Stable isotope views on ecosystem function: challenging or challenged?

PubMed Central

Resco, Víctor; Querejeta, José I.; Ogle, Kiona; Voltas, Jordi; Sebastià, Maria-Teresa; Serrano-Ortiz, Penélope; Linares, Juan C.; Moreno-Gutiérrez, Cristina; Herrero, Asier; Carreira, José A.; Torres-Cañabate, Patricia; Valladares, Fernando

2010-01-01

Stable isotopes and their potential for detecting various and complex ecosystem processes are attracting an increasing number of scientists. Progress is challenging, particularly under global change scenarios, but some established views have been challenged. The IX meeting of the Spanish Association of Terrestrial Ecology (AAET, Úbeda, 18–22 October 2009) hosted a symposium on the ecology of stable isotopes where the linear mixing model approach of partitioning sinks and sources of carbon and water fluxes within an ecosystem was challenged, and new applications of stable isotopes for the study of plant interactions were evaluated. Discussion was also centred on the need for networks that monitor ecological processes using stable isotopes and key ideas for fostering future research with isotopes. PMID:20015858

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.

High Precision Isotope Analyses Using Multi-Collector SIMS: Applications to Earth and Planetary Science.

NASA Astrophysics Data System (ADS)

Kita, N. T.; Ushikubo, T.; Valley, J. W.

2008-05-01

The CAMECA IMS-1280 large radius, multicollector ion microprobe at the Wisc-SIMS National Facility is capable of high accuracy and precision for in situ analysis of isotope ratios. With improved hardware stability and software capability, high precision isotope analyses are routinely performed, typically 5 min per spot. We have developed analytical protocols for stable isotope analyses of oxygen, carbon, Mg, Si and Sulfur using multi-collector Faraday Cups (MCFC) and achieved precision of 0.1-0.2 ‰ (1SD) from a typically 10μm spot analyses. A number of isotopically homogeneous mineral standards have been prepared and calibrated in order to certify the accuracy of analyses in the same level. When spatial resolution is critical, spot size is reduced down to sub- μm for δ 18O to obtain better than 0.5‰ (1SD) precision by using electron multiplier (EM) on multi-collection system. Multi-collection EM analysis is also applied at 10 ppm level to Li isotope ratios in zircon with precision better than 2‰ (1SD). A few applications will be presented. (1) Oxygen three isotope analyses of chondrules in ordinary chondrites revealed both mass dependent and mass independent oxygen isotope fractionations among chondrules as well as within individual chondrules. The results give constraints on the process of chondrule formation and origin of isotope reservoirs in the early solar system. (2) High precision 26Al-26Mg (half life of 0.73 Ma) chronology is applied to zoned melilite and anorthite from Ca, Al-rich inclusions (CAI) in Leoville meteorite, and a well-defined internal isochron is obtained. The results indicate the Al- Mg system was remained closed within 40ky of the crystallization of melilite and anorthite in this CAI. (3) Sub- μm spot analyses of δ18O in isotopically zoned zircon from high-grade metamorphism reveals a diffusion profile of ~6‰ over 2μm, indicating slow diffusion of oxygen in zircon. This result also implies that old Archean detrital zircons (> 4Ga) might preserve their primary oxygen isotopic records, which allows us to trace the geological processes of the early earth [1]. Lithium isotope analyses of pre- 4Ga zircon from Jack Hills show high Li abundance and low δ 7Li, indicating existence of highly weathered crustal material as early as 4.3Ga. In conclusion, these new techniques allow us to study small natural variations of stable isotopes at μm-scale that permit exciting and fundamental research where samples are small, precious, or zoned. [1] Page FZ et al. (2007) Am Min 92, 1772-1775.

Influence of methane addition on selenium isotope sensitivity and their spectral interferences.

PubMed

Floor, Geerke H; Millot, Romain; Iglesias, Mónica; Négrel, Philippe

2011-02-01

The measurements of stable selenium (Se) isotopic signatures by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) are very challenging, due to the presence of spectral interferences and the low abundance of Se in environmental samples. We systematically investigated the effect of methane addition on the signal of Se isotopes and their interferences. It is the first time that the effect of methane addition has been assessed for all Se isotopes and its potential interferences using hydride generator multi-collector inductively coupled plasma mass spectrometry (HG-MC-ICP-MS). Our results show that a small methane addition increases the sensitivity. However, the response differs between a hydride generator and a standard introduction system, which might be related to differences in the ionization processes. Both argon and hydrogen-based interferences, the most common spectral interferences on selenium isotopes in HG-MC-ICP-MS, decrease with increasing methane addition. Therefore, analyte-interference ratios and precision are improved. Methane addition has thus a high potential for the application to stable Se isotopes ratios by HG-MC-ICP-MS. Copyright © 2011 John Wiley & Sons, Ltd.

Evaluating Snowmelt Runoff Processes Using Stable Isotopes in a Permafrost Hillslope

NASA Astrophysics Data System (ADS)

Carey, S. K.

2004-05-01

Conceptual understanding of runoff generation in permafrost regions have been derived primarily from hydrometric information, with isotope and hydrochemical data having only limited application in delineating sources and pathways of water. Furthermore, when stable isotope data are used to infer runoff processes, it often provides conflicting results from hydrometric measurements. In a small subarctic alpine catchment within the Wolf Creek Research Basin, Yukon, Canada, experiments were conducted during the melt period of 2002 and 2003 to trace the stable isotopic signature (d18O) of meltwater from a melting snowpack into permafrost soils and laterally to the stream to identify runoff processes and evaluate sources of error for traditional hydrograph separation studies in snowmelt-dominated permafrost basins. Isotopic variability in the snowpack was recorded at 0.1 m depth intervals during the melt period and compared with the meltwater isotopic signature at the snowpack base collected in lysimeters. Throughout the melt period in both years, there was an isotopic enrichment of meltwater as the season progressed. A downslope transect of wells and piezometers were used to evaluate the influence of infiltrating meltwater and thawing ground on the subsurface d18O signature. As melt began, meltwater infiltrated the frozen porous organic layer, leading to liquid water saturation in the unsaturated pore spaces. Water sampled during this initial melt stage show soil water d18O mirroring that of the meltwater signal. As the melt season progressed, frozen soil began to melt, mixing enriched pre-melt soil water with meltwater. This mixing increased the overall value of d18O obtained from the soil, which gradually increased as thaw progressed. At the end of snowmelt, soil water had a d18O value similar to values from the previous fall, suggesting that much of the initial snowmelt water had been flushed from the hillslope. Results from the hillslope scale are compared with two-component hydrograph separations and sources of error are discussed.

Resonance ionization laser ion sources for on-line isotope separators (invited).

PubMed

Marsh, B A

2014-02-01

A Resonance Ionization Laser Ion Source (RILIS) is today considered an essential component of the majority of Isotope Separator On Line (ISOL) facilities; there are seven laser ion sources currently operational at ISOL facilities worldwide and several more are under development. The ionization mechanism is a highly element selective multi-step resonance photo-absorption process that requires a specifically tailored laser configuration for each chemical element. For some isotopes, isomer selective ionization may even be achieved by exploiting the differences in hyperfine structures of an atomic transition for different nuclear spin states. For many radioactive ion beam experiments, laser resonance ionization is the only means of achieving an acceptable level of beam purity without compromising isotope yield. Furthermore, by performing element selection at the location of the ion source, the propagation of unwanted radioactivity downstream of the target assembly is reduced. Whilst advances in laser technology have improved the performance and reliability of laser ion sources and broadened the range of suitable commercially available laser systems, many recent developments have focused rather on the laser/atom interaction region in the quest for increased selectivity and/or improved spectral resolution. Much of the progress in this area has been achieved by decoupling the laser ionization from competing ionization processes through the use of a laser/atom interaction region that is physically separated from the target chamber. A new application of gas catcher laser ion source technology promises to expand the capabilities of projectile fragmentation facilities through the conversion of otherwise discarded reaction fragments into high-purity low-energy ion beams. A summary of recent RILIS developments and the current status of laser ion sources worldwide is presented.

Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

NASA Astrophysics Data System (ADS)

Kritee, K.; Barkay, Tamar; Blum, Joel D.

2009-03-01

Controlling bioaccumulation of toxic monomethylmercury (MMHg) in aquatic food chains requires differentiation between biotic and abiotic pathways that lead to its production and degradation. Recent mercury (Hg) stable isotope measurements of natural samples suggest that Hg isotope ratios can be a powerful proxy for tracing dominant Hg transforming pathways in aquatic ecosystems. Specifically, it has been shown that photo-degradation of MMHg causes both mass dependent (MDF) and mass independent fractionation (MIF) of Hg isotopes. Because the extent of MDF and MIF observed in natural samples (e.g., fish, soil and sediments) can potentially be used to determine the relative importance of pathways leading to MMHg accumulation, it is important to determine the potential role of microbial pathways in contributing to the fractionation, especially MIF, observed in these samples. This study reports the extent of fractionation of Hg stable isotopes during degradation of MMHg to volatile elemental Hg and methane via the microbial Hg resistance ( mer) pathway in Escherichia coli carrying a mercury resistance ( mer) genetic system on a multi-copy plasmid. During experimental microbial degradation of MMHg, MMHg remaining in reactors became progressively heavier (increasing δ202Hg) with time and underwent mass dependent Rayleigh fractionation with a fractionation factor α202/198 = 1.0004 ± 0.0002 (2SD). However, MIF was not observed in any of the microbial MMHg degradation experiments indicating that the isotopic signature left by mer mediated MMHg degradation is significantly different from fractionation observed during DOC mediated photo-degradation of MMHg. Additionally, a clear suppression of Hg isotope fractionation, both during reduction of Hg(II) and degradation of MMHg, was observed when the cell densities increased, possibly due to a reduction in substrate bioavailability. We propose a multi-step framework for understanding the extent of fractionation seen in our MMHg degradation experiments and, based on estimates of the rates of the various steps involved in this mer mediated pathway, suggest which steps in the process could contribute towards the observed extent of fractionation. This framework suggests that at lower cell densities catalysis by MerB was the rate limiting step while at higher cell densities transport into the cell, which does not cause fractionation, became the rate limiting step. In addition to presenting evidence for absence of MIF during mer mediated Hg transformations, based on the nature of Hg compounds and microbe-Hg interactions, we suggest that the nuclear spin dependent MIF (i.e., the magnetic isotope effect) is also unlikely to occur during other non mer mediated 'dark' microbial Hg transformations (e.g., formation of MMHg and oxidative degradation of MMHg). Because of the important implications of the absence of MIF during biological processes on Hg isotope systematics, we discuss theoretical considerations and experimental strategies that could be used to confirm this suggestion.

Determining and quantifying specific sources of light alkane

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.

2015-12-01

Determining and quantifying specific sources of emission of methane (an important greenhouse gas) and light alkanes from abandoned gas and oil wells, hydraulic fracturing or associated with CO2 sequestration are a challenge in determining their contribution to the atmospheric greenhouse gas budget or to identify source of groundwater contamination. Here, we review organic biogeochemistry proprieties and isotopic fingerprinting of C1-C5 alkanes to address this problem. For instance, the concentration ratios of CH4 to C2-C5 alkanes can be used to distinguish between thermogenic and microbial generated CH4. Together C and H isotopes of CH4 are used to differentiate bacterial generated sources and thermogenic CH4 and may also identify processes such as alteration and source mixing. Carbon isotope ratios pattern of C1-C5 alkanes highlight sources and oxidation processes in the gas reservoirs. Stable carbon isotope measurements are a viable tool for monitoring the degradation progress of methane and light hydrocarbons. The carbon isotope ratios of the reactants and products are independent of the concentration and only depend on the relative progress of the particular reaction. Oxidation/degradation of light alkanes are typically associated with increasing ð13C values. Isotopic mass balances offer the possibility to independently determine the fractions coming from microbial versus thermogenic and would also permit differentiation of the isotope fractionations associated with degradation. Unlike conventional concentration measurements, this approach is constrained by the different isotopic signatures of various sources and sinks.

Present status of the KISS project

NASA Astrophysics Data System (ADS)

Miyatake, H.; Wada, M.; Watanabe, X. Y.; Hirayama, Y.; Schury, P.; Ahmed, M.; Ishiyama, H.; Jeong, S. C.; Kakiguchi, Y.; Kimura, S.; Moon, J. Y.; Mukai, M.; Oyaizu, M.; Park, J. H.

2018-04-01

KISS project aims at finding an astrophysical condition for synthesizing r-process heavy element isotopes, which are characterized as the third peak in the solar abundance pattern. This is an experimental challenge in nuclear physics to measure ground and isomeric state properties of unknown nuclei around the region of N=126 isotones. So far we have constructed and developed new type of mass separation system, KISS (KEK Isotope Separation System) and performed measurements of lifetimes and hyperfine structures of some platinum and iridium neutron-rich radioactive isotopes by applying multi-nucleon transfer reactions and in-gas laser ionization and spectroscopy (IGLIS) methods. In this report, recent physics results, updated KISS performance, and future's research plan including a challenge of a systematic mass measurement with MRTOF (Multi-Reflection Time-Of-Flight mass spectrograph) are presented.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Iron isotope behavior during fluid/rock interaction in K-feldspar alteration zone - A model for pyrite in gold deposits from the Jiaodong Peninsula, East China

NASA Astrophysics Data System (ADS)

Zhu, Zhi-Yong; Jiang, Shao-Yong; Mathur, Ryan; Cook, Nigel J.; Yang, Tao; Wang, Meng; Ma, Liang; Ciobanu, Cristiana L.

2018-02-01

Mechanisms for Fe isotope fractionation in hydrothermal mineral deposits and in zones of associated K-feldspar alteration remain poorly constrained. We have analyzed a suite of bulk samples consisting of granite displaying K-feldspar alteration, Precambrian metamorphic rocks, and pyrite from gold deposits of the Jiaodong Peninsula, East China, by multi-collector inductively-coupled plasma mass spectrometry. Pyrites from disseminated (J-type) ores show a δ56Fe variation from +0.01 to +0.64‰, overlapping with the signature of the host granites (+0.08 to +0.39‰). In contrast, pyrites from quartz veins (L-type ores) show a wide range of Fe-isotopic composition from -0.78 to +0.79‰. Negative values are never seen in the J-type pyrites. The Fe isotope signature of the host granite with K-feldspar alteration is significantly heavier than that of the bulk silicate Earth. The Fe isotopic compositions of Precambrian metamorphic rocks across the district display a narrow range between -0.16‰ and +0.19‰, which is similar to most terrestrial rocks. Concentrations of major and trace elements in bulk samples were also determined, so as to evaluate any correlation between Fe isotope composition and degree of alteration. We note that during progressive K-feldspar alteration to rocks containing >70 wt% SiO2, >75 ppm Rb, and <1.2 wt% total Fe2O3, the Fe isotope composition of the granite changes systematically. The Fe isotope signature becomes heavier as the degree of alteration increases. The extremely light Fe isotopic compositions in L-type gold deposits may be explained by Rayleigh fractionation during pyrite precipitation in an open fracture system. We note that the sulfur isotopic compositions of pyrite in the two types of ores are also different. Pyrite from J-type ores has a systematically 3.5‰-higher δ34S value (11.2‰) than those of pyrite from the L-type ores (7.7‰). There is, however, no correlation between Fe and S isotope signatures. The isotopic fractionation of sulfur is used to constrain a change in the fO2 of the hydrothermal fluids from which pyrite precipitated. This work demonstrates that the Fe isotope composition of pyrite displays a significant response to the process of pyrite precipitation in hydrothermal systems, and that systematic fractionation of iron isotopes occurs during fluid/rock reaction in the K-feldspar alteration zone of the Linglong granite. The implications of the results are that processes of mineralization and associated fluid-rock interaction, which are ubiquitously observed in porphyry-style Cu-Au-Mo and other hydrothermal deposits, may be readily traceable using Fe isotopes.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Nuclear and non-nuclear techniques for area-wide assessment of water use efficiency and ecohydrology outcomes among mixed land uses

NASA Astrophysics Data System (ADS)

Burgess, S. S. O.; Nguyen, M. L.

