioactive 26Al to 26Mg (half-life of 730,000 years) is postulated to have been the main energy source promoting asteroidal melting and differentiation in the nascent solar system. High-resolution chronological information provided by the 26Al−26Mg decay system is, therefore, intrinsically linked to the thermal evolution of early-formed planetesimals. In this paper, we explore the timing and style of asteroidal differentiation by combining high-precision Mg isotope measurements of meteorites with thermal evolution models for planetesimals. In detail, we report Mg isotope data for a suite of olivine-rich [Al/Mg ~ 0] achondritic meteorites, as well as a few chondrites. Main Group, pyroxene and the Zinder pallasites as well as the lodranite all record deficits in the mass-independent component of μ26Mg (μ26Mg*) relative to chondrites and Earth. This isotope signal is expected for the retarded ingrowth of radiogenic 26Mg* in olivine-rich residues produced through partial silicate melting during 26Al decay and consistent with their marginally heavy Mg isotope composition relative to ordinary chondrites, which may reflect the early extraction of isotopically light partial melts from the source rock. We propose that their parent planetesimals started forming within ~250,000 years of solar system formation from a hot (>~500 K) inner protoplanetary disk region characterized by a reduced initial (26Al/27Al)0 abundance (~1–2 × 10−5) relative to the (26Al/27Al)0 value in CAIs of 5.25 × 10−5. This effectively reduced the total heat production and allowed for the preservation of solid residues produced through progressive silicate melting with depth within the planetesimals. These ‘non-carbonaceous’ planetesimals acquired their mass throughout an extended period (>3 Myr) of continuous accretion, thereby generating onion-shell structures of incompletely differentiated zones, consisting of olivine-rich residues, overlaid by metachondrites and undifferentiated chondritic crusts. In contrast, individual olivine crystals from Eagle Station pallasites record variable μ26Mg* excesses, suggesting that these crystals captured the 26Mg* evolution of a magmatic reservoir controlled by fractional crystallization processes during the lifespan of 26Al. Similar to previous suggestions based on isotopic evidence, we suggest that Eagle Station pallasites formed from precursor material similar in composition to carbonaceous chondrites from a cool outer protoplanetary disk region characterized by (26Al/27Al)0 ≥ 2.7 × 10−5. Protracted planetesimal accretion timescales at large orbital distances, with onset of accretion 0.3–1 Myr post-CAIs, may have resulted in significant radiative heat loss and thus efficient early interior cooling of slowly accreting ‘carbonaceous’ planetesimals. PMID:27445415

Accretion timescales and style of asteroidal differentiation in an 26Al-poor protoplanetary disk

NASA Astrophysics Data System (ADS)

Larsen, K. K.; Schiller, M.; Bizzarro, M.

2016-03-01

The decay of radioactive 26Al to 26Mg (half-life of 730,000 years) is postulated to have been the main energy source promoting asteroidal melting and differentiation in the nascent solar system. High-resolution chronological information provided by the 26Al-26Mg decay system is, therefore, intrinsically linked to the thermal evolution of early-formed planetesimals. In this paper, we explore the timing and style of asteroidal differentiation by combining high-precision Mg isotope measurements of meteorites with thermal evolution models for planetesimals. In detail, we report Mg isotope data for a suite of olivine-rich [Al/Mg ∼ 0] achondritic meteorites, as well as a few chondrites. Main Group, pyroxene and the Zinder pallasites as well as the lodranite all record deficits in the mass-independent component of μ26Mg (μ26Mg∗) relative to chondrites and Earth. This isotope signal is expected for the retarded ingrowth of radiogenic 26Mg∗ in olivine-rich residues produced through partial silicate melting during 26Al decay and consistent with their marginally heavy Mg isotope composition relative to ordinary chondrites, which may reflect the early extraction of isotopically light partial melts from the source rock. We propose that their parent planetesimals started forming within ∼250,000 years of solar system formation from a hot (>∼500 K) inner protoplanetary disk region characterized by a reduced initial (26Al/27Al)0 abundance (∼1-2 × 10-5) relative to the (26Al/27Al)0 value in CAIs of 5.25 × 10-5. This effectively reduced the total heat production and allowed for the preservation of solid residues produced through progressive silicate melting with depth within the planetesimals. These 'non-carbonaceous' planetesimals acquired their mass throughout an extended period (>3 Myr) of continuous accretion, thereby generating onion-shell structures of incompletely differentiated zones, consisting of olivine-rich residues, overlaid by metachondrites and undifferentiated chondritic crusts. In contrast, individual olivine crystals from Eagle Station pallasites record variable μ26Mg∗ excesses, suggesting that these crystals captured the 26Mg∗ evolution of a magmatic reservoir controlled by fractional crystallization processes during the lifespan of 26Al. Similar to previous suggestions based on isotopic evidence, we suggest that Eagle Station pallasites formed from precursor material similar in composition to carbonaceous chondrites from a cool outer protoplanetary disk region characterized by (26Al/27Al)0 ⩾ 2.7 × 10-5. Protracted planetesimal accretion timescales at large orbital distances, with onset of accretion 0.3-1 Myr post-CAIs, may have resulted in significant radiative heat loss and thus efficient early interior cooling of slowly accreting 'carbonaceous' planetesimals.

Methane as a biomarker in the search for extraterrestrial life: Lessons learned from Mars analog hypersaline environments

NASA Astrophysics Data System (ADS)

Bebout, B.; Tazaz, A.; Kelley, C. A.; Poole, J. A.; Davila, A.; Chanton, J.

2010-12-01

Methane released from discrete regions on Mars, together with previous reports of methane determined with ground-based telescopes, has revived the possibility of past or even extant life near the surface on Mars, since 90% of the methane on Earth has a biological origin. This intriguing possibility is supported by the abundant evidence of large bodies of liquid water, and therefore of conditions conducive to the origin of life, early in the planet's history. The detection and analysis of methane is at the core of NASA’s strategies to search for life in the solar system, and on extrasolar planets. Because methane is also produced abiotically, it is important to generate criteria to unambiguously assess biogenicity. The stable carbon and hydrogen isotopic signature of methane, as well as its ratio to other low molecular weight hydrocarbons (the methane/(ethane + propane) ratio: C1/(C2 + C3)), has been suggested to be diagnostic for biogenic methane. We report measurements of the concentrations and stable isotopic signature of methane from hypersaline environments. We focus on hypersaline environments because spectrometers orbiting Mars have detected widespread chloride bearing deposits resembling salt flats. Other evaporitic minerals, e.g., sulfates, are also abundant in several regions, including those studied by the Mars Exploration Rovers. The presence of evaporitic minerals, together with the known evolution of the Martian climate, from warmer and wetter to cold and hyper-arid, suggest that evaporitic and hypersaline environments were common in the past. Hypersaline environments examined to date include salt ponds located in Baja California, the San Francisco Bay, and the Atacama Desert. Methane was found in gas produced both in the sediments, and in gypsum- and halite-hosted (endolithic) microbial communities. Maximum methane concentrations were as high as 40% by volume. The methane carbon isotopic (δ13C) composition showed a wide range of values, from about -60 ‰ to -30 ‰, while the hydrogen isotopic composition (δ2H) ranged from about -350 to -300‰. These isotopic values are outside the range generally considered to be biogenic, however incubations of the sediments and salt crusts revealed that the methane is indeed produced there. The highest rate of methane production was 20 nmol/g/d, in a gypsum crust with endolithic microbial communities. Currently we are studying the mechanisms that control the isotopic signatures of methane in these environments. These studies are of special relevance given the projected analysis of Mars atmospheric methane by the Mars Science Laboratory in 2012, and by the ExoMars Trace Gas Orbiter in 2017.

Lithium abundance and 6Li/7Li ratio in the active giant HD 123351. I. A comparative analysis of 3D and 1D NLTE line-profile fits

NASA Astrophysics Data System (ADS)

Mott, A.; Steffen, M.; Caffau, E.; Spada, F.; Strassmeier, K. G.

2017-08-01

Context. Current three-dimensional (3D) hydrodynamical model atmospheres together with detailed spectrum synthesis, accounting for departures from local thermodynamic equilibrium (LTE), permit to derive reliable atomic and isotopic chemical abundances from high-resolution stellar spectra. Not much is known about the presence of the fragile 6Li isotope in evolved solar-metallicity red giant branch (RGB) stars, not to mention its production in magnetically active targets like HD 123351. Aims: A detailed spectroscopic investigation of the lithium resonance doublet in HD 123351 in terms of both abundance and isotopic ratio is presented. From fits of the observed spectrum, taken at the Canada-France-Hawaii telescope, with synthetic line profiles based on 1D and 3D model atmospheres, we seek to estimate the abundance of the 6Li isotope and to place constraints on its origin. Methods: We derive the lithium abundance A(Li) and the 6Li/7Li isotopic ratio by fitting different synthetic spectra to the Li-line region of a high-resolution CFHT spectrum (R = 120 000, S/N = 400). The synthetic spectra are computed with four different line lists, using in parallel 3D hydrodynamical CO5BOLD and 1D LHD model atmospheres and treating the line formation of the lithium components in non-LTE (NLTE). The fitting procedure is repeated with different assumptions and wavelength ranges to obtain a reasonable estimate of the involved uncertainties. Results: We find A(Li) = 1.69 ± 0.11 dex and 6Li/7Li = 8.0 ± 4.4% in 3D-NLTE, using the line list of Meléndez et al. (2012, A&A, 543, A29), updated with new atomic data for V I, which results in the best fit of the lithium line profile of HD 123351. Two other line lists lead to similar results but with inferior fit qualities. Conclusions: Our 2σ detection of the 6Li isotope is the result of a careful statistical analysis and the visual inspection of each achieved fit. Since the presence of a significant amount of 6Li in the atmosphere of a cool evolved star is not expected in the framework of standard stellar evolution theory, non-standard, external lithium production mechanisms, possibly related to stellar activity or a recent accretion of rocky material, need to be invoked to explain the detection of 6Li in HD 123351.

Astrophysics with Presolar Stardust

NASA Astrophysics Data System (ADS)

Clayton, Donald D.; Nittler, Larry R.

2004-09-01

Meteorites and interplanetary dust particles contain presolar stardust grains: solid samples of stars that can be studied in the laboratory. The stellar origin of the grains is indicated by enormous isotopic ratio variations compared with Solar System materials, explainable only by nuclear reactions occurring in stars. Known presolar phases include diamond, SiC, graphite, Si3N4, Al2O3, MgAl2O4, CaAl12O19, TiO2, Mg(Cr,Al)2O4, and most recently, silicates. Subgrains of refractory carbides (e.g., TiC), and Fe-Ni metal have also been observed within individual presolar graphite grains. We review the astrophysical implications of these grains for the sciences of nucleosynthesis, stellar evolution, grain condensation, and the chemical and dynamic evolution of the Galaxy. Unique scientific information derives primarily from the high precision (in some cases <1%) of the measured isotopic ratios of large numbers of elements in single stardust grains. Stardust science is just now reaching maturity and will play an increasingly important role in nucleosynthesis applications.

Evolution of the El Nino-Southern Oscillation in the late Holocene and insolation driven change in the tropical annual SST cycle

NASA Astrophysics Data System (ADS)

Loubere, Paul; Creamer, Winifred; Haas, Jonathan

2013-01-01

South American lake sediment records indicate that El Nino events in the eastern equatorial Pacific (EEP) became more frequent after 3000 calendar years BP. The reason for this evolution of ENSO behavior remains in question. An important trigger for ocean-atmosphere state switching in the tropical ocean is the annual cycle of sea surface temperature south of the equator along the margin of South America. This annual cycle can be reconstructed from the oxygen isotope records of the surf clam Mesodesma donacium. We provide evidence that these isotope records, as preserved in archeological deposits in coastal central Peru, reflect seasonal paleo-SST. We find that the annual SST cycle in the eastern equatorial Pacific became larger over the 4500-2500 calendar year BP interval. This is consistent with increased ENSO variability. The magnification of the annual SST cycle can be attributed to changing insolation, indicating that ENSO is sensitive to the intensity and seasonal timing of solar heating of the southern EEP.

Morphology, geology and geochemistry of the "Salar del Gran Bajo del Gualicho" (Rio Negro, Argentina)

USGS Publications Warehouse

Angelucci, A.; Barbieri, M.; Brodtkorb, A.; Ciccacci, S.; Civitelli, G.; De Barrio, R.; Di, Filippo M.; Fredi, P.; Friedman, I.; Lombardi, S.; Schalamuk, A.I.; Toro, B.