2009-04-01

Managing water use efficiency and ecohydrology is important for providing food, water and essential ecosystem services. Many agricultural, ecological, atmospheric and hydrological processes cannot be meaningfully managed without an area-wide or catchment-level perspective. However a vast number of factors, including mixed land uses are incorporated at such scales. There is a need for integrative, mobile and adaptable techniques to make water related measurements over large areas and mixed land uses. Nuclear techniques and analogous non-nuclear techniques may be deployed in a number of spheres within the soil-plant-atmosphere continuum (e.g. rhizosphere and above-canopy microclimate) with nuclear techniques having a distinct contribution owing to their unique ability to trace biogeochemical processes including the movement and transformation of water, nutrients and agrochemicals. 1) Soils. Isotopes can be used to trace water sources to understand groundwater dependence, rooting depth, etc. but not at all sites: early success in central USA studies has not always been repeatable in climates which produce more uniform isotopic signatures in various water sources. Soil water resources available to crops can also be studied using neutron moisture meters, but training, transport and safety issues argue for stringent management and inclusion of electrical capacitance probes for routine or automated applications. Results from capacitance probes can benefit from benchmarking against neutron probe measurements, which remain more powerful for sampling larger volumes in cases of heterogenous soils or where salinity levels are problematic. Because interpretation of soil water content in terms of plant available water also requires knowledge of soil organic matter characteristics, 13C and compound specific stable isotopes can help to identify changes in soil organic matter composition and hence water and plant nutrient availability. 2) Plants. Analysis of carbon isotope discrimination can be used to monitor water use efficiency and seasonal water stress. This includes analysis of carbon in structural leaf material and soluble sugars for different temporal scales. Some progress is also being made using 18O signatures to estimate transpiration. Furthermore xylem sap can be measured for isotopic composition can be used and absolute flow rates in the plant can be measured with thermometric tracers. Information on transpiration can help differentiate between wasteful evaporative processes versus efficient plant gas exchange. 3) Atmosphere (above & within canopy). Whilst traditional vapour related techniques such as Bowen ratio and eddy flux can measure total ET, modern cavity ring-down laser spectrometers can sample isotopes in water vapour. These devices hold much promise to identify water sources and evaporative processes using dual isotope mixing models and Keeling plots analysis: the result is improved partitioning of transpiration and evaporation. This above suite of measurements can provide knowledge to choose correct plant species, manage irrigation and microclimate, compare land uses and predict impacts on the environment, including nutrient and agrochemical movement in the landscape. We discuss current progress in IAEA and related projects which are aimed at bringing an integrated, multi-disciplinary framework for area-wide water management that can promote food security, water resources and essential ecosystem services.

Coupling meteorology, metal concentrations, and Pb isotopes for source attribution in archived precipitation samples.

PubMed

Graney, Joseph R; Landis, Matthew S

2013-03-15

A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16month period (July 1994-October 1995) at Bondville were parsed into six unique meteorological flow regimes using a minimum variance clustering technique on back trajectory endpoints. Pb isotope ratios and multi-element concentrations were measured using high resolution inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) on the archived precipitation samples. Bondville is located in central Illinois, ~250km downwind from smelters in southeast Missouri. The Mississippi Valley Type ore deposits in Missouri provided a unique multi-element and Pb isotope fingerprint for smelter emissions which could be contrasted to industrial emissions from the Chicago and Indianapolis urban areas (~125km north and east, of Bondville respectively) and regional emissions from electric utility facilities. Differences in Pb isotopes and element concentrations in precipitation corresponded to flow regime. Industrial sources from urban areas, and thorogenic Pb from coal use, could be differentiated from smelter emissions from Missouri by coupling Pb isotopes with variations in element ratios and relative mass factors. Using a three endmember mixing model based on Pb isotope ratio differences, industrial processes in urban airsheds contributed 56±19%, smelters in southeast Missouri 26±13%, and coal combustion 18±7%, of the Pb in precipitation collected in Bondville in the mid-1990s. Copyright © 2012 Elsevier B.V. All rights reserved.

Hydrogeological and multi-isotopic approach to define nitrate pollution and denitrification processes in a coastal aquifer (Sardinia, Italy)

NASA Astrophysics Data System (ADS)

Pittalis, Daniele; Carrey, Raul; Da Pelo, Stefania; Carletti, Alberto; Biddau, Riccardo; Cidu, Rosa; Celico, Fulvio; Soler, Albert; Ghiglieri, Giorgio

2018-02-01

Agricultural coastal areas are frequently affected by the superimposition of various processes, with a combination of anthropogenic and natural sources, which degrade groundwater quality. In the coastal multi-aquifer system of Arborea (Italy)—a reclaimed morass area identified as a nitrate vulnerable zone, according to Nitrate Directive 91/676/EEC—intensive agricultural and livestock activities contribute to substantial nitrate contamination. For this reason, the area can be considered a bench test for tuning an appropriate methodology aiming to trace the nitrate contamination in different conditions. An approach combining environmental isotopes, water quality and hydrogeological indicators was therefore used to understand the origins and attenuation mechanisms of nitrate pollution and to define the relationship between contaminant and groundwater flow dynamics through the multi-aquifer characterized by sandy (SHU), alluvial (AHU), and volcanic hydrogeological (VHU) units. Various groundwater chemical pathways were consistent with both different nitrogen sources and groundwater dynamics. Isotope composition suggests a mixed source for nitrate (organic and synthetic fertilizer), especially for the AHU and SHU groundwater. Moreover, marked heterotrophic denitrification and sulfate reduction processes were detected; although, for the contamination related to synthetic fertilizer, the attenuation was inefficient at removing NO3 - to less than the human consumption threshold of 50 mg/L. Various factors contributed to control the distribution of the redox processes, such as the availability of carbon sources (organic fertilizer and the presence of lagoon-deposited aquitards), well depth, and groundwater flow paths. The characterization of these processes supports water-resource management plans, future actions, and regulations, particularly in nitrate vulnerable zones.

The role of stable isotopes in understanding rainfall ...