1996-01-01

A multidisciplinary study of the Gran Bajo del Gualicho area (Rio Negro - Argentina) was carried out; the aim was to delineate its geological and geomorphological evolution and to estabilish the genesis of salts filling the depression. Climatic conditions were analized first to individuate their role in the present morphogenetic processes; moreover the main morphological features of present landscape were examined as well as the stratigraphy of the outcropping formations, and of the Gran Bajo del Gualicho Formation in particular. Finally, a possible geomorphological evolution of the studied area was traced. Geophysical analyses allowed to estabilish that the paleosurface shaped on the crystalline basement is strongly uneven and shows evidence of the strong tectonic phases it underwent. The result of isotope analyses confirmed that the salt deposits on the Gran Bajo del Gualicho bottom were produced by fresh water evaporation, while strontium isotope ratio suggested that such waters were responsible for solubilization of more ancient evaporitic deposits.

Origin and tectonic evolution of early Paleozoic arc terranes abutting the northern margin of North China Craton

NASA Astrophysics Data System (ADS)

Zhou, Hao; Pei, Fu-Ping; Zhang, Ying; Zhou, Zhong-Biao; Xu, Wen-Liang; Wang, Zhi-Wei; Cao, Hua-Hua; Yang, Chuan

2017-12-01

The origin and tectonic evolution of the early Paleozoic arc terranes abutting the northern margin of the North China Craton (NCC) are widely debated. This paper presents detrital zircon U-Pb and Hf isotopic data of early Paleozoic strata in the Zhangjiatun arc terrane of central Jilin Province, northeast (NE) China, and compares them with the Bainaimiao and Jiangyu arc terranes abutting the northern margin of the NCC. Detrital zircons from early Paleozoic strata in three arc terranes exhibit comparable age groupings of 539-430, 1250-577, and 2800-1600 Ma. The Paleoproterozoic to Neoarchean ages and Hf isotopic composition of the detrital zircons imply the existence of the Precambrian fragments beneath the arc terranes. Given the evidences from geology, igneous rocks, and detrital zircons, we proposed that the early Paleozoic arc terranes abutting the northern margin of the NCC are a united arc terrane including the exotic Precambrian fragments, and these fragments shared a common evolutionary history from Neoproterozoic to early-middle Paleozoic.

From Titan’s tholins to Titan’s aerosols: Isotopic study and chemical evolution at Titan’s surface

NASA Astrophysics Data System (ADS)

Nguyen, Mai-Julie; Raulin, François; Coll, Patrice; Derenne, Sylvie; Szopa, Cyril; Cernogora, Guy; Israël, Guy; Bernard, Jean-Michel

2008-07-01

In the present work, we focused on the possible isotopic fractionation of carbon during the processes involved in the formation of Titan’s tholins. We present the first results obtained on the 12C/13C isotopic ratios measured on Titan’s tholins synthesized in laboratory with cold plasma discharges. Measurements of isotopic ratio 12C/13C, done both on tholins and on the initial gas mixture (N2:CH4 (98:2)) used to produce them, do not show any evident deficit or enrichment in 13C relatively to 12C in the synthesized tholins, compared to the initial gas mixture. This observation allows to go further in the analyses of the ACP experiment data, including part of the Cassini Huygens mission. We also focused on the chemical evolution of the aerosols at Titan surface by studying species coming from acid hydrolysis treatment of Titan’s tholins. Preliminary results show a wide diversity of chemical families, going from carboxylic acids to amino acids. Advanced studies could bring at short-term clues on the still unidentified mixture that induces the decrease of the reflectivity as measure by the DISR instrument [Tomasko, M.G., Archinal, B., Becker, T., Bézard, B., Bushroe, M., Combes, M., Cook, D., Coustenis, A., de Bergh, C., Dafoe, L.E., Doose, L., Douté, S., Eibl, A., Engel, S., Gliem, F., Grieger, B., Holso, K., Howington-Kraus, E., Karkoschka, E., Keller, H.U., Kirk, R., Kramm, R., Küppers, M., Lanagan, P., Lellouch, E., Lemmon, M., Lunine, J., McFarlane, E., Moores, J., Prout, G.M., Rizk, B., Rosiek, M., Rueffer, P., Schröder, S.E., Schmitt, B., See, C., Smith, P., Soderblom, L., Thomas, N., West, R. Rain, winds and haze during the Huygens probe’s descent to Titan’s surface. Nature 438(7069), 765 778, 2005]. At longer-term it could allow to better understand the possible chemical evolution of the Titan’s aerosols after falling down at the surface when brought into contact with water.

Crustal contamination and crystal entrapment during polybaric magma evolution at Mt. Somma-Vesuvius volcano, Italy: Geochemical and Sr isotope evidence

USGS Publications Warehouse

Piochi, M.; Ayuso, R.A.; de Vivo, B.; Somma, R.

2006-01-01

New major and trace element analyses and Sr-isotope determinations of rocks from Mt. Somma-Vesuvius volcano produced from 25 ky BP to 1944 AD are part of an extensive database documenting the geochemical evolution of this classic region. Volcanic rocks include silica undersaturated, potassic and ultrapotassic lavas and tephras characterized by variable mineralogy and different crystal abundance, as well as by wide ranges of trace element contents and a wide span of initial Sr-isotopic compositions. Both the degree of undersaturation in silica and the crystal content increase through time, being higher in rocks produced after the eruption at 472 AD (Pollena eruption). Compositional variations have been generally thought to reflect contributions from diverse types of mantle and crust. Magma mixing is commonly invoked as a fundamental process affecting the magmas, in addition to crystal fractionation. Our assessment of geochemical and Sr-isotopic data indicates that compositional variability also reflects the influence of crustal contamination during magma evolution during upward migration to shallow crustal levels and/or by entrapment of crystal mush generated during previous magma storage in the crust. Using a variant of the assimilation fractional crystallization model (Energy Conservation-Assimilation Fractional Crystallization; [Spera and Bohrson, 2001. Energy-constrained open-system magmatic processes I: General model and energy-constrained assimilation and fractional crystallization (EC-AFC) formulation. J. Petrol. 999-1018]; [Bohrson, W.A. and Spera, F.J., 2001. Energy-constrained open-system magmatic process II: application of energy-constrained assimilation-fractional crystallization (EC-AFC) model to magmatic systems. J. Petrol. 1019-1041]) we estimated the contributions from the crust and suggest that contamination by carbonate rocks that underlie the volcano (2 km down to 9-10 km) is a fundamental process controlling magma compositions at Mt. Somma-Vesuvius in the last 8 ky BP. Contamination in the mid- to upper crust occurred repeatedly, after the magma chamber waxed with influx of new mantle- and crustal-derived magmas and fluids, and waned as a result of magma withdrawal and production of large and energetic plinian and subplinian eruptions. ?? 2005 Elsevier B.V. All rights reserved.

Chondrites and the Protoplanetary Disk, Part 2

NASA Technical Reports Server (NTRS)

2004-01-01

Contents include the following: On the Dynamical Evolution of a Nebula and Its Effect on Dust Coagulation and the Formation of Centimeter-sized Particles. The Mineralogy and Grain Properties of the Disk Surfaces in Three Herbig Ae/Be Stars. Astrophysical Observations of Disk Evolution Around Solar Mass Stars. The Systematic Petrology of Chondrites: A Consistent Approach to Assist Classification and Interpretation. Understanding Our Origins: Formation of Sun-like Stars in H II Region Environments. Chondrule Crystallization Experiments. Formation of SiO2-rich Chondrules by Fractional Condensation. Refractory Forsterites from Murchison (CM2) and Yamato 81020 (CO3.0) Chondrites: Cathodoluminescence, Chemical Compositions and Oxygen Isotopes. Apparent I-Xe Cooling Rates of Chondrules Compared with Silicates from the Colomera Iron Meteorite. Chondrule Formation in Planetesimal Bow Shocks: Physical Processes in the Near Vicinity of the Planetesimal. Genetic Relationships Between Chondrules, Rims and Matrix. Chondrite Fractionation was Cosmochemical; Chondrule Fractionation was Geochemical. Chondrule Formation and Accretion of Chondrite Parent Bodies: Environmental Constraints. Amoeboid Olivine Aggregates from the Semarkona LL3.0 Chondrite. The Evolution of Solids in Proto-Planetary Disks. New Nickel Vapor Pressure Measurements: Possible Implications for Nebular Condensates. Chemical, Mineralogical and Isotopic Properties of Chondrules: Clues to Their Origin. Maximal Size of Chondrules in Shock-Wave Heating Model: Stripping of Liquid Surface in Hypersonic Rarefied Gas Flow. The Nature and Origin of Interplanetary Dust: High Temperature Components. Refractory Relic Components in Chondrules from Ordinary Chondrites. Constraints on the Origin of Chondrules and CAIs from Short-lived and Long-lived Radionuclides. The Genetic Relationship Between Refractory Inclusions and Chondrules. Contemporaneous Chondrule Formation Between Ordinary and Carbonaceous Chondrites. Chondrules and Isolated Grains in the Fountain Hills Bencubbinite. Implications of Chondrule Formation in a Gas of Solar Composition. Implications of Meteoritic Cl-36 Abundance for the Origin of Short-lived Radionuclides in the Early Solar System. Size Sorting and the Chondrule Size Spectrum. Comparative Study of Refractory Inclusions from Different Groups of Chondrites. In Situ Investigation of Mg Isotope Distributions in an Allende CAI by Combined LA-ICPMS and SIMS Analyses Photochemical Speciation of Oxygen Isotopes in the Solar Nebula.

Why we need a centralized repository for isotopic data

USDA-ARS?s Scientific Manuscript database

Stable isotopes encode the origin and integrate the history of matter; thus, their analysis offers tremendous potential to address questions across diverse scientific disciplines. Indeed, the broad applicability of stable isotopes, coupled with advancements in high-throughput analysis, have created ...

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

Late Eocene to present isotopic (Sr-Nd-Pb) and geochemical evolution of sediments from the Lomonosov Ridge, Arctic Ocean: Implications for continental sources and linkage with the North Atlantic Ocean

NASA Astrophysics Data System (ADS)

Stevenson, Ross; Poirier, André; Véron, Alain; Carignan, Jean; Hillaire-Marcel, Claude

2015-09-01

New geochemical and isotopic (Sr, Nd, Pb) data are presented for a composite sedimentary record encompassing the past 50 Ma of history of sedimentation on the Lomonosov Ridge in the Arctic Ocean. The sampled sediments encompass the transition of the Arctic basin from an enclosed anoxic basin to an open and ventilated oxidized ocean basin. The transition from anoxic basin to open ventilated ocean is accompanied by at least three geochemical and isotopic shifts and an increase in elements (e.g., K/Al) controlled by detrital minerals highlighting significant changes in sediment types and sources. The isotopic compositions of the sediments prior to ventilation are more variable but indicate a predominance of older crustal contributions consistent with sources from the Canadian Shield. Following ventilation, the isotopic compositions are more stable and indicate an increased contribution from younger material consistent with Eurasian and Pan-African crustal sources. The waxing and waning of these sources in conjunction with the passage of water through Fram Strait underlines the importance of the exchange of water mass between the Arctic and North Atlantic Oceans.

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Bose-Fermi symmetry in the odd-even gold isotopes

NASA Astrophysics Data System (ADS)

Thomas, T.; Régis, J.-M.; Jolie, J.; Heinze, S.; Albers, M.; Bernards, C.; Fransen, C.; Radeck, D.

2014-05-01

In this work the results of an in-beam experiment on 195Au are presented, yielding new spins, multipole mixing ratios, and new low-lying states essential for the understanding of this nucleus. The positive-parity states from this work together with compiled data from the available literature for 185-199Au are compared to Interacting Boson Fermion Model calculations employing the Spin(6) Bose-Fermi symmetry. The evolution of the parameters for the τ splitting and the J splitting reveals a smooth behavior. Thereby, a common description based on the Bose-Fermi symmetry is found for 189-199Au. Furthermore, the calculated E2 transition strengths are compared to experimental values with fixed effective boson and fermion charges for all odd-even gold isotopes, emphasizing that the Spin(6) Bose-Fermi symmetry is valid for the gold isotopes.