EPA Pesticide Factsheets

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interception. As a whole, the studies suggest a set of controlling factors including fractionation, exchange among liquid and vapor phase water, and spatiotemporal redistribution along varying canopy flowpaths. However, our limited understanding of physical processes and water routing in the canopy limits the ability to discern all details for predicting interception isotope effects. We suggest that the isotopic composition of throughfall and stemflow may be the key to improve our understanding of water storage and transport in the canopy, similar to how isotopic analysis contributed to progress in our understanding of watershed runoff processes. While interception isotope effects have largely been studied under the premise that they are a source of error, previous works also indicate a wide range of possible interactions that intercepted water may have with the canopy and airspace. We identify new research questions that may be answered by stable isotopes as a path forward in examining and generalizing small-scale interception processes that could facilitate integration of interception into watershed ecohydrological concepts. Evaporation from forest canopies (interception loss) is a prominent

Multi-isotope tracers to investigate processes in the Elbe, Weser and Ems river catchment using B, Mo, Sr, and Pb isotope ratios assessed by MC ICP-MS

NASA Astrophysics Data System (ADS)

Irrgeher, Johanna; Reese, Anna; Zimmermann, Tristan; Prohaska, Thomas; Retzmann, Anika; Wieser, Michael E.; Zitek, Andreas; Proefrock, Daniel

2017-04-01

Environmental monitoring of complex ecosystems requires reliable sensitive techniques based on sound analytical strategies to identify the source, fate and sink of elements and matter. Isotopic signatures can serve to trace pathways by making use of specific isotopic fingermarks or to distinguish between natural and anthropogenic sources. The presented work shows the potential of using the isotopic variation of Sr, Pb (as well-established isotopic systems), Mo and B (as novel isotopic system) assessed by MC ICP-MS in water and sediment samples to study aquatic ecosystem transport processes. The isotopic variation of Sr, Pb, Mo and B was determined in different marine and estuarine compartments covering the catchment of the German Wadden Sea and its main tributaries, the Elbe, Weser and Ems River. The varying elemental concentrations, the complex matrix and the expected small variations in the isotopic composition required the development and application of reliable analytical measurement approaches as well as suited metrological data evaluation strategies. Aquatic isoscapes were created using ArcGIS® by relating spatial isotopic data with geographical and geological maps. The elemental and isotopic distribution maps show large variation for different parameters and also reflect the numerous impact factors (e.g. geology, anthropogenic sources) influencing the catchment area.

Reactive transport modeling of stable carbon isotope fractionation in a multi-phase multi-component system during carbon sequestration

DOE PAGES

Zhang, Shuo; DePaolo, Donald J.; Zheng, Liange; ...

2014-12-31

Carbon stable isotopes can be used in characterization and monitoring of CO 2 sequestration sites to track the migration of the CO 2 plume and identify leakage sources, and to evaluate the chemical reactions that take place in the CO 2-water-rock system. However, there are few tools available to incorporate stable isotope information into flow and transport codes used for CO 2 sequestration problems. We present a numerical tool for modeling the transport of stable carbon isotopes in multiphase reactive systems relevant to geologic carbon sequestration. The code is an extension of the reactive transport code TOUGHREACT. The transport modulemore » of TOUGHREACT was modified to include separate isotopic species of CO 2 gas and dissolved inorganic carbon (CO 2, CO 3 2-, HCO 3 -,…). Any process of transport or reaction influencing a given carbon species also influences its isotopic ratio. Isotopic fractionation is thus fully integrated within the dynamic system. The chemical module and database have been expanded to include isotopic exchange and fractionation between the carbon species in both gas and aqueous phases. The performance of the code is verified by modeling ideal systems and comparing with theoretical results. Efforts are also made to fit field data from the Pembina CO 2 injection project in Canada. We show that the exchange of carbon isotopes between dissolved and gaseous carbon species combined with fluid flow and transport, produce isotopic effects that are significantly different from simple two-component mixing. These effects are important for understanding the isotopic variations observed in field demonstrations.« less

A status of progress for the Laser Isotope Separation (LIS) process

NASA Technical Reports Server (NTRS)

Delionback, L. M.

1976-01-01

An overview of the Laser Isotope Separation (LIS) methodology is given together with illustrations showing a simplified version of the LIS technique, an example of the two-photon photoionization category, and a diagram depicting how the energy levels of various isotope influence the LIS process. Applications were proposed for the LIS system which, in addition to enriching uranium, could in themselves develop into programs of tremendous scope and breadth. These include the treatment of radioactive wastes from light-water nuclear reactors, enriching the deuterium isotope to make heavy-water, and enriching the light isotopes of such elements as titanium for aerospace weight-reducing programs. Economic comparisons of the LIS methodology with the current method of gaseous diffusion indicate an overwhelming advantage; the laser process promises to be 1000 times more efficient. The technique could also be utilized in chemical reactions with the tuned laser serving as a universal catalyst to determine the speed and direction of a chemical reaction.

Development of Optical Crystals for High Power and Tunable Visible and Infrared Light Generation

DTIC Science & Technology

2015-02-11

ultra high chemical purity (5N), 95% isotopically enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by...enriched 6Li was purified in a multi-stage vacuum distillation process previously reported by Stowe et al.[4]. 6LiIn alloy was synthesized in a... quantum mechanics, it has been determined that atoms, molecules, ions have discrete energy levels. Therefore there exists allowed atomic transitions

Sedimentary organic molecules: Origins and information content

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Multi-element compound specific stable isotope analysis of chlorinated aliphatic contaminants derived from chlorinated pitches.

PubMed

Filippini, Maria; Nijenhuis, Ivonne; Kümmel, Steffen; Chiarini, Veronica; Crosta, Giovanni; Richnow, Hans H; Gargini, Alessandro

2018-05-30

Tetrachloroethene and trichloroethene are typical by-products of the industrial production of chloromethanes. These by-products are known as "chlorinated pitches" and were often dumped in un-contained waste disposal sites causing groundwater contaminations. Previous research showed that a strongly depleted stable carbon isotope signature characterizes chlorinated compounds associated with chlorinated pitches whereas manufactured commercial compounds have more enriched carbon isotope ratios. The findings were restricted to a single case study and one element (i.e. carbon). This paper presents a multi-element Compound-Specific Stable Isotope Analysis (CSIA, including carbon, chlorine and hydrogen) of chlorinated aliphatic contaminants originated from chlorinated pitches at two sites with different hydrogeology and different producers of chloromethanes. The results show strongly depleted carbon signatures at both sites whereas the chlorine and the hydrogen signatures are comparable to those presented in the literature for manufactured commercial compounds. Multi-element CSIA allowed the identification of sources and site-specific processes affecting chloroethene transformation in groundwater as a result of emergency remediation measures. CSIA turned out to be an effective forensic tool to address the liability for the contamination, leading to a conviction for the crimes of unintentional aggravated public water supply poisoning and environmental disaster. Copyright © 2018 Elsevier B.V. All rights reserved.

Simulation of multi-photon emission isotopes using time-resolved SimSET multiple photon history generator

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

Chiang, Chih-Chieh; Lin, Hsin-Hon; Lin, Chang-Shiun

Abstract-Multiple-photon emitters, such as In-111 or Se-75, have enormous potential in the field of nuclear medicine imaging. For example, Se-75 can be used to investigate the bile acid malabsorption and measure the bile acid pool loss. The simulation system for emission tomography (SimSET) is a well-known Monte Carlo simulation (MCS) code in nuclear medicine for its high computational efficiency. However, current SimSET cannot simulate these isotopes due to the lack of modeling of complex decay scheme and the time-dependent decay process. To extend the versatility of SimSET for simulation of those multi-photon emission isotopes, a time-resolved multiple photon history generatormore » based on SimSET codes is developed in present study. For developing the time-resolved SimSET (trSimSET) with radionuclide decay process, the new MCS model introduce new features, including decay time information and photon time-of-flight information, into this new code. The half-life of energy states were tabulated from the Evaluated Nuclear Structure Data File (ENSDF) database. The MCS results indicate that the overall percent difference is less than 8.5% for all simulation trials as compared to GATE. To sum up, we demonstrated that time-resolved SimSET multiple photon history generator can have comparable accuracy with GATE and keeping better computational efficiency. The new MCS code is very useful to study the multi-photon imaging of novel isotopes that needs the simulation of lifetime and the time-of-fight measurements. (authors)« less

Multi-isotope approach: a tool to better constrain both sources and processes affecting NO3 pollution in watersheds

NASA Astrophysics Data System (ADS)

Widory, D.

2006-12-01

Nitrate is one of the major pollutants of drinking water resources worldwide. Recent European directives reduced inputs from intensive agriculture, but in most places NO3 levels are approaching the potable limit of 50 mg.l-1 in groundwater. Determining the source(s) of contamination in groundwater is an important first step for improving its quality by emission control. It is with this aim that we review here the benefit of using a multi- isotope approach (d15N, d180, d11B and 87Sr/86Sr), in addition to conventional hydrogeological analysis, to both constrain the watersheds hydrology and trace the origin of their NO3 pollution. Watersheds presented here include both fractured bedrock and alluvial (subsurface and deep) hydrogeological contexts. The strontium budget in watersheds is mainly controlled by the water-rock interactions (human inputs usually represents negligible fluxes). With the example of the Allier river (Central France), we show that, even on a very small watershed, the main water flows can usually be determined by the use of the 87Sr/86Sr ratios, thus helping understanding the hydrology controlling pollution processes. The characterisation of the different usual nitrate sources of pollution in groundwater (mineral fertilisers, wastewater and animals manure) shows that they can clearly be discriminated using isotopes. The isotopic composition of the dissolved nitrogen species has been used extensively to better constrain the sources and fate of nitrate in groundwater. The possibility of quantifying both origin and secondary processes affecting N concentrations by means of a single tracer appears more limited however. Nitrogen cannot be considered conservative because it is biologically modified through nitrification and denitrification reactions, both during infiltration of the water and in the groundwater body, causing isotopic fractionation that modifies the d15N-n signatures of the dissolved N species. Discriminating multiple NO3 sources by their N isotopic composition alone becomes impossible whenever heterogenic or autogenic denitrification occurs, thus arising the need for establishing co-migrating discriminators of NO3 sources: addition of the d180 from NO3 and of the d11B. The use of the strontium isotope systematic for discriminating sources of pollution is also discussed. The use of this multi-isotope approach, in each of the studied contexts, clearly deciphers the origin of NO3 in groundwater and allows a semi-quantification of the contributions of the respective pollution sources.

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

NASA Technical Reports Server (NTRS)

Kerridge, J. F.

1983-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2011-12-01

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

Methane clumped isotopes: Progress and potential for a new isotopic tracer

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

Douglas, Peter M. J.; Stolper, Daniel A.; Eiler, John M.

The isotopic composition of methane is of longstanding geochemical interest, with important implications for understanding hydrocarbon systems, atmospheric greenhouse gas concentrations, the global carbon cycle, and life in extreme environments. Recent analytical developments focusing on multiply substituted isotopologues (‘clumped isotopes’) are opening a potentially valuable new window into methane geochemistry. When methane forms in internal isotopic equilibrium, clumped isotopes can provide a direct record of formation temperature, making this property particularly valuable for identifying different methane origins. However, it has also become clear that in certain settings methane clumped isotope measurements record kinetic rather than equilibrium isotope effects. Here wemore » present a substantially expanded dataset of methane clumped isotope analyses, and provide a synthesis of the current interpretive framework for this parameter. We review different processes affecting methane clumped isotope compositions, describe the relationships between conventional isotope and clumped isotope data, and summarize the types of information that this measurement can provide in different Earth and planetary environments.« less

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

PubMed

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

2003-06-01

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

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

PubMed

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

2014-03-15

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

Chromatographic hydrogen isotope separation

DOEpatents

Aldridge, F.T.

Intermetallic compounds with the CaCu/sub 5/ type of crystal structure, particularly LaNiCo/sub 4/ and CaNi/sub 5/, exhibit high separation factors and fast equilibrium times and therefore are useful for packing a chromatographic hydrogen isotope separation column. The addition of an inert metal to dilute the hydride improves performance of the column. A large scale multi-stage chromatographic separation process run as a secondary process off a hydrogen feedstream from an industrial plant which uses large volumes of hydrogen cn produce large quantities of heavy water at an effective cost for use in heavy water reactors.

Water Isotopes in Precipitation: Data/Model Comparison for Present-Day and Past Climates

NASA Technical Reports Server (NTRS)

Jouzel, J.; Hoffmann, G.; Masson, V.

1998-01-01

Variations of HDO and H2O-18 concentrations are observed in precipitation both on a geographical and on a temporal basis. These variations, resulting from successive isotopic fractionation processes at each phase change of water during its atmospheric cycle, are well documented through the IAEA/WMO network and other sources. Isotope concentrations are, in middle and high latitudes, linearly related to the annual mean temperature at the precipitation site. Paleoclimatologists have used this relationship to infer paleotemperatures from isotope paleodata extractable from ice cores, deep groundwater and other such sources. For this application to be valid, however, the spatial relationship must also hold in time at a given location as the location undergoes a series of climatic changes. Progress in water isotope modeling aimed at examining and evaluating this assumption has been recently reviewed with a focus on polar regions and, more specifically, on Greenland. This article was largely based on the results obtained using the isotopic version of the NASA/GISS Atmospheric General Circulation Model (AGCM) fitted with isotope tracer diagnostics. We extend this review in comparing the results of two different isotopic AGCMs (NASA/GISS and ECHAM) and in examining, with a more global perspective, the validity of the above assumption, i.e. the equivalence of the spatial and temporal isotope-temperature relationship. We also examine recent progress made in modeling the relationship between the conditions prevailing in moisture source regions for precipitation and the deuterium-excess of that precipitation.

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.

IsoMAP (Isoscape Modeling, Analysis, and Prediction)

NASA Astrophysics Data System (ADS)

Miller, C. C.; Bowen, G. J.; Zhang, T.; Zhao, L.; West, J. B.; Liu, Z.; Rapolu, N.

2009-12-01

IsoMAP is a TeraGrid-based web portal aimed at building the infrastructure that brings together distributed multi-scale and multi-format geospatial datasets to enable statistical analysis and modeling of environmental isotopes. A typical workflow enabled by the portal includes (1) data source exploration and selection, (2) statistical analysis and model development; (3) predictive simulation of isotope distributions using models developed in (1) and (2); (4) analysis and interpretation of simulated spatial isotope distributions (e.g., comparison with independent observations, pattern analysis). The gridded models and data products created by one user can be shared and reused among users within the portal, enabling collaboration and knowledge transfer. This infrastructure and the research it fosters can lead to fundamental changes in our knowledge of the water cycle and ecological and biogeochemical processes through analysis of network-based isotope data, but it will be important A) that those with whom the data and models are shared can be sure of the origin, quality, inputs, and processing history of these products, and B) the system is agile and intuitive enough to facilitate this sharing (rather than just ‘allow’ it). IsoMAP researchers are therefore building into the portal’s architecture several components meant to increase the amount of metadata about users’ products and to repurpose those metadata to make sharing and discovery more intuitive and robust to both expected, professional users as well as unforeseeable populations from other sectors.

Sulphur stable isotope systematics in diagenetic pyrite from the North Sea hydrocarbon reservoirs revealed by laser combustion analysis.

PubMed

Fallick, Anthony E; Boyce, Adrian J; McConville, Paul

2012-01-01

Our study focuses on pyrite nodules developed in the Brent Group sandstones, which host the Brent Oilfield, one of the North Sea's greatest oil and gas producers. Timing of nodule formation is equivocal, but due to the forceful, penetrative textures that abound, it is considered late. This pyrite offers a research opportunity because it records the development of the supply of H(2)S in a hydrocarbon reservoir and its sulphur isotopic composition. Laser-based analysis of δ(34)S reveals an extraordinary diversity in values and patterns. The values range from-27 to+72‰, covering half the terrestrial range, with large variations at the submillimetre scale. Isotopically heavy (δ(34)S ∼+30‰ or higher) sulphide is endemic, but low δ(34)S pyrite is also present and appears to represent a temporally though not spatially (on the ∼cm scale) distinct pyritisation event. The distribution of δ(34)S values within individual concretions can be normal (Gaussian), but in some cases may reflect progressive isotope fractionation process(es), conceivably of Rayleigh type. The source of the sulphur and the identity of the isotope fractionation process(es) remain enigmatic.