IBM-2 calculation with configuration mixing for Ge isotopes

NASA Astrophysics Data System (ADS)

Padilla-Rodal, Elizabeth; Galindo-Uribarri, Alfredo

2005-04-01

Recent results on Coulomb excitation experiments of radioactive neutron-rich Ge isotopes at the Holifield Radioactive Ion Beam Facility allow the study of the systematic trend of B(E2; 0^+ ->2^+) between the sub-shell closures at N=40 and the N=50 [1]. The new information on the E2 transition strengths constitutes a stringent test for the nuclear models and has motivated us to revisit the use of Interacting Boson Model in this region. We show that the IBM-2 with configuration mixing is a successful model to describe the shape transition phenomena that take place around N=40 in stable germanium isotopes, as well as the predictions given by this model about the evolution of the structure for the radioactive ^78, 80, 82Ge nuclei. [1] E. Padilla-Rodal Ph.D. Thesis UNAM; submitted for publication.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-01-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-09-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment, employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e., equivalent to ~8 ng of amino sugar carbon. Compound-specific stable carbon isotopic analysis of amino sugars obtained from marine sediment extracts indicated that glucosamine and galactosamine were mainly derived from organic detritus, whereas muramic acid showed isotopic imprints from indigenous bacterial activities. The δ13C analysis of amino sugars provides a valuable addition to the biomarker-based characterization of microbial metabolism in the deep marine biosphere, which so far has been lipid oriented and biased towards the detection of archaeal signals.

High-resolution continuous flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

NASA Astrophysics Data System (ADS)

Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

2014-12-01

Here we present an experimental setup for water stable isotopes (δ18O and δD) continuous flow measurements. It is the first continuous flow laser spectroscopy system that is using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research - LGR) in combination with an evaporation unit to continuously analyze sample from an ice core. A Water Vapor Isotopic Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to: (1) increase the temporal resolution by reducing the response time (2) enable measurements on several water standards, and (3) to reduce the influence from memory effects. While this setup was designed for the Continuous Flow Analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The modified setup provides a shorter response time (~54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the modified setup has a reduced memory effect. Stability tests comparing the modified WVISS and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the 2013 modified setup the precision after integration times of 103 s are 0.060 and 0.070‰ for δ18O and δD, respectively. For the WVISS setup the corresponding σAllan values are 0.030, 0.060 and 0.043‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042‰ after 103 s for δ18O, δD and δ17O, respectively. Both the modified setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O of 0.30 and 0.18‰ for the modified (2013) and WVISS setup, respectively after averaging times of 104 s (2.78 h). The Isotopic Water Analyzer (IWA)-modified WVISS setup used during the 2013 Roosevelt Island Climate Evolution (RICE) ice core processing campaign achieved high precision measurements, in particular for δD, with high temporal resolution for the upper part of the core, where a seasonally resolved isotopic signal is preserved.

Ion microprobe U-Pb dating and strontium isotope analysis of biogenic apatite

NASA Astrophysics Data System (ADS)

Sano, Y.; Toyoshima, K.; Takahata, N.; Shirai, K.

2012-12-01

Conodonts are micro-fossils chemically composed of apatite which occurred in the body of one animal. They are guide fossils to show formation ages of sedimentary sequences with the highest resolution [1] and good samples to verify the dating method. We developed the ion microprobe U-Pb dating of apatite [2] and applied the method to a Carboniferous conodont [3] by using a SHRIMP II installed at Department of Earth and Planetary Sciences, Hiroshima University. Recently we have developed the NanoSIMS U-Pb dating method and successfully measured the formation ages of monazite [4] and zircon [5] at Atmosphere and Ocean Research Institute, University of Tokyo. In this work we carried out the NanoSIMS U-Pb dating of biogenic apatite such as conodont. Since the spot size of NanoSIMS is smaller than SHRIMP II, it is easier to have multi-spots on the single fragment of biogenic apatite. Based on the isochron method of U-Pb system, we have calculated the formation ages. They are consistent with those in literature. In order to study the chemical evolution of ocean during the past 600 Million years, strontium isotopes (87Sr/86Sr) of fossil marine carbonate such as coral skeletons and foraminifera tests were measured and compiled [6]. However they are not robust when the age is older than 500Ma, partly due to post-depositional histories. Apatite is more stable and more resistant to the alteration than carbonate [7]. Recently we have developed the method of NanoSIMS strontium isotopic analysis of a fish otolith, which composed of aragonite [8]. In this work we carried out the strontium isotopic analysis of biogenic apatite. The advantage of the ion microprobe technique over the TIMS (thermal ionization mass spectrometer) and MC-ICP-MS (multi-collector inductively coupled argon plasma mass spectrometer) method is preservation of the important textural context and to provide an opportunity for other simultaneous analytical work with high spatial resolution. This is the case for the combination of U-Pb dating and strontium isotope analysis of biogenic apatite. This method may be useful to extract the information of the chemistry of Past ocean in future. [1] Sweet and Donoghue (2001) J. Paleont. 75, 1174-1184. [3] Sano et al., (1999) Chem. Geol. 153, 249-258. [3] Sano and Terada (2001) Geophys. Res. Lett. 28, 831-834. [4] Sano et al. (2006) Geochem. J. 40, 597-608. [5] Takahata et al. (2008) Gondwana Res. 14, 587-596. [6] Prokoph et al. (2008) Earth Sci. Rev. 87, 113-133. [7] Karhu and Epstein (1986) Geochim. Cosmochim. Acta 50, 1745-1756. [8] Sano et al. (2008) App. Geochem. 23, 2406-2413.

Isotopic Biogeochemistry

NASA Technical Reports Server (NTRS)

Hayes, J. M.

1985-01-01

An overview is provided of the biogeochemical research. The funding, productivity, personnel and facilities are reviewed. Some of the technical areas covered are: carbon isotopic records; isotopic studies of banded iron formations; isotope effects in microbial systems; studies of organic compounds in ancient sediments; and development in isotopic geochemistry and analysis.

Advances in natural stable isotope ratio analysis of human hair to determine nutritional and metabolic status.

PubMed

Petzke, Klaus J; Fuller, Benjamin T; Metges, Cornelia C

2010-09-01

We review the literature on the use of stable isotope ratios at natural abundance to reveal information about dietary habits and specific nutrient intakes in human hair protein (keratin) and amino acids. In particular, we examine whether hair isotopic compositions can be used as unbiased biomarkers to provide information about nutritional status, metabolism, and diseases. Although the majority of research on the stable isotope ratio analysis of hair has focused on bulk protein, methods have been recently employed to examine amino acid-specific isotope ratios using gas chromatography or liquid chromatography coupled to an isotope ratio mass spectrometer. The isotopic measurement of amino acids has the potential to answer research questions on amino acid nutrition, metabolism, and disease processes and can contribute to a better understanding of the variations in bulk protein isotope ratio values. First results suggest that stable isotope ratios are promising as unbiased nutritional biomarkers in epidemiological research. However, variations in stable isotope ratios of human hair are also influenced by nutrition-dependent nitrogen balance, and more controlled clinical research is needed to examine these effects in human hair. Stable isotope ratio analysis at natural abundance in human hair protein offers a noninvasive method to reveal information about long-term nutritional exposure to specific nutrients, nutritional habits, and in the diagnostics of diseases leading to nutritional stress and impaired nitrogen balance.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Calcium and titanium isotopes in refractory inclusions from CM, CO, and CR chondrites

NASA Astrophysics Data System (ADS)

Kööp, Levke; Davis, Andrew M.; Krot, Alexander N.; Nagashima, Kazuhide; Simon, Steven B.

2018-05-01

Previous studies have shown that CV and CM chondrites incorporated Ca, Al-rich inclusions (CAIs) with different isotopic characteristics, which may represent different snapshots in the isotopic evolution of the early Solar System. To better understand how the isotopic characteristics of CAIs vary between different chondrite groups, we have studied calcium and titanium isotopes in CAIs from CM, CO, and CR chondrites. We show that all three chondrite groups contain CAIs with large anomalies in 48Ca and/or 50Ti (10s of ‰ or 100s of ε-units) as well as CAIs with no anomalies resolved beyond measurement uncertainties. Isotopically, the anomalous CO and CR chondrite CAIs resemble the platy hibonite crystals (PLACs) from CM chondrites, but they are more mineralogically complex. The new data are consistent with the well-established mutual exclusivity relationship between incorporation of 26Al and the presence of large anomalies in 48Ca and 50Ti. The two highly anomalous CO chondrite CAIs have correlated anomalies in 46Ti and 50Ti, while most other highly anomalous CAIs do not. This result could indicate that the reservoir with coupled 46Ti and 50Ti that was sampled by bulk meteorites and CV chondrite CAIs already existed before arrival and/or homogeneous distribution of 26Al in the protoplanetary disk. Among the studied CM chondrite CAIs are ten spinel-hibonite inclusions (SHIBs) with known oxygen isotopic compositions. Our results show that these objects sampled a reservoir that was well-mixed in oxygen, calcium, and titanium isotopes. We further show that SHIBs tend to be slightly enriched in the heavy calcium isotopes, suggesting that their formation history was different from CV chondrite CAIs.

Isotopes as tracers of the sources of the lunar material and processes of lunar origin.

PubMed

Pahlevan, Kaveh

2014-09-13

Ever since the Apollo programme, isotopic abundances have been used as tracers to study lunar formation, in particular to study the sources of the lunar material. In the past decade, increasingly precise isotopic data have been reported that give strong indications that the Moon and the Earth's mantle have a common heritage. To reconcile these observations with the origin of the Moon via the collision of two distinct planetary bodies, it has been proposed (i) that the Earth-Moon system underwent convective mixing into a single isotopic reservoir during the approximately 10(3) year molten disc epoch after the giant impact but before lunar accretion, or (ii) that a high angular momentum impact injected a silicate disc into orbit sourced directly from the mantle of the proto-Earth and the impacting planet in the right proportions to match the isotopic observations. Recently, it has also become recognized that liquid-vapour fractionation in the energetic aftermath of the giant impact is capable of generating measurable mass-dependent isotopic offsets between the silicate Earth and Moon, rendering isotopic measurements sensitive not only to the sources of the lunar material, but also to the processes accompanying lunar origin. Here, we review the isotopic evidence that the silicate-Earth-Moon system represents a single planetary reservoir. We then discuss the development of new isotopic tracers sensitive to processes in the melt-vapour lunar disc and how theoretical calculations of their behaviour and sample observations can constrain scenarios of post-impact evolution in the earliest history of the Earth-Moon system. © 2014 The Author(s) Published by the Royal Society. All rights reserved.

Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

USGS Publications Warehouse

Brown, Shaun T.; Kennedy, B. Mack; DePaolo, Donald J.; Hurwitz, Shaul; Evans, William C.

2013-01-01

We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO2. Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO2, and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

Insulin sensitivity index (ISI0, 120) potentially linked to carbon isotopes of breath CO2 for pre-diabetes and type 2 diabetes

PubMed Central

Ghosh, Chiranjit; Mukhopadhyay, Prabuddha; Ghosh, Shibendu; Pradhan, Manik

2015-01-01

New strategies for an accurate and early detection of insulin resistance are important to delay or prevent the acute onset of type 2 diabetes (T2D). Currently, insulin sensitivity index (ISI0,120) is considered to be a viable invasive method of whole-body insulin resistance for use in clinical settings in comparison with other invasive sensitivity indexes like homeostasis model assessment (HOMA), and quantitative insulin sensitivity check index (QUICKI). To investigate how these sensitivity indexes link the 13C/12C-carbon isotopes of exhaled breath CO2 to pre-diabetes (PD) and type 2 diabetes in response to glucose ingestion, we studied excretion dynamics of 13C/12C-isotopic fractionations of breath CO2. Here, we show that 13C/12C-isotope ratios of breath CO2 were well correlated with blood glucose, insulin, glycosylated-hemoglobin as well as with HOMA-IR and 1/QUICKI. Conversely, the strongest correlation was observed between 1/ISI0,120 and breath CO2 isotopes. Consequently, we determined several optimal diagnostic cut-off points of 1/ISI0,120 and 13CO2/12CO2-isotope ratios to distinctively track the evolution of PD prior to the onset of T2D. Our findings suggest that isotopic breath CO2 is a novel method for accurate estimation of ISI0,120 and thus may open new perspectives into the isotope-specific non-invasive evaluation of insulin resistance for large-scale real-time diabetes screening purposes. PMID:26148706

Effects of mining activities on evolution of water chemistry in coal-bearing aquifers in karst region of Midwestern Guizhou, China: evidences from δ13C of dissolved inorganic carbon and δ34S of sulfate.

PubMed

Li, Qingguang; Wu, Pan; Zha, Xuefang; Li, Xuexian; Wu, Linna; Gu, Shangyi

2018-04-24

The generation of acid mine drainage (AMD) may accelerate watershed erosion and promote the migration of heavy metals, then threaten local ecosystems such as aquatic life and even human health. Previous studies have focused primarily on influence of AMD in surface environment. In order to reveal the acidizing processes in karst high-sulfur coalfield in Southwest China, this study, by contrast, focused on the hydrogeochemical evolution process and acidification mechanism of mine water in Zhijin coalfield, western Guizhou Province. The oxidation of pyrite and other sulfides induced strong acidification of mine water according to the water chemical analysis. As a result, a series of geochemical processes such as dissolution of carbonates and silicates, hydrolysis of metal ions, and degassing of CO 2 complicated water chemical evolution. The dissolution of silicates controlled the chemical composition of mine water, but more carbonates might be dissolved during the acidification of mine water. The sources of sulfate are quite different in water samples collected from the two selected mine. According to sulfur isotope analysis, the dissolution of gypsum is the primary source of sulfate in samples from Hongfa mine, whereas sulfide oxidation contributed a large amount of sulfate to the mine water in Fenghuangshan mine. The dissolution of carbonates should be an important source of DIC in mine water and CO 2 originating from organic mineralization might also have a certain contribution. This study elucidated the groundwater chemical evolution processes in high-sulfur coal-bearing strata and provided a foundation for further study of carbonates erosion and carbon emission during acidification of mine water.

Hydrology of the Poverty Bay flats aquifers, New Zealand: recharge mechanisms, evolution of the isotopic composition of dissolved inorganic carbon, and ground-water ages

NASA Astrophysics Data System (ADS)

Taylor, C. B.

1994-06-01

With the exception of water-bearing remnants of earlier fluvial gravels overlying basement, the sediments of the Poverty Bay flats have accumulated during the postglacial period of the past 14 000 years, and have been tilted and deformed by recent tectonism. A sequence of gravel aquifers, separated by poorly permeable silt layers, lies between surface and basement, which is at depths varying between 50 and 200 m. A shallow sand/silt aquifer is situated near the coast. This study applies evidence of chemical and isotopic properties of river and ground water to clarify the recharge mechanisms, chemical evolution and age of the ground water in the aquifers. Particular attention is paid to the evolution of dissolved inorganic carbon content, applying carbon-14 data measured by accelerator mass spectrometry. Most of the ground water is recharged from the Waipaoa River, which flows across the flats and discharges into Poverty Bay. The two deepest aquifers (Matokitoki and Makauri) are both tritium-free; the deeper Matokitoki Gravels yield water of age about 4300 years since recharge (possibly up to 1300 years greater), but the Makauri water is no older than 100-200 years, discharging slowly through overlying aquitards near the limit of closest approach to the present coast.

Chasing Neoproterozoic Atmospheric Oxygen Ghosts

NASA Astrophysics Data System (ADS)

Bjerrum, C. J.; Canfield, D. E.; Dahl, T. W.

2016-12-01

Increasing atmospheric oxygen has been considered a necessary condition for the evolution of animal life for over half a century. While direct proxies for atmospheric oxygen are difficult to obtain, a number of indirect proxies have been giving us a ghost image of rising atmospheric oxygen at the close of the Precambrian. In this context, redox sensitive elements and isotopes represent the hallmark for a significant reduction in anoxic areas of the world ocean, implicating a significant rise of atmospheric oxygen during the Neoproterozoic. Here, we test to what degree redox sensitive elements in ancient marine sediments are proxies of atmospheric oxygen. We model the redox-chemical evolution of the shelf seas and ocean using a combination of 3D high resolution shelf sea models and a simpler global ocean biogeochemical model including climate weathering feedbacks, a free sea level and parameterized icecaps. We find that ecosystem evolution would have resulted in reorganization of the nutrient and redox balance of the shelf-ocean system causing a significant increase in oxygenated areas that permitted a boosting of trace metal concentrations in the remaining anoxic areas. While this reorganization takes place there is limited net change in the modelled atmospheric oxygen, warning us against interpreting changing trace metal concentrations and isotopes as reflecting a rise in atmospheric oxygen.

Use of stable isotope analysis in determining aquatic food webs

EPA Science Inventory

Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

PubMed Central

Canfield, Donald E.

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly on interpretations of the isotope record of seawater sulfates and sedimentary pyrites. The isotope record, however, does not give a complete picture of the ancient sulfur cycle. This is because, in standard isotope mass balance models, there are more variables than constraints. Typically, in interpretations of the isotope record and in the absence of better information, one assumes that the isotopic composition of the input sulfate to the oceans has remained constant through time. It is argued here that this assumption has a constraint over the last 390 Ma from the isotopic composition of sulfur in coal. Indeed, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through the Phanerozoic Eon. PMID:23650346

Oxygen Isotope Evidence for the Relationship between CM and CO Chondrites: Could they Both Coexist on a Single Asteroid

NASA Technical Reports Server (NTRS)

Greenwood, R. C.; Howard, K. T.; Franchi, I. A.; Zolensky, M. E.; Buchanan, P. C.; Gibson, J. M.

2014-01-01

Water played a critical role in the early evolution of asteroids and planets, as well as being an essential ingredient for life on Earth. However, despite its importance, the source of water in the inner solar system remains controversial. Delivery of water to Earth via comets is inconsistent with their relatively elevated D/H ratios, whereas carbonaceous chondrites (CCs) have more terrestrial-like D/H ratios [1]. Of the eight groups into which the CCs are divided, only three (CI, CM, CR) show evidence of extensive aqueous alteration. Of these, the CMs form the single most important group, representing 34% of all CC falls and a similar percentage of finds (Met. Bull. Database). CM material also dominates the population of CC clasts in extraterrestrial samples [2, 3]. The Antarctic micrometeorites population is also dominated by CM and CI-like material and similar particles may have transported water and volatiles to the early Earth [4]. CCs, and CMs in particular, offer the best opportunity for investigating the evolution of water reservoirs in the early solar system. An important aspect of this problem involves identifying the anhydrous silicate component which co-accreted with ice in the CM parent body. A genetic relationship between the essentially anhydrous CO group and the CMs was proposed on the basis of oxygen isotope evidence [5]. However, previous CM whole-rock oxygen isotope data scattered about a line of approximately 0.5 that did not intersect the field of CO chondrites [5]. Here we discuss new oxygen isotope data which provides additional constraints on the relationship between CO and CM chondrites.

An 11,000-year record of depositional environmental change based upon particulate organic matter and stable isotopes (C and N) in a lake sediment in southeastern Brazil

NASA Astrophysics Data System (ADS)

Lorente, Flávio Lima; Pessenda, Luiz Carlos Ruiz; Oboh-Ikuenobe, Francisca; Buso Junior, Antonio Alvaro; Rossetti, Dilce de Fátima; Giannini, Paulo César Fonseca; Cohen, Marcelo Cancela Lisboa; de Oliveira, Paulo Eduardo; Mayle, Francis Edward; Francisquini, Mariah Izar; França, Marlon Carlos; Bendassolli, José Albertino; Macario, Kita

2018-07-01

The aim of this paper is to reconstruct an 11,000-year history of depositional environmental change in southeastern Brazil, based upon the integration of particulate organic matter and stable isotope (C and N) data from a 136-cm sediment core from Lake Canto Grande. These proxies are used to explore the evolution of terrestrial and marine influence on the lake. Isotopic (δ13C: -27.87‰ to -31.9‰; δ15N: -0.07‰-4.9‰) and elemental (total organic carbon - TOC: 0.58%-37.19%; total nitrogen - TN: 0.08%-1.73%; C/N: 0.3 to 54.7) values recorded in Lake Canto Grande suggest that the sedimentary organic matter was derived from mostly C3 land plants and freshwater phytoplankton. Particulate organic matter and cluster analyses distinguished four associations characterized by the predominance of amorphous organic matter, followed by phytoclasts and palynomorphs. These results indicate two different phases of lake evolution. The first phase (136 - 65 cm; ∼10,943 cal yr. B.P. to ∼8529 cal yr. B.P.) is recorded by sand layers interbedded with mud, which contain amorphous organic matter (AOM, 45-59%) and phytoclasts (opaques - OP: 6-18%; non-opaques - NOP: 17-23%) which indicate a floodplain area. The second phase (65-0 cm; ∼8529 cal yr. B.P. to ∼662 cal yr. B.P.) comprises mud, AOM (68-86%) and palynomorphs (PAL, 8-16%) related to lake establishment comparable to modern conditions. Thus, characterizing particulate organic matter, in combination with stable isotopes, proved to be invaluable proxies for lacustrine paleoenvironmental change through the Holocene.

Measuring N2 Pressure Using Cyanobacteria Discipline: Geomicrobiology

NASA Technical Reports Server (NTRS)

Silverman, Shaelyn N.; Kopf, Sebastian; Gordon, Richard; Bebout, Brad M.; Som, Sanjoy

2017-01-01

The evolution of Earth's atmosphere has been governed by biological evolution. Dinitrogen (N2) has been a major constituent of Earth's atmosphere throughout the planet's history, yet only a few constraints exist for the partial pressure of N2 (pN2). In this study we evaluate two new potential proxies for pN2: the physical spacing between heterocysts and the isotopic signature of nitrogen fixation in filamentous cyanobacteria. Heterocyst-forming filamentous cyanobacteria are some of the oldest photosynthetic microorganisms on Earth, and debated fossilized specimens have been found in sedimentary rocks as old as 2 Ga. These organisms overcome nitrogen limitation in their aqueous environment through cellular differentiation along their filaments. The specialized cells that develop, known as heterocysts, fix the nitrogen and laterally distribute it to neighboring cells along the filaments. Because the concentration of the dissolved N2 available to the filaments correlates directly with pN2, any preservable physiological response of the organism to the changed N2 availability constitutes a potential proxy for pN2. In the laboratory, we have examined how pN2 is reflected in the heterocyst spacing pattern and in the isotopic signature of nitrogen fixation by subjecting the representative species Anabaena cylindrica and Anabaena variabilis to different N2 partial pressures during growth at constant temperature and lighting (in media free of combined nitrogen). We show experimentally that the distance between heterocysts and the nitrogen isotope fractionation measured in bulk biomass reflect the pN2 experienced by Anabaena cylindrica. Current work is investigating these responses in Anabaena variabilis. When heterocystous cyanobacteria fossilize, these morphological and isotopic signatures should preserve information about pN2 at that time. Application of this relationship to the rock record may provide a paleoproxy to complement the two existing geobarometers.

A geochemical study of Nea-Kameni hyalodacites (Santorini Volcano, Aegean island arc). Inferences concerning the origin and effects of solfataras and magmatic evolution

NASA Astrophysics Data System (ADS)

Briqueu, Louis; Lancelot, Joël R.

1984-03-01

Since the Santorini Volcano (Aegean arc, eastern Mediterranean Sea) collapsed, volcanic activity has been located at the center of the flooded caldera. Over the past 800 years, five lava flows have formed one of the central islets (Nea-Kameni). Since 1951, when the last eruption occurred, a permanent fumarolic activity has remained. We present chemical analyses (major elements, trace-elements and Sr isotopic ratios) of ten samples from the five hyalodacitic lava flows, showing different stages of alteration, from a completely fresh lava up to one bearing native sulfur and other sublimates. Only the macroscopic aspect of these hyalodacites is affected by fumarolic activity. The elements that are mobile as a result of hydrothermal processes, such as the alkaline (K, Rb) or the chalcophile elements (Zn, Pb), show great homogeneity; the same can be said for the Sr isotopic compositions which range from 0.7046 to 0.7049. None of the analyzed samples has an Sr isotopic composition as high as those reported by Puchelt and Hoefs (1971) for rock samples collected in the same lava flows. If we take into account the marine surroundings of Nea-Kameni islet, these observations put severe restraints on the different hypotheses regarding the origin of the halogens (seawater or meteoric water). The contamination processes of these dacitic lavas are clearly less important than assumed by other authors according to previous Sr isotopic data. Finally, the homogeneity of the elements with low partition coefficients is sufficient to show that the magma has not undergone any perceptible evolution during the last 300 years.