Re-187 Os-187 Isotopic and Highly Siderophile Element Systematics of Group IVB Irons

NASA Technical Reports Server (NTRS)

Honesto, J.; McDonough, W. F.; Walker, R. J.; McCoy, T. J.; Ash, R. D.

2005-01-01

Study of the magmatic iron meteorite groups permits constraints to be placed on the chemical and isotopic composition of parent bodies, and the timing of, and crystal-liquid fractionation processes involved in the crystallization of asteroidal cores. Here we examine Re-Os isotopic and trace elemental systematics of group IVB irons. Compared to most irons, the irons comprising this group are enriched in some of the most refractory siderophile elements, yet highly-depleted in most volatile siderophile elements. These characteristics have been attributed to processes such as high temperature condensation of precursor materials and oxidation in the parent body. Most recently it has been suggested that both processes may be involved in the chemical complexity of the group. Here, high precision isotopic and highly siderophile element (HSE) concentrations are used to further examine these possible origins, and the crystallization history of the group. In addition, we have begun to assess the possibility of relating certain ungrouped irons with major groups via multi-element, trace element modeling. In a companion abstract, the isotopic and trace element systematics of the ungrouped iron Tishomingo are compared with the IVB irons.

Comprehensive Isotopic and Elemental Analysis of a Multi-Oxide Glass By Multicollector ICP-MS in Isotope Substitution Studies

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

v, Mitroshkov; JV, Ryan

2016-04-07

Multicollector ICP-MS was used to comprehensively analyze different types of isotopically-modified glass created in order to investigate the processes of glass corrosion in the water. The analytical methods were developed for the analyses of synthesized, isotopically-modified solid glass and the release of glass constituents upon contact with deionized water. To validate the methods, results from an acid digestion sample of the Analytical Reference Glass (ARG) showed good agreement when compared to data from multiple prior analyses on the same glass [Smith-1]. In this paper, we present the results of this comprehensive analysis from the acid digestion of six types ofmore » isotopically-modified glass and the release of glass constituents into water corrosion after one year of aqueous corrosion.« less

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.

Physics overview of AVLIS

NASA Astrophysics Data System (ADS)

Solarz, R. W.

1985-02-01

Atomic vapor laster isotope separation (AVLIS) represents the largest-scale potential application of tunable lasers that has received serious attention. The underlying physical principles were identified and optimized, the major technology components were developed, and the integrated enrichment performance of the process was tested. The central physical processes are outlined, progress to date on the technology elements is reviewed, and scaling laws are fomulated. Two primary applications are the production of light-water reactor fuel and the conversion of fuel-grade plutonium to weapons-grade material. A variety of applications exist that all potentially use a common base of AVLIS technology. These include missions such as the enrichment of mercury isotopes to improve fluorescent lamp efficiency, the enrichment of iodine isotopes for medical isotope use, and the cleanup of strontium from defense waste for recovering strontium isotopes for radiothermal mechanical generators. The ability to radidly assess the economic and technical feasibility of each mission is derived from the general applicability of AVLIS physics and AVLIS technology.

Thermal Diffusion Fractionation of Cr and V Isotope in Silicate Melt

NASA Astrophysics Data System (ADS)

Lin, X.; Lundstrom, C.

2017-12-01

Earth's mantle is isotopically heavy relative to chondrites for V, Cr and some other siderophile elements. A possible solution is that isotopic fractionation by thermal diffusion occurs in a thermal boundary layer between solid mantle and an underlying basal magma ocean (BMO:Labrosse et al.,2007). If so, isotopically light composition might partition into the core, resulting in a complimentary isotopically heavy solid mantle. To verify how much fractionation could happen in this process, piston cylinder experiment were conducted to investigate the fractionation of Cr and V isotope ratios in partially molten silicate under an imposed temperature gradient from 1650 °C to 1350 °C at 1 GPa for 10 to 50 hours to reach a steady state isotopic profile. The temperature profile for experiments was determined by the spinel-growth method at the same pressure and temperature. Experimental runs result in 100% glass at the hot end progressing to nearly 100 % olivine at the cold end. Major and minor element concentrations of run products show systematic changes with temperature. Glass MgO contents increase and Al2O3 and CaO contents decrease by several weight percent as temperature increases across the charge. These are well modeled using IRIDIUM (Boudreau 2003) to simulate the experiments. Isotopic composition measurements of Cr and V at different temperatures are in progress, providing the first determinations of thermal diffusion isotopic sensitivity, Ω (permil isotopic fractionation per temperature offset per mass unit) for these elements. These results will be compared with previously determined Ω for network formers and modifiers and used in a BMO-based thermal diffusion model for formation of Earth's isotopically heavy mantle.

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.

U.S. Department of Energy Isotope Program

ScienceCinema

None

2018-01-16

The National Isotope Development Center (NIDC) interfaces with the User Community and manages the coordination of isotope production across the facilities and business operations involved in the production, sale, and distribution of isotopes. A virtual center, the NIDC is funded by the Isotope Development and Production for Research and Applications (IDPRA) subprogram of the Office of Nuclear Physics in the U.S. Department of Energy Office of Science. PNNL’s Isotope Program operates in a multi-program category-2 nuclear facility, the Radiochemical Processing Laboratory (RPL), that contains 16 hot cells and 20 gloveboxes. As part of the DOE Isotope Program, the Pacific Northwest National Laboratory dispenses strontium-90, neptunium-237, radium-223, and thorium-227. PNNL’s Isotope Program uses a dedicated hot-cell for strontium-90 dispensing and a dedicated glovebox for radium-223 and thorium-227 dispensing. PNNL’s Isotope Program has access to state of the art analytical equipment in the RPL to support their research and production activities. DOE Isotope Program funded research at PNNL has advanced the application of automated radiochemistry for isotope such as zirconium-89 and astatine-211 in partnership with the University of Washington.

U.S. Department of Energy Isotope Program

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

None

The National Isotope Development Center (NIDC) interfaces with the User Community and manages the coordination of isotope production across the facilities and business operations involved in the production, sale, and distribution of isotopes. A virtual center, the NIDC is funded by the Isotope Development and Production for Research and Applications (IDPRA) subprogram of the Office of Nuclear Physics in the U.S. Department of Energy Office of Science. PNNL’s Isotope Program operates in a multi-program category-2 nuclear facility, the Radiochemical Processing Laboratory (RPL), that contains 16 hot cells and 20 gloveboxes. As part of the DOE Isotope Program, the Pacific Northwestmore » National Laboratory dispenses strontium-90, neptunium-237, radium-223, and thorium-227. PNNL’s Isotope Program uses a dedicated hot-cell for strontium-90 dispensing and a dedicated glovebox for radium-223 and thorium-227 dispensing. PNNL’s Isotope Program has access to state of the art analytical equipment in the RPL to support their research and production activities. DOE Isotope Program funded research at PNNL has advanced the application of automated radiochemistry for isotope such as zirconium-89 and astatine-211 in partnership with the University of Washington.« less

New perspectives in tracing vector-borne interaction networks.

PubMed

Gómez-Díaz, Elena; Figuerola, Jordi

2010-10-01

Disentangling trophic interaction networks in vector-borne systems has important implications in epidemiological and evolutionary studies. Molecular methods based on bloodmeal typing in vectors have been increasingly used to identify hosts. Although most molecular approaches benefit from good specificity and sensitivity, their temporal resolution is limited by the often rapid digestion of blood, and mixed bloodmeals still remain a challenge for bloodmeal identification in multi-host vector systems. Stable isotope analyses represent a novel complementary tool that can overcome some of these problems. The utility of these methods using examples from different vector-borne systems are discussed and the extents to which they are complementary and versatile are highlighted. There are excellent opportunities for progress in the study of vector-borne transmission networks resulting from the integration of both molecular and stable isotope approaches. Copyright © 2010 Elsevier Ltd. All rights reserved.