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Chlorine Isotopes: As a Possible Tracer of Fluid/Bio-Activities on Mars and a Progress Report on Chlorine Isotope Analysis by TIMs

NASA Technical Reports Server (NTRS)

Nakamura, N.; Nyquist, L.E.; Reese, Y.; Shih, C-Y.; Numata, M.; Fujitani, T.; Okano, O.

2009-01-01

Significantly large mass fractionations between chlorine isotopes (Cl-35, Cl-37) have been reported for terrestrial materials including both geological samples and laboratory materials. Also, the chlorine isotopic composition can be used as a tracer for early solar system processes. Moreover, chlorine is ubiquitous on the Martian surface. Typical chlorine abundances in Gusev soils are approx.0.5 %. The global surface average chlorine abundance also is approx.0.5 %. Striking variations among outcrop rocks at Meridiani were reported with some chlorine abundances as high as approx.2%. Characterizing conditions under which chlorine isotopic fractionation may occur is clearly of interest to planetary science. Thus, we have initiated development of a chlorine isotopic analysis technique using TIMS at NASA-JSC. We present here a progress report on the current status of development at JSC and discuss the possible application of chlorine isotopic analysis to Martian meteorites in a search for fluid- and possibly biological activity on Mars.

Lithium in Brachiopods - proxy for seawater evolution?

NASA Astrophysics Data System (ADS)

Gaspers, Natalie; Magna, Tomas; Tomasovych, Adam; Henkel, Daniela

2017-04-01

Marine biogenic carbonates have the potential to serve as a proxy for evolution of seawater chemistry. In order to compile a record of the past and recent δ7Li in the oceans, foraminifera shells, scleractinian corals and belemnites have been used. However, only a foraminifera-based record appears to more accurately reflect the Li isotope composition of ocean water. At present, this record is available for the Cenozoic with implications for major events during this period of time, including K/T event [1]. A record for the entire Phanerozoic has not yet been obtained. In order to extend this record to the more distant past, Li elemental/isotope systematics of brachiopods were investigated because these marine animals were already present in Early Cambrian oceans and because they are less sensitive to diagenesis-induced modifications due to their shell mineralogy (low-Mg calcite). The preliminary data indicates a species-, temperature- and salinity-independent behavior of Li isotopes in brachiopod shells. Also, no vital effects have been observed for different shell parts. The consistent offset of -4‰ relative to modern seawater is in accordance with experimental data [2]. Further data are now being collected for Cenozoic specimens to more rigorously test brachiopods as possible archives of past seawater in comparison to the existing foraminiferal records. [1] Misra & Froelich (2012) Science 335, 818-823 [2] Marriott et al. (2004) Chem Geol 212, 5-15

Workshop on Oxygen in the Terrestrial Planets

NASA Technical Reports Server (NTRS)

2004-01-01

This volume contains abstracts that have been accepted for presentation at the Workshop on Oxygen in the Terrestrial Planets, July 20-23,2004, Santa Fe, New Mexico. The contents include: 1) Experimental Constraints on Oxygen and Other Light Element Partitioning During Planetary Core Formation; 2) In Situ Determination of Fe(3+)/SigmaFe of Spinels by Electron Microprobe: An Evaluation of the Flank Method; 3) The Effect of Oxygen Fugacity on Large-Strain Deformation and Recrystallization of Olivine; 4) Plagioclase-Liquid Trace Element Oxygen Barometry and Oxygen Behaviour in Closed and Open System Magmatic Processes; 5) Core Formation in the Earth: Constraints from Ni and Co; 6) Oxygen Isotopic Compositions of the Terrestrial Planets; 7) The Effect of Oxygen Fugacity on Electrical Conduction of Olivine and Implications for Earth s Mantle; 8) Redox Chemical Diffusion in Silicate Melts: The Impact of the Semiconductor Condition; 9) Ultra-High Temperature Effects in Earth s Magma Ocean: Pt and W Partitioning; 10) Terrestrial Oxygen and Hydrogen Isotope Variations: Primordial Values, Systematics, Subsolidus Effects, Planetary Comparisons, and the Role of Water; 11) Redox State of the Moon s Interior; 12) How did the Terrestrial Planets Acquire Their Water?; 13) Molecular Oxygen Mixing Ratio and Its Seasonal Variability in the Martian Atmosphere; 14) Exchange Between the Atmosphere and the Regolith of Mars: Discussion of Oxygen and Sulfur Isotope Evidence; 15) Oxygen and Hydrogen Isotope Systematics of Atmospheric Water Vapor and Meteoric Waters: Evidence from North Texas; 16) Implications of Isotopic and Redox Heterogeneities in Silicate Reservoirs on Mars; 17) Oxygen Isotopic Variation of the Terrestrial Planets; 18) Redox Exchanges in Hydrous Magma; 19) Hydrothermal Systems on Terrestrial Planets: Lessons from Earth; 20) Oxygen in Martian Meteorites: A Review of Results from Mineral Equilibria Oxybarometers; 21) Non-Linear Fractionation of Oxygen Isotopes Implanted in Lunar Metal Grains: Solar, Lunar or Terrestrial Origin? 22) Isotopic Zoning in the Inner Solar System; 23) Redox Conditions on Small Bodies; 24) Determining the Oxygen Fugacity of Lunar Pyroclastic Glasses Using Vanadium Valence - An Update; 25) Mantle Redox Evolution and the Rise of Atmospheric O2; 26) Variation of Kd for Fe-Mg Exchange Between Olivine and Melt for Compositions Ranging from Alkaline Basalt to Rhyolite; 27) Determining the Partial Pressure of Oxygen (PO,) in Solutions on Mars; 28) The Influence of Oxygen Environment on Kinetic Properties of Silicate Rocks and Minerals; 29) Redox Evolution of Magmatic Systems; 30) The Constancy of Upper Mantlefo, Through Time Inferred from V/Sc Ratios in Basalts: Implications for the Rise in Atmospheric 0 2; 31) Nitrogen Solubility in Basaltic Melt. Effects of Oxygen Fugacity, Melt Composition and Gas Speciation; 32) Oxygen Isotope Anomalies in the Atmospheres of Earth and Mars; 33) The Effect of Oxygen Fugacity on Interdiffusion of Iron and Magnesium in Magnesiowiistite 34) The Calibration of the Pyroxene Eu-Oxybarometer for the Martian Meteorites; 35) The Europium Oxybarometer: Power and Pitfalls; 36) Oxygen Fugacity of the Martian Mantle from PigeoniteMelt Partitioning of Samarium, Europium and Gadolinium; 37) Oxidation-Reduction Processes on the Moon: Experimental Verification of Graphite Oxidation in the Apollo 17 Orange Glasses; 38) Oxygen and Core Formation in the Earth; 39) Geologic Record of the Atmospheric Sulfur Chemistry Before the Oxygenation of the Early Earth s Atmosphere; 40) Comparative Planetary Mineralogy: V/(CrCAl) Systematics in Chromite as an Indicator of Relative Oxygen Fugacity; 41) How Well do Sulfur Isotopes Constrain Oxygen Abundance in the Ancient Atmospheres? 42) Experimental Constraints on the Oxygen Isotope (O-18/ O-16) Fractionation in the Ice vapor and Adsorbant vapor Systems of CO2 at Conditions Relevant to the Surface of Mars; 43) Micro-XANES Measurements on Experimental Spinels andhe Oxidation State of Vanadium in Spinel-Melt Pairs; 44) Testing the Magma Ocean Hypothesis Using Metal-Silicate Partitioning of Te, Se and S; 45) Solubility of Oxygen in Liquid Iron at High Pressure and Consequences for the Early Differentiation of Earth and Mars Metallic Liquid Segregation in Planetesimals; 46) Oxygen Fugacity of Lunar Basalts and the Lunar Mantle. Range of fo2 and the Effectiveness of Oxybarometers; 47) Thermodynamic Study of Dissociation Processes of Molecular Oxygen in Vapor over Oxide Compounds; 48) Oxygen Profile of a Thermo-Haliophilic Community in the Badwater Salt Flat; 49) Oxygen Barometry Using Synchrotron MicroXANES of Vanadium; 50) Mass-Independent Isotopic Fractionation of Sulfur from Sulfides in the Huronian Supergroup, Canada; 51) Mass Independent Isotopes and Applications to Planetary Atmospheres; 52) Electrical Conductivity, Oxygen Fugacity, and Mantle Materials; 53) Crustal Evolution and Maturation on Earth: Oxygen Isotope Evidence; 54) The Oxygen Isotope Composition of the Moon: Implications for Planet Formation; 55) Oxygen Isotope Composition of Eucrites and Implications for the Formation of Crust on the HED Parent Body; and 56) The Role of Water in Determining the Oxygen Isotopic Composition of Planets.

Role of Short-Range Chemical Ordering in (GaN) 1–x (ZnO) x for Photodriven Oxygen Evolution

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

Chen, Dennis P.; Neuefeind, Joerg C.; Koczkur, Kallum M.

(GaN)1–x(ZnO)x (GZNO) is capable of visible-light driven water splitting, but its bandgap at x ≤ 0.15 (>2.7 eV) results in poor visible-light absorption. Unfortunately, methods to narrow its bandgap by incorporating higher ZnO concentrations are accompanied by extensive Urbach tailing near the absorption-edge, which is indicative of structural disorder or chemical inhomogeneities. We evaluated whether this disorder is intrinsic to the bond-length distribution in GZNO or is a result of defects introduced from the loss of Zn during nitridation. Here, the synthesis of GZNO derived from layered double hydroxide (LDH) precursors is described which minimizes Zn loss and chemical inhomogeneitiesmore » and enhances visible-light absorption. The average and local atomic structures of LDH-derived GZNO were investigated using X-ray and neutron scattering and are correlated with their oxygen evolution rates. An isotope-contrasted neutron-scattering experiment was conducted in conjunction with reverse Monte Carlo (RMC) simulations. We showed that a bond-valence bias in the RMC refinements reproduces the short-range ordering (SRO) observed in structure refinements using isotope-contrasted neutron data. The findings suggest that positional disorder of cation–anion pairs in GZNO partially arises from SRO and influences local bond relaxations. Furthermore, particle-based oxygen evolution reactions (OERs) in AgNO3 solution reveal that the crystallite size of GZNO correlates more than positional disorder with oxygen evolution rate. These findings illustrate the importance of examining the local structure of multinary photocatalysts to identify dominant factors in particulate-based photodriven oxygen evolution.« less

Integrated elemental and Sr-Nd-Pb-Hf isotopic studies of Mesozoic mafic dykes from the eastern North China Craton: implications for the dramatic transformation of lithospheric mantle

NASA Astrophysics Data System (ADS)

Liu, Shen; Feng, Caixia; Santosh, M.; Feng, Guangying; Coulson, Ian M.; Xu, Mengjing; Guo, Zhuang; Guo, Xiaolei; Peng, Hao; Feng, Qiang

2018-02-01

Evolution of the lithospheric mantle beneath the North China Craton (NCC) from its Precambrian cratonic architecture until Paleozoic, and the transformation to an oceanic realm during Mesozoic, with implications on the destruction of cratonic root have attracted global attention. Here we present geochemical and isotopic data on a suite of newly identified Mesozoic mafic dyke swarms from the Longwangmiao, Weijiazhuang, Mengjiazhuang, Jiayou, Huangmi, and Xiahonghe areas (Qianhuai Block) along the eastern NCC with an attempt to gain further insights on the lithospheric evolution of the region. The Longwangmiao dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 4.3) and EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.706; ε Nd (t) < -6.3, (206Pb/204Pb) i > 16.6, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.8, ε Hf (t) < -22.4). The Weijiazhuang dykes are sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7), and display similar EM1-like isotopic features ((87Sr/86Sr) i > 0.706; ε Nd (t) < -7.0, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -23.3). The Mengjiazhuang dykes are also sub-alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 2.4) and EM1-like isotopic features((87Sr/86Sr) i > 0.706; ε Nd (t) < -18.4, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). The Jiayou dykes also display sub-alkaline affinity with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 3.7) and EM1-like Sr-Nd-Pb-Hf isotopic features ((87Sr/86Sr) i > 0.706; ε Nd(t) < -15.3, (206Pb/204Pb) i > 16.7, (207Pb/204Pb) i > 15.4, (208Pb/204Pb) i > 36.9, ε Hf (t) < -18.4). The Huangmi dykes are alkaline (with Na2O + K2O ranging to more than 5.9 wt.%)) with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N > 9.3) and EM1-like isotopic composition ((87Sr/86Sr) i > 0.705; ε Nd (t) < -15.1, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -12.2). The Xiahonghe dykes are alkaline with LILE (Ba and K)- and LREE-enrichment ((La/Yb) N = 2.12-2.84) and similar EM1-like Sr-Nd-Pb-Hf isotopic signature ((87Sr/86Sr) i > 0.705; ε Nd (t)<-18.0, (206Pb/204Pb) i > 16.9, (207Pb/204Pb) i > 15.5, (208Pb/204Pb) i > 36.9, ε Hf (t) < -8.6). Our data from the various mafic dyke suites suggest that the magmas were derived from EM1-like lithospheric mantle, corresponding to lithospheric mantle modified by the previously foundered lower crust beneath the eastern NCC. Our results suggest contrasting lithospheric evolution from Triassic (212 Ma) to Cretaceous (123 Ma) beneath the NCC. These mafic dykes mark an important phase of lithospheric thinning in the eastern North China Craton.

Reconstruction of paleoenvironment recorded in the Ediacaran Lantain black shales

NASA Astrophysics Data System (ADS)

Liu, Y. H.; Lee, D. C.; You, C. F.; Zhou, C.

2016-12-01

The Ediacaran period (635-542 Ma) was a critical time in the history of life and Earth, during which profound changes in complex megascopic life and probably ocean oxygenation occurred. A growing evidence demonstrates that the Early Ediacaran ocean was not simply a largely anoxic basin as previous thought. Pulsed oxidation or a multilayered water column had been proposed to explain the presence of Lantain macrofossils. To verify these models, in-situ isotopic analysis becomes critical in identifying the isotopic signatures of authigenic minerals, and to avoid mixing in the signals from detrital and diagenetic phases. In this study, samples from Lantain Member II, a 40 m thick black shale unit containing macrofossils and overlaying the cap carbonate, were analyzed, including one sample from the lower part of Member II and six samples from upper part of Member II. Abundant xenotimes were overgrown on the detrital zircon grains during early diagenesis in all the samples. This authigenic phosphate mineral provides the best constraint of depositional age. In addition, framboidal pyrites and microbial mats are alternatively present on the top of Member II, where layered barites are found in one sample, supporting the model of frequent changes of redox conditions. Preliminary results show that the depositional age of barite-bearing black shale is > 520 Ma. In this study, we will combine the in-situ U-Pb xenotime dating and sulfur isotopes in barite and pyrite to discuss the evolution of redox conditions in the Ediacaran ocean.

Trophic hierarchies revealed via amino acid isotopic analysis

USDA-ARS?s Scientific Manuscript database

Despite the potential of isotopic methods to illuminate trophic function, accurate estimates of lifetime feeding tendencies have remained elusive. A relatively new approach—referred to as compound-specific isotopic analysis (CSIA)—has emerged, centering on the measurement of 15N:14N ratios in amino ...

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

Sulfur record of rising and falling marine oxygen and sulfate levels during the Lomagundi event

PubMed Central

Planavsky, Noah J.; Bekker, Andrey; Hofmann, Axel; Owens, Jeremy D.; Lyons, Timothy W.

2012-01-01

Carbonates from approximately 2.3–2.1 billion years ago show markedly positive δ13C values commonly reaching and sometimes exceeding +10‰. Traditional interpretation of these positive δ13C values favors greatly enhanced organic carbon burial on a global scale, although other researchers have invoked widespread methanogenesis within the sediments. To resolve between these competing models and, more generally, among the mechanisms behind Earth’s most dramatic carbon isotope event, we obtained coupled stable isotope data for carbonate carbon and carbonate-associated sulfate (CAS). CAS from the Lomagundi interval shows a narrow range of δ34S values and concentrations much like those of Phanerozoic and modern marine carbonate rocks. The δ34S values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition. These observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone. Toward the end of the carbon isotope excursion there is an increase in the δ34S values of CAS. We propose that these trends in C and S isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion. PMID:23090989

Pb-Pb systematics of lunar rocks: differentiation, magmatic and impact history of the Moon

NASA Astrophysics Data System (ADS)

Nemchin, A.; Martin, W.; Norman, M. D.; Snape, J.; Bellucci, J. J.; Grange, M.

2016-12-01

Two independent decay chains in U-Pb system allow the determination of both ages and initial isotope compositions by analyzing only Pb in the samples. A typical Pb analysis represents a mixture of radiogenic Pb produced from the in situ U decay, initial Pb and laboratory contamination. Utilizing the ability of ion probes to analyse 10-30 micrometer-sized spots in the samples while avoiding fractures and other imperfections that commonly host contamination, permits extraction of pure lunar Pb compositions from the three component mixtures. This results in both accurate and precise ages of the rocks and their initial compositions. Lunar Mare and KREEP basalts postdating the major lunar bombardment are likely to represent such three component mixtures and are therefore appropriate for this approach, also giving an opportunity to investigate Pb evolution in their sources. A source evolution model constrained using available data indicates a major differentiation on the Moon at 4376±18 Ma and very radiogenic lunar mantle at this time. This age is likely to reflect the mean time of KREEP formation during the last stage of Magma Ocean differentiation. Rocks older than about 3.9 Ga are more complex than basalts and may include an extra Pb component, if modified by impacts. An example of this is presented by Pb-Pb data obtained for the anorthosite sample 62236, where the age of the rock is determined as 4367±29 Ma from analyses of CPx lamellae inside the large Opx grains: however large plagioclase crystals do not contain Pb in quantities sufficient for ion probe analysis, precluding determination of the initial Pb composition of the sample. Most of Pb is found in the brecciated parts of the anorthosite between the large grains. The composition of this Pb is similar to the initial Pb of 3909±17 Ma Apollo 16 breccia 66095, suggesting that is was injected into the anorthosite during a 3.9 Ga impact. Similar ca 3.9 Ga ages were determined for 1-2 millimeter size feldspathic clasts from several Apollo 14 breccias, where they are likely to date Pb homogenization during the Imbrium impact. Combined with U-Pb data obtained previously using U-bearing minerals such as zircon and phosphates, the new Pb-Pb data sets open an opportunity for a detailed chronological and isotopic investigation of lunar differentiation, magmatic evolution and impact history.

Syntectic Reactions involving Limestones and Limestone-Derived Carbonatitic Melts in the Generation of some Peralkalic Magmas: Reflections on Reginald Daly's Insights 100 Years Later

NASA Astrophysics Data System (ADS)

Lentz, D.

2017-12-01

The theoretical analysis of how sedimentary limestones and marbles could melt as a result of infiltrative contact metasomatism associated with silicate magmas, enables reconsideration of the limestone syntectic (assimilation) hypothesis for the origin of some peralkalic rocks. Reginald Daly's syntectic model published in detail in early 1918 fell out of favor because experimental evidence from the early 1960's suggested; 1) that limestone assimilation would increase P(CO2) and cause solidification of the silicate intrusion, 2) that there is a thermal barrier between silica-saturated and undersaturated magmas that would inhibit extensive desilication of the magma, and 3) the endothermic decarbonation reactions would require heat via magmatic crystallization of near-solidus magmas. However, these concerns were not as critical for high-T mafic melts relative to more low-T silicic melts, although most subsequent researchers dismissed syntexis as isotopic arguments also seemed robust. However, skarn-related limestone melts can interact much more easily with silicate magma, resulting in calc-silicate-forming (endoskarn-like) limestone syntectic (desilication - calcification-magnesification processes) decarbonation reactions with compositional evolution into the silica-undersaturated field. If mafic in composition originally when syntectically modified, then the CO2-bearing derivative peralkalic melt may subsequently react with the dominant volume magma or fractionate separately into a more evolved composition. As well, an increase in P(CO2) within the modified silicate fraction coupled with compositional evolution to more silica-undersaturated compositions enhances the stability of the immiscible, extremely low viscosity carbonate melt fraction. In addition, dynamic interaction of these co-existing immiscible melts (analogous to the current hypothesis) would partition elements, as well as isotopic signatures, such that they would be virtually unrecognizable as having a crustal level syntectic origin, based on mass-balance principles and Rayleigh decarbonation isotopic equilibria, as they do in many infiltrative skarn systems. Essentially, this partly vindicates the basic premise of Daly's limestone syntectic hypothesis for the origin of some peralkalic igneous rocks.

Identification of anthropogenic and natural inputs of sulfate into a karstic coastal groundwater system in northeast China: evidence from major ions, δ13CDIC and δ34SSO4

NASA Astrophysics Data System (ADS)

Han, Dongmei; Song, Xianfang; Currell, Matthew J.

2016-05-01

The hydrogeochemical processes controlling groundwater evolution in the Daweijia area of Dalian, northeast China, were characterised using hydrochemistry and isotopes of carbon and sulfur (δ13CDIC and δ34SSO4). The aim was to distinguish anthropogenic impacts as distinct from natural processes, with a particular focus on sulfate, which is found at elevated levels (range: 54.4 to 368.8 mg L-1; mean: 174.4 mg L-1) in fresh and brackish groundwater. The current investigation reveals minor seawater intrusion impact (not exceeding 5 % of the overall solute load), in contrast with extensive impacts observed in 1982 during the height of intensive abstraction. This indicates that measures to restrict groundwater abstraction have been effective. However, hydrochemical facies analysis shows that the groundwater remains in a state of ongoing hydrochemical evolution (towards Ca-Cl type water) and quality degradation (increasing nitrate and sulfate concentrations). The wide range of NO3 concentrations (74.7-579 mg L-1) in the Quaternary aquifer indicates considerable input of fertilisers and/or leakage from septic systems. Both δ13C (-14.5 to -5.9 permil) and δ34SSO4 (+5.4 to +13.1 permil) values in groundwater show increasing trends along groundwater flow paths. While carbonate minerals may contribute to increasing δ13CDIC and δ34SSO4 values in deep karstic groundwater, high loads of agricultural fertilisers reaching the aquifer via irrigation return flow are likely the main source of the dissolved sulfate in Quaternary groundwater, as shown by distinctive isotopic ratios and a lack of evidence for other sources in the major ion chemistry. According to isotope mass balance calculations, the fertiliser contribution to overall sulfate has reached an average of 62.1 % in the Quaternary aquifer, which has a strong hydraulic connection to the underlying carbonate aquifer. The results point to an alarming level of impact from the local intensive agriculture on the groundwater system, a widespread problem throughout China.

Identification of anthropogenic and natural inputs of sulfate into a karstic coastal groundwater system in northeast China: evidence from major ions, δ13CDIC and δ34SSO4

NASA Astrophysics Data System (ADS)

Han, D.; Song, X.; Currell, M. J.

2015-11-01

The hydrogeochemical processes controlling groundwater evolution in the Daweijia area of Dalian, northeast China, were characterized using hydrochemistry and isotopes of carbon and sulfur (δ13CDIC and δ34SSO4). The aim was to distinguish anthropogenic impacts as distinct from natural processes, with a particular focus on sulfate, which is found at elevated levels (range: 54.4 to 368.8 mg L-1; mean: 174.4 mg L-1) in fresh and brackish groundwater. The current investigation reveals minor seawater intrusion impact (not exceeding 5 % of overall solute load), in contrast with extensive impacts observed in 1982 during the height of intensive abstraction. This indicates that measures to restrict groundwater abstraction have been effective. However, hydrochemical facies analysis shows that the groundwater remains in a state of ongoing hydrochemical evolution (towards Ca-Cl type water) and quality degradation (increasing nitrate and sulphate concentrations). The wide range of NO3 concentrations (74.7-579 mg L-1) in the Quaternary aquifer indicates considerable input of fertilizers and/or leakage from septic systems. Both δ13C (-14.5 to -5.9 ‰) and δ34SSO4 (+5.4-+13.1 ‰) values in groundwater show increasing trends along groundwater flow paths. While carbonate minerals may contribute to increasing δ13CDIC and δ34SSO4 values in deep karstic groundwater, high loads of agricultural fertilizers reaching the aquifer via irrigation return flow are likely the main source of the dissolved sulfate in Quaternary groundwater, as shown by distinctive isotopic ratios and a lack of evidence for other sources in the major ion chemistry. According to isotope mass balance calculations, the fertilizer contribution to overall sulfate has reached an average of 62.1 % in the Quaternary aquifer, which has a strong hydraulic connection to the underlying carbonate aquifer. The results point to an alarming level of impact from the local intensive agriculture on the groundwater system, a widespread problem throughout China.

Evolution of Subducted Oceanic Crust in Dynamic Mantle Models

NASA Astrophysics Data System (ADS)

Brandenburg, J.; van Keken, P. E.; Ballentine, C.; Hauri, E.