Mean-field studies of time reversal breaking states in super-heavy nuclei with the Gogny force

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

Robledo, L. M., E-mail: luis.robledo@uam.es

2015-10-15

Recent progress on the description of time reversal breaking (odd mass and multi-quasiparticle excitation) states in super-heavy nuclei within a mean field framework and using several flavors of the Gogny interaction is reported. The study includes ground and excited states in selected odd mass isotopes of nobelium and mendelevium as well as high K isomeric states in {sup 254}No. These are two and four-quasiparticle excitations that are treated in the same self-consistent HFB plus blocking framework as the odd mass states.

Multi-tracer investigation of river and groundwater interactions: a case study in Nalenggele River basin, northwest China

NASA Astrophysics Data System (ADS)

Xu, Wei; Su, Xiaosi; Dai, Zhenxue; Yang, Fengtian; Zhu, Pucheng; Huang, Yong

2017-11-01

Environmental tracers (such as major ions, stable and radiogenic isotopes, and heat) monitored in natural waters provide valuable information for understanding the processes of river-groundwater interactions in arid areas. An integrated framework is presented for interpreting multi-tracer data (major ions, stable isotopes (2H, 18O), the radioactive isotope 222Rn, and heat) for delineating the river-groundwater interactions in Nalenggele River basin, northwest China. Qualitative and quantitative analyses were undertaken to estimate the bidirectional water exchange associated with small-scale interactions between groundwater and surface water. Along the river stretch, groundwater and river water exchange readily. From the high mountain zone to the alluvial fan, groundwater discharge to the river is detected by tracer methods and end-member mixing models, but the river has also been identified as a losing river using discharge measurements, i.e. discharge is bidirectional. On the delta-front of the alluvial fan and in the alluvial plain, in the downstream area, the characteristics of total dissolved solids values, 222Rn concentrations and δ18O values in the surface water, and patterns derived from a heat-tracing method, indicate that groundwater discharges into the river. With the environmental tracers, the processes of river-groundwater interaction have been identified in detail for better understanding of overall hydrogeological processes and of the impacts on water allocation policies.

Cu isotope fractionation response to oxidative stress in a hepatic cell line studied using multi-collector ICP-mass spectrometry.

PubMed

Flórez, María R; Costas-Rodríguez, Marta; Grootaert, Charlotte; Van Camp, John; Vanhaecke, Frank

2018-03-01

Reactive oxygen species (ROS) are generated in biological processes involving electron transfer reactions and can act in a beneficial or deleterious way. When intracellular ROS levels exceed the cell's anti-oxidant capacity, oxidative stress occurs. In this work, Cu isotope fractionation was evaluated in HepG2 cells under oxidative stress conditions attained in various ways. HepG2 is a well-characterised human hepatoblastoma cell line adapted to grow under high oxidative stress conditions. During a pre-incubation stage, cells were exposed to a non-toxic concentration of Cu for 24 h. Subsequently, the medium was replaced and cells were exposed to one of three different external stressors: H 2 O 2 , tumour necrosis factor α (TNFα) or UV radiation. The isotopic composition of the intracellular Cu was determined by multi-collector ICP-mass spectrometry to evaluate the isotope fractionation accompanying Cu fluxes between cells and culture medium. For half of these setups, the pre-incubation solution also contained N-acetyl-cysteine (NAC) as an anti-oxidant to evaluate its protective effect against oxidative stress via its influence on the extent of Cu isotope fractionation. Oxidative stress caused the intracellular Cu isotopic composition to be heavier compared to that in untreated control cells. The H 2 O 2 and TNFα exposures rendered similar results, comparable to those obtained after mild UV exposure. The heaviest Cu isotopic composition was observed under the strongest oxidative conditions tested, i.e., when the cell surfaces were directly exposed to UV radiation without apical medium and in absence of NAC. NAC mitigated the extent of isotope fractionation in all cases.

Multi-isotope (C - O - S - H - B - Mg - Ca - Ba) and trace element variations along a vertical pore water profile across a brackish-fresh water transition, Baltic Sea

NASA Astrophysics Data System (ADS)

Böttcher, Michael E.; Lapham, Laura; Gussone, Nikolaus; Struck, Ulrich; Buhl, Dieter; Immenhauser, Adrian; Moeller, Kirsten; Pretet, Chloé; Nägler, Thomas F.; Dellwig, Olaf; Schnetger, Bernhard; Huckriede, Hermann; Halas, Stan; Samankassou, Elias

2013-04-01

The Holocene Baltic Sea has been switched several times between fresh water and brackish water modes. Modern linear sedimentation rates, based on 210-Pb, 137-Cs, and Hg dating of surface sediments, are between 0.1 and 0.2 mm per year. The change in paleo-environmental conditions caused downcore gradients in the concentrations of dissolved species from modern brackish waters towards fresh paleo-pore waters, interrupted by the brief brackish Yoldia stage. These strong physico-chemical changes had consequences for e.g., microbial activity and further physical and chemical water-solid interactions associated with multiple stable isotope fractionation processes, and, in turn, have strong implications for isotope and trace element partitioning upon early diagenetic mineral (trans)formations. In this communication, we present the results from the first integrated multi-isotope and trace element investigation conducted in this type of salinity-gradient system. It is found that concentrations of conservative elements (e.g., Na, Cl) decrease with depth due to diffusion of ions from brackish waters into underlying fresh waters. This is associated with pronounced depletions in H-2 and O-18 of pore water with depth. Covariations of both isotope systems are close to the meteoric water line as defined by modern Baltic Sea surface waters. A downward increase and decrease of Ca and Mg concentrations, respectively, is associated with decreasing Ca-44 and Mg-26 isotope values. B-11 isotope values decrease in the limnic part of the sediments, too. On the other hand, an increase in Ba concentrations with depth is associated with an increase in Ba-137/134 isotope values. Microbial sulfate reduction and organic matter oxidation lead to an increase in DIC, but a decrease in sulfate concentrations and in C-13 contents of DIC with depth. Suess (1981) was probably the first to propose, that desorption of Ca and Ba from glacial sediments due to downward diffusing ions may be responsible for a downcore increase in pore water concentrations of earth alkaline ions and the formation of authigenic barites. Coupled S-34 and O-18 isotope signals in authigenic barites suggest that they were formed in pre-Yoldia sediments from pore waters strongly depleted in O-18 (as low as -20 per mil vs. VSMOW). In the present communication, we will discuss possible impacts of diagenetic processes on multi-isotope signals in pore waters and authigenic phases. A combination of mixing between brackish and fresh water, ion exchange, precipitation/dissolution, and transport reactions is considered to explain most of the observed isotope variations along the vertical pore water profile. This work was supported by the Leibniz IOW, BONUS+ program, the Universities of Bern, Geneva, Bochum, Münster, and Oldenburg, and the Natural Museum of History, Berlin.

Isotopic and trace element characteristics of an unusual refractory inclusion from Essebi

NASA Technical Reports Server (NTRS)

Deloule, E.; Kennedy, A. K.; Hutcheon, I. D.; Elgoresy, A.

1993-01-01

The isotopic and chemical properties of Ca-Al-rich inclusions (CAI) provide important clues to the early solar nebula environment. While the abundances of refractory major and trace elements are similar to those expected for high temperature condensates, the variety of textural, chemical, and isotopic signatures indicate most CAI experienced complex, multi-stage histories involving repeated episodes of condensation, evaporation, and metamorphism. Evidence of multiple processes is especially apparent in an unusual refractory inclusion from Essebi (URIE) described by El Goresy et al. The melilite (mel)-rich core of URIE contains polygonal framboids of spinel (sp) and hibonite (hb) or sp and fassaite (fas) and is surrounded by a rim sequence consisting of five layers. In contrast to rims on Allende, the mineralogy of the URIE rim layers becomes increasingly refractory from the core outwards, ending in a layer of spinel-Al2O3 solid solution + Sc-rich fassaite. The chemical and mineralogical features of URIE are inconsistent with crystallization from a homogeneous melt, and El Goresy et al. proposed a multi-step history involving condensation of sp + hb and aggregation into framboids, capture of framboids by a refractory silicate melt droplet, condensation of rim layers, and alteration of mel to calcite and feldspathoid. The PANURGE ion probe was used to investigate the isotopic and trace element characteristics of URIE to develop a more complete picture of the multiple processes leading to formation and metamorphism.