2006-12-01

Isotopic ratios measured in oceanic basalts indicate the persistence of a highly differentiated and ancient mantle component. The provenance and distribution of this component are the subject of much discussion. A number of geodynamic studies have focused on the preservation of a chemically dense layer in the deepest mantle, while a smaller set of studies have explored the possibilities for its generation. We present an evaluation of the hypothesis that such a layer may represent the accumulation of subducted oceanic crust, with critical examination of the role that plate tectonics plays in mantle differentiation. In geodynamic models the treatment of plate tectonics controls crust production, subduction, and modulates the remixing rate. We use two methods for approximating plates in our models; prescription of a velocity boundary condition, and the force-balance method [1]. Emphasis is placed on the force-balance method, in which a numerical solution for the conservation of momentum is constructed by superposition. The force balance method has a minimum of free parameters compared to complex rheological descriptions that yield plate like behavior, and does not have the potential to artificially drive or hinder convection introduced by prescribing velocity boundary conditions. The mixing properties of the various methods are examined by comparison of embedded geochemical models for the isotopic evolution of Pb,U,Sm,Nd,Re,Os, and the noble gases. We find that the incorporation of strong plates leads to a mantle with increased stratification of heterogeneity. Sequestration of old oceanic crust in dense pools in the lowermost mantle is observed. However, the size and longevity of these dense pools decline considerably as realistic convective vigor is approached. Parameter space analysis is used to quantify this variability within the selection of models that reproduce Earth-like heat flow and plate velocities, and for comparison with the work of other authors. The residence time of old crust in pools and other areas of the mantle is examined with respect to the constraints imposed by isotope ratios observed in oceanic basalts. [1] Gable, C.W., R.J. O'Connell, B.J. Travis (1991) "Convection in 3 dimensions with surface plates; generation of a toroidal flow," J. Geophys. Res., 89, 8391--8405

Lipid Correction for Carbon Stable Isotope Analysis of Deep-sea Fishes

EPA Science Inventory

Lipid extraction is used prior to stable isotope analysis of fish tissues to remove variability in the carbon stable isotope ratio (d13C) caused by varying lipid content among samples. Our objective was to evaluate an application of a mass balance correction for the effect of lip...

Stable isotopes in juvenile marine fishes and their invertebrate prey from the Thames Estuary, UK, and adjacent coastal regions

NASA Astrophysics Data System (ADS)

Leakey, Chris D. B.; Attrill, Martin J.; Jennings, Simon; Fitzsimons, Mark F.

2008-04-01

Estuaries are regarded as valuable nursery habitats for many commercially important marine fishes, potentially providing a thermal resource, refuge from predators and a source of abundant prey. Stable isotope analysis may be used to assess relative resource use from isotopically distinct sources. This study comprised two major components: (1) development of a spatial map and discriminant function model of stable isotope variation in selected invertebrate groups inhabiting the Thames Estuary and adjacent coastal regions; and (2) analysis of stable isotope signatures of juvenile bass ( Dicentrarchus labrax), sole ( Solea solea) and whiting ( Merlangius merlangus) for assessment of resource use and feeding strategies. The data were also used to consider anthropogenic enrichment of the estuary and potential energetic benefits of feeding in estuarine nursery habitat. Analysis of carbon (δ 13C), nitrogen (δ 15N) and sulphur (δ 34S) isotope data identified significant differences in the 'baseline' isotopic signatures between estuarine and coastal invertebrates, and discriminant function analysis allowed samples to be re-classified to estuarine and coastal regions with 98.8% accuracy. Using invertebrate signatures as source indicators, stable isotope data classified juvenile fishes to the region in which they fed. Feeding signals appear to reflect physiological (freshwater tolerance) and functional (mobility) differences between species. Juvenile sole were found to exist as two isotopically-discrete sub-populations, with no evidence of mixing between the two. An apparent energetic benefit of estuarine feeding was only found for sole.

Escape and fractionation of volatiles and noble gases from Mars-sized planetary embryos and growing protoplanets

NASA Astrophysics Data System (ADS)

Odert, P.; Lammer, H.; Erkaev, N. V.; Nikolaou, A.; Lichtenegger, H. I. M.; Johnstone, C. P.; Kislyakova, K. G.; Leitzinger, M.; Tosi, N.

2018-06-01

Planetary embryos form protoplanets via mutual collisions, which can lead to the development of magma oceans. During their solidification, significant amounts of the mantles' volatile contents may be outgassed. The resulting H2O/CO2 dominated steam atmospheres may be lost efficiently via hydrodynamic escape due to the low gravity of these Moon- to Mars-sized objects and the high stellar EUV luminosities of the young host stars. Protoplanets forming from such degassed building blocks after nebula dissipation could therefore be drier than previously expected. We model the outgassing and subsequent hydrodynamic escape of steam atmospheres from such embryos. The efficient outflow of H drags along heavier species like O, CO2, and noble gases. The full range of possible EUV evolution tracks of a young solar-mass star is taken into account to investigate the atmospheric escape from Mars-sized planetary embryos at different orbital distances. The estimated envelopes are typically lost within a few to a few tens of Myr. Furthermore, we study the influence on protoplanetary evolution, exemplified by Venus. In particular, we investigate different early evolution scenarios and constrain realistic cases by comparing modeled noble gas isotope ratios with present observations. Isotope ratios of Ne and Ar can be reproduced, starting from solar values, under hydrodynamic escape conditions. Solutions can be found for different solar EUV histories, as well as assumptions about the initial atmosphere, assuming either a pure steam atmosphere or a mixture with accreted hydrogen from the protoplanetary nebula. Our results generally favor an early accretion scenario with a small amount of residual hydrogen from the protoplanetary nebula and a low-activity Sun, because in other cases too much CO2 is lost during evolution, which is inconsistent with Venus' present atmosphere. Important issues are likely the time at which the initial steam atmosphere is outgassed and/or the amount of CO2 which may still be delivered at later evolutionary stages. A late accretion scenario can only reproduce present isotope ratios for a highly active young Sun, but then unrealistically massive steam atmospheres (few kbar) would be required.

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.

Osmium Isotopic Composition of the Sumbar Cretaceous- Tertiary Boundary, Turkmenia

NASA Astrophysics Data System (ADS)

Meisel, T.; Krahenbuhl, U.; Nazarov, M. A.

1992-07-01

Turekian (1982) propagated the use of the osmium isotopic composition as a cosmic indicator for the origin of the high osmium (and iridium) layers at the K/T boundaries. He did not consider the osmium isotopic signature of the terrestrial mantle, which also has a chondritic evolution of the Re-Os system. Osmium cannot serve alone as an infallible indicator of the impact theory, but interesting results can be obtained from their investigation. Different K/T boundary section have been analyzed so far for ^187Os/^186Os. An overview of the values is presented in the table. Boundary Clay layer Os ratio Reference Stevns Klint fish clay 1.66 Luck and Turekian, 1983 Woodside Creek 1.12 Lichte et al., 1986 Raton Basin 1.23 Kraehenbuehl et al., 1988 Raton Basin (several) 1.15-1.23 Esser and Turekian, 1989 Sumbar (0-1 cm) 1.16 This work We obtained a complete marine section of the K/T boundary in southern Turkmenia (decribed by Alekseyev, 1988). It shows a very high Ir concentration (66 ppb) at the boundary layer and a remarkable Ir enrichment over crustal rocks continuing up to 30 cm above the boundary. Our aim of this investigation is to analyze several samples from above and below the boundary for the ^187Os/^186Os ratio to obtain a complete picture of the isotopic evolution of the section. We want to evaluate mixing of Os with chondritic ratios with Os from upper crustal rocks. Another goal is to investigate a mobilization of Os. So far only one sample has been analyzed with NTI-MS after fire assay digestion of the sample. The sample 0 to 1 cm has an ^187Os/^186Os ratio of 1.162 +- 13, which is quite low. We expect an even lower value for the boundary clay (0 cm) itself not taking into account a contribution of radiogenic osmium from the decay of terrestrial rhenium. This might put this K/T boundary section closest of all to the present day chondritic value (approx. 1.05). Further analysis will be presented at the meeting. References Alekseyev A. S., Nazarov M. A., Barsukova L. D., Koselov G. M., Nizhegorodova I. V. and Amanniyazov K. N. (1988) The Cretaceous- Paleogene boundary in southern Turkmenia and its geochemical characteristics. Int. Geol. Rev. 30, 121-135. Esser B. K. and Turekian K. K. (1989) Osmium isotopic composition of the Raton Basin Cretaceous-Tertiary boundary interval. 70, 717. Kraehenbuehl U., Geissbuehler M., Buehler F. and Eberhardt P. (1988) The measurement of osmium isotopes in samples from a Cretaceous/Tertiary (K/T) section of the Raton Basin, USA. Meteoritics 23, 282. Lichte F. E., Wilson S. M., Brooks R. R., Reeves R. D., Holzbecher J. and Ryan D. E. (1986) New method for the measurement of osmium isotopes applied to a New Zealand Cretaceous/Tertiary boundary shale. Nature 322, 816-817. Luck J. M. and Turekian K. K. (1983) Osmium-^187/Osmium-^186 in manganese nodules and the Cretaceous-Tertiary boundary. Science 222, 613- 615. Turekian K. K. (1982) Potential of ^187Os/^186Os as a cosmic versus terrestrial indicator in high iridium layers of sedimentary strata. Geol. Bull. Am. Spec. Pap. 190, 243-249.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

2018-04-20

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

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

2018-04-20

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

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

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

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

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

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

Development of high through-put Sr isotope analysis for monitoring reservoir integrity for CO{sub 2} storage.

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

Wall, Andy; Jain, Jinesh; Stewart, Brian

2012-01-01

Recent innovations in multi-collector ICP-mass spectrometry (MC-ICP-MS) have allowed for rapid and precise measurements of isotope ratios in geological samples. Naturally occurring Sr isotopes has the potential for use in Monitoring, Verification, and Accounting (MVA) associated with geologic CO2 storage. Sr isotopes can be useful for: Sensitive tracking of brine migration; Determining seal rock leakage; Studying fluid/rock reactions. We have optimized separation chemistry procedures that will allow operators to prepare samples for Sr isotope analysis off site using rapid, low cost methods.

Optical spectroscopy of laser-produced plasmas for standoff isotopic analysis

DOE PAGES

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

2018-06-01

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

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

USGS Publications Warehouse

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

2015-01-01

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

CNO isotopes in red giant stars

NASA Technical Reports Server (NTRS)

Wannier, P. G.

1985-01-01

The production and distribution of the CNO nuclides is discussed in light of observed abundance ratios in red giants and in the interstellar medium. Isotope abundances have been measured in the atmospheres and in the recent ejecta of cool giants, including carbon stars, S-type stars and red supergiants as well as in oxygen-rich giants making their first ascent of the giant branch. Several of the observations suggest revision of currently accepted nuclear cross-sections and of the mixing processes operating in giant envelopes. By comparing red giant abundances with high-quality observations of the interstellar medium, conclusions are reached about the contribution of intermediate-mass stars to galactic nuclear evolution. The three oxygen isotopes, O-16, -17 and -18, are particularly valuable for such comparison because they reflect three different stages of stellar nucleosynthesis. One remarkable result comes from observations of O-17/O-18 in several classes of red giant stars. The observed range of values for red giants excludes the entire range of values seen in interstellar molecular clouds. Furthermore, both the observations of stars and interstellar clouds exclude the isotopic ratio found in the solar system.

The energy dependence of the neon-22 excess in the cosmic radiation

NASA Technical Reports Server (NTRS)

Herrstroem, N. Y.; Lund, N.

1985-01-01

It has been recognized now for some time that the heavy neon isotope, neon-22, is overabundant by a factor of 3 to 4 with respect to neon-22 in the cosmic ray source compared to the ratio of these isotopes in the Solar System. In view of the otherwise remarkable similarity of the chemical composition of the cosmic ray source and the composition of the Solar Energetic Particles, the anomaly regarding the neon isotopes is so much more striking. The observed excess of neon-22 is too large to be explained as a result of the chemical evolution of the Galaxy since the formation of the Solar System. Further information on the origin of the neon-22 excess may come from a comparison of the energy spectra of the two neon isotopes. If the cosmic radiation in the solar neighborhood is a mixture of material from several sources, one of which has an excess of neon-22, then the source energy spectra of neon-20 and neon-22 may differ significantly.

Riverine dissolved lithium isotopic signatures in low-relief central Africa and their link to weathering regimes

NASA Astrophysics Data System (ADS)

Henchiri, Soufian; Gaillardet, Jérôme; Dellinger, Mathieu; Bouchez, Julien; Spencer, Robert G. M.

2016-05-01

The isotopic composition of dissolved lithium (δ7Li) near the Congo River mouth varied from 14‰ to 22‰ in 2010 and was negatively correlated to discharge. From the relationship between dissolved δ7Li and strontium isotopes, we suggest that this large variation is due to mixing of waters from two contrasting continental weathering regimes. One end-member (high δ7Li ≈ 25‰) represents waters sourced from active lateritic soils covering the periphery of the basin (Li highly sequestered into secondary mineral products) and another representing blackwater rivers (low δ7Li ≈ 5.7‰) derived from the swampy central depression where high organic matter content in water leads to congruent dissolution of the Tertiary sedimentary bedrock. This suggests that the lithium isotopic signature of tropical low-relief surfaces is not unique and traces the long-term, large-scale vertical motions of the continental crust that control geomorphological settings. This evolution should be recorded in the oceanic secular δ7Li curve.

THE NITROGEN ISOTOPIC COMPOSITION OF METEORITIC HCN

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

Pizzarello, Sandra, E-mail: pizzar@asu.edu

2014-12-01

HCN is ubiquitous in extraterrestrial environments and is central to current theories on the origin of early solar system organic compounds such as amino acids. These compounds, observed in carbonaceous meteorites, were likely important in the origin and/or evolution of early life. As part of our attempts to understand the origin(s) of meteoritic CN{sup –}, we have analyzed the {sup 15}N/{sup 14}N isotopic composition of HCN gas released from water extracts of the Murchison meteorite and found its value to be near those of the terrestrial atmosphere. The findings, when evaluated viz-a-viz molecular abundances and isotopic data of meteoritic organicmore » compounds, suggest that HCN formation could have occurred during the protracted water alteration processes known to have affected the mineralogy of many asteroidal bodies during their solar residence. This was an active synthetic stage, which likely involved simple gasses, organic molecules, their presolar precursors, as well as mineral catalysts and would have lead to the formation of molecules of differing isotopic composition, including some with solar values.« less

Impact Histories of Vesta and Vestoids inferred from Howardites, Eucrites, and Diogenites

NASA Technical Reports Server (NTRS)

Scott, E. R. D.; Bogard, D. D.; Bottke, W. F.; Taylor, G. J.; Greenwood, R. C.; Franchi, I. A.; Keil, K.; Moskovitz, N. A.; Nesvorny, D.

2009-01-01

The parent body of the howardites, eucrites and diogenites (HEDs) is thought to be asteroid (4) Vesta [1]. However, several eucrites have now been recognized, like NWA 011 and Ibitira, with major element compositions and mineralogy like normal eucrites but with different oxygen isotope compositions and minor element concentrations suggesting they are not from the same body [2, 3]. The discoveries of abnormal eucrites and V-type asteroids that are probably not from Vesta [see 4] raise the question whether the HEDs with normal oxygen isotopes are coming from Vesta [3]. To address this issue and understand more about the evolution of Vesta in preparation for the arrival of the Dawn spacecraft, we integrate fresh insights from Ar-Ar dating and oxygen isotope analyses of HEDs, radiometric dating of differentiated meteorites, as well as dynamical and astronomical studies of Vesta, the Vesta asteroid family (i.e., the Vestoids), and other V-type asteroids.

Isotope Fractionation by Diffusion in Liquids (Final Technical Report)

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

Richter, Frank

The overall objective of the DOE-funded research by grant DE-FG02-01ER15254 was document and quantify kinetic isotope fractionations during chemical and thermal (i.e., Soret) diffusion in liquids (silicate melts and water) and in the later years to include alloys and major minerals such as olivine and pyroxene. The research involved both laboratory experiments and applications to natural settings. The key idea is that major element zoning on natural geologic materials is common and can arise for either changes in melt composition during cooling and crystallization or from diffusion. The isotope effects associated with diffusion that we have documented are the keymore » for determining whether or not the zoning observed in a natural system was the result of diffusion. Only in those cases were the zoning is demonstrably due to diffusion can use independently measured rates of diffusion to constrain the thermal evolution of the system.« less

Lithospheric Contributions to Arc Magmatism: Isotope Variations Along Strike in Volcanoes of Honshu, Japan

PubMed

Kersting; Arculus; Gust

1996-06-07

Major chemical exchange between the crust and mantle occurs in subduction zone environments, profoundly affecting the chemical evolution of Earth. The relative contributions of the subducting slab, mantle wedge, and arc lithosphere to the generation of island arc magmas, and ultimately new continental crust, are controversial. Isotopic data for lavas from a transect of volcanoes in a single arc segment of northern Honshu, Japan, have distinct variations coincident with changes in crustal lithology. These data imply that the relatively thin crustal lithosphere is an active geochemical filter for all traversing magmas and is responsible for significant modification of primary mantle melts.

Nuclear Astrophysics at DANCE

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

Reifarth, R.; Bredeweg, T.A.; Esch, E.-I.

2005-05-24

One of the most interesting nuclear physics challenges is obtaining a detailed understanding of the nucleosynthesis processes of the elements. Knowledge about the stellar sites, and how they are governed by stellar evolution and cosmology are crucial in understanding the overall picture. Information on reaction rates for neutron- and charged-particle-induced reactions have a direct impact on existing stellar models. Except for the stable isotopes, very few neutron-induced reactions in the energy range of interest have been measured to date. DANCE measurements on stable and unstable isotopes will provide many of the missing key reactions that are needed to understand themore » nucleosynthesis of the heavy elements.« less

Lifetime Measurements in Neutron-Rich Xe Isotopes — Evolution of Quadrupole Collectivity Beyond 132Sn

NASA Astrophysics Data System (ADS)

Ilieva, S.; Bönig, S.; Hartig, A.-L.; Henrich, C.; Ignatov, A.; Kröll, Th.; Thürauf, M.; Jolie, J.; Régis, J.-M.; Saed-Samii, N.; Blanc, A.; de France, G.; Jentschel, M.; Köster, U.; Mutti, P.; Simpson, G. S.; Soldner, T.; Urban, W.; Mǎrginean, N.; Ur, C. A.; Mach, H.; Fraile, L. M.; Paziy, V.; Regan, P. H.; Bruce, A. M.; Lalkovski, S.; Korten, W.

Picosecond lifetimes of excited states in neutron-rich Xe isotopes were measured at the Institut Laue-Langevin via γ-ray spectroscopy of fission fragments from neutron-induced fission of 235U and 241Pu targets. The data collected with the recently installed fast timing array FATIMA in combination with the EXOGAM Ge array were analysed using the new generalized centroid difference method. Our aim is to study the quadrupole and octupole collectivity, arising in the mass region beyond the doubly magic 132Sn, by means of transition probabilities. These can be calculated from the directly measured lifetimes.

Preparative separation of underivatized amino acids for compound-specific stable isotope analysis and radiocarbon dating of hydrolyzed bone collagen.

PubMed

Tripp, Jennifer A; McCullagh, James S O; Hedges, Robert E M

2006-01-01

Analysis of stable and radioactive isotopes from bone collagen provides useful information to archaeologists about the origin and age of bone artifacts. Isolation and analysis of single amino acids from the proteins can provide additional and more accurate information by removing contamination and separating a bulk isotope signal into its constituent parts. In this paper, we report a new method for the separation and isolation of underivatized amino acids from bone collagen, and their analysis by isotope ratio MS and accelerator MS. RP chromatography is used to separate the amino acids with nonpolar side chains, followed by an ion pair separation to isolate the remaining amino acids. The method produces single amino acids with little or no contamination from the separation process and allows for the measurement of accurate stable isotope ratios and pure samples for radiocarbon dating.

Soil-geomorphology relationships and landscape evolution in a southwestern Atlantic tidal salt marsh in Patagonia, Argentina

NASA Astrophysics Data System (ADS)

Ríos, Ileana; Bouza, Pablo José; Bortolus, Alejandro; Alvarez, María del Pilar

2018-07-01

Salt marshes in Patagonia ecosystem are nowadays fully recognized by ecological, pollution and phytoremediation studies but a soil genesis and geomorphology approach is currently unknown. The aim of this study was to establish the soil-geomorphology relationship in Fracasso salt marsh and to determine the successional vegetation dynamics associated with the landscape evolution. This work was carried out in Fracasso salt marsh sited in Península Valdés, Argentina, where an integrated study on soil-geomorphology relationship and landscape evolution was performed along with sedimentological analysis and vegetation changes (C3 photosynthesis pathway vs. C4 photosynthesis pathway plants). This last was determined through the δ13C composition from soil organic matter (SOM). Soil descriptions and laboratory analysis of soil samples were performed. A marked relationship between the vegetation unit, the dominant landform and the type of associated soil was found. Limonium brasiliense (Lb) and Sarcocornia perennis (Sp), both C3 plants, are dominant in levees associated with tidal creeks, and soils were classified as Typic Fluvaquents, while Spartina alterniflora (Sa) soils were classified as Sodic Endoaquents and Sodic Psammaquents. Although no sulfidic materials were identified by incubation test, they were identified by hydrogen peroxide treatment in Sa soils, and now are considered potential acid sulfate soils (PASS). Sedimentological analysis from deepest sandy C horizons indicates a beach depositional environment. On the other hand, the δ13C stable isotope composition of SOM preserved into these buried soil acting as parent materials shows the dominance of C4 plants presumably belonging to Spartina species, suggesting a possible colonization and stabilization as the pioneer salt marsh.

System and method for high precision isotope ratio destructive analysis

DOEpatents

Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

2013-07-02

A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

High-Precision Measurement of 13C/12C Isotopic Ratio Using Gas Chromatography-Combustion-Cavity Ring-Down Spectroscopy

NASA Astrophysics Data System (ADS)

Saad, N.; Kuramoto, D. S.; Haase, C.; Crosson, E.; Tan, S.; Zare, R. N.

2009-12-01

Light stable isotope analysis, and in particular, compound specific isotopic analysis (CSIA), is a valuable tool to elucidate pathways and provide a better insight into biological, ecological, and geological systems. We present here the results of compound-specific isotopic carbon analysis of short chain hydrocarbons using the world’s first combination of gas chromatography, combustion interface, and cavity ring-down spectroscopy (GC-C-CRDS). Cavity ring-down spectroscopy (CRDS) is a highly sensitive optical spectroscopy, one application of which is to measure the stable isotopic ratios in small molecules. Because it uses a highly reflective optical cavity with many kilometers effective path length, CRDS provides some of the most sensitive and precise optical absorption measurements. Most optical spectroscopy isotopic analysis measures the quantities of each isotopologue independently using their distinct ro-vibrational spectra. The most common isotopes measured with optical spectroscopy are 13C and 12C in carbon dioxide. However, the isotopes of hydrogen, oxygen, and sulfur have also been measured. Unlike isotope ratio mass spectrometry (IRMS), optical spectroscopy can distinguish among isobars, which have essentially identical m/z ratios. The combination of chemical separation, chemical conversion, and CRDS makes a nearly universal tool for isotopic analysis of mixtures. In addition, CRDS can tolerate a variety of compounds mixed with the target. For example, CRDS can measure carbon dioxide and its isotopic 13C/12C ratio in the presence of oxygen. Using the novel GC-C-CRDS system, we injected a 75-microliter mixture of approximately equal quantities of methane, ethane, and propane into a gas chromatograph using helium as carrier gas. The methane, ethane, and propane were separated in time by 100 to 200 seconds after the chromatograph. Oxygen gas was added, and the hydrocarbons were combusted in a catalytic combustor with platinum and nickel, held at 1150oC. The combusted products were combined with dry nitrogen gas to provide sufficient gas flow for the CRDS analyzer, which measured the 13C/12C isotopic ratio of the separated methane, ethane, and propane, obtaining a precision of 0.95 permil or better. The calibration accuracy was within 3 permil of the values determined using IRMS. The current CRDS-based system is less expensive, does not require highly trained personnel to operate, and is portable, compared with IRMS. We anticipate that advances in spectroscopic analysis will improve the precision and accuracy of the CRDS isotopic measurement, making it comparable with IRMS.

Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

PubMed

Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

2010-12-15

Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. Copyright © 2010 Elsevier B.V. All rights reserved.