A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site

NASA Astrophysics Data System (ADS)

Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50 years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in 13C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, 13C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas.

A stable isotope approach for source apportionment of chlorinated ethene plumes at a complex multi-contamination events urban site.

PubMed

Nijenhuis, Ivonne; Schmidt, Marie; Pellegatti, Eleonora; Paramatti, Enrico; Richnow, Hans Hermann; Gargini, Alessandro

2013-10-01

The stable carbon isotope composition of chlorinated aliphatic compounds such as chlorinated methanes, ethanes and ethenes was examined as an intrinsic fingerprint for apportionment of sources. A complex field site located in Ferrara (Italy), with more than 50years history of use of chlorinated aliphatic compounds, was investigated in order to assess contamination sources. Several contamination plumes were found in a complex alluvial sandy multi-aquifer system close to the river Po; sources are represented by uncontained former industrial and municipal dump sites as well as by spills at industrial areas. The carbon stable isotope signature allowed distinguishing 2 major sources of contaminants. One source of chlorinated aliphatic contaminants was strongly depleted in ¹³C (<-60‰) suggesting production lines which have used depleted methane for synthesis. The other source had typical carbon isotope compositions of >-40‰ which is commonly observed in recent production of chlorinated solvents. The degradation processes in the plumes could be traced interpreting the isotope enrichment and depletion of parent and daughter compounds, respectively. We demonstrate that, under specific production conditions, namely when highly chlorinated ethenes are produced as by-product during chloromethanes production, ¹³C depleted fingerprinting of contaminants can be obtained and this can be used to track sources and address the responsible party of the pollution in urban areas. © 2013 Elsevier B.V. All rights reserved.

Critical Need for Plutonium and Uranium Isotopic Standards with Lower Uncertainties

DOE PAGES

Mathew, Kattathu Joseph; Stanley, Floyd E.; Thomas, Mariam R.; ...

2016-09-23

Certified reference materials (CRMs) traceable to national and international safeguards database are a critical prerequisite for ensuring that nuclear measurement systems are free of systematic biases. CRMs are used to validate measurement processes associated with nuclear analytical laboratories. Diverse areas related to nuclear safeguards are impacted by the quality of the CRM standards available to analytical laboratories. These include: nuclear forensics, radio-chronometry, national and international safeguards, stockpile stewardship, nuclear weapons infrastructure and nonproliferation, fuel fabrication, waste processing, radiation protection, and environmental monitoring. For the past three decades the nuclear community is confronted with the strange situation that improvements in measurementmore » data quality resulting from the improved accuracy and precision achievable with modern multi-collector mass spectrometers could not be fully exploited due to large uncertainties associated with CRMs available from New Brunswick Laboratory (NBL) that are used for instrument calibration and measurement control. Similar conditions prevail for both plutonium and uranium isotopic standards and for impurity element standards in uranium matrices. Herein, the current status of U and Pu isotopic standards available from NBL is reviewed. Critical areas requiring improvement in the quality of the nuclear standards to enable the U. S. and international safeguards community to utilize the full potential of modern multi-collector mass spectrometer instruments are highlighted.« less

Critical Need for Plutonium and Uranium Isotopic Standards with Lower Uncertainties

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

Mathew, Kattathu Joseph; Stanley, Floyd E.; Thomas, Mariam R.

Certified reference materials (CRMs) traceable to national and international safeguards database are a critical prerequisite for ensuring that nuclear measurement systems are free of systematic biases. CRMs are used to validate measurement processes associated with nuclear analytical laboratories. Diverse areas related to nuclear safeguards are impacted by the quality of the CRM standards available to analytical laboratories. These include: nuclear forensics, radio-chronometry, national and international safeguards, stockpile stewardship, nuclear weapons infrastructure and nonproliferation, fuel fabrication, waste processing, radiation protection, and environmental monitoring. For the past three decades the nuclear community is confronted with the strange situation that improvements in measurementmore » data quality resulting from the improved accuracy and precision achievable with modern multi-collector mass spectrometers could not be fully exploited due to large uncertainties associated with CRMs available from New Brunswick Laboratory (NBL) that are used for instrument calibration and measurement control. Similar conditions prevail for both plutonium and uranium isotopic standards and for impurity element standards in uranium matrices. Herein, the current status of U and Pu isotopic standards available from NBL is reviewed. Critical areas requiring improvement in the quality of the nuclear standards to enable the U. S. and international safeguards community to utilize the full potential of modern multi-collector mass spectrometer instruments are highlighted.« less

Carbon isotope fractionation during diamond growth in depleted peridotite: Counterintuitive insights from modelling water-maximum CHO fluids as multi-component systems

NASA Astrophysics Data System (ADS)

Stachel, T.; Chacko, T.; Luth, R. W.

2017-09-01

Because of the inability of depleted cratonic peridotites to effectively buffer oxygen fugacities when infiltrated by CHO or carbonatitic fluids, it has been proposed recently (Luth and Stachel, 2014) that diamond formation in peridotites typically does not occur by rock-buffered redox reactions as previously thought but by an oxygen-conserving reaction in which minor coexisting CH4 and CO2 components in a water-rich fluid react to form diamond (CO2 + CH4 = 2C + 2H2O). In such fluid-buffered systems, carbon isotope fractionation during diamond precipitation occurs in the presence of two dominant fluid carbon species. Carbon isotope modelling of diamond precipitation from mixed CH4- and CO2-bearing fluids reveals unexpected fundamental differences relative to diamond crystallization from a single carbon fluid species: (1) irrespective of which carbon fluid species (CH4 or CO2) is dominant in the initial fluid, diamond formation is invariably associated with progressive minor (<1‰) enrichment of diamond in 13C as crystallization proceeds. This is in contrast to diamond precipitation by rock-buffered redox processes from a fluid containing only a single carbon species, which can result in either progressive 13C enrichment (CO2 or carbonate fluids) or 13C depletion (CH4 fluids) in the diamond. (2) Fluid speciation is the key factor controlling diamond δ13 C values; as XCO2 (XCO2 = CO2/[CO2 + CH4]) in the initial fluid increases from 0.1 to 0.9 (corresponding to an increase in fO2 of 0.8 log units), the carbon isotope composition of the first-precipitated diamond decreases by 3.7‰. The tight mode in δ13C of - 5 ± 1 ‰ for diamonds worldwide places strict constraints on the dominant range of XCO2 in water-rich fluids responsible for diamond formation. Specifically, precipitation of diamonds with δ13C values in the range -4 to -6‰ from mantle-derived fluids with an average δ13C value of -5‰ (derived from evidence not related to diamonds) requires that diamond-forming fluids were relatively reduced and had methane as the dominant carbon species (XCO2 = 0.1-0.5). Application of our model to a recently published set of in-situ carbon isotope analyses for peridotitic diamonds from Marange, Zimbabwe (Smit et al., 2016), which contain CH4 fluid inclusions, allows us to perfectly match the observed co-variations in δ13 C, δ15 N and N content and at the same time explain the previously counter-intuitive observation of progressive 13C enrichment in diamonds that appear to have grown from a fluid with methane as the dominant carbon species. Similarly, the almost complete absence in the published record of progressive 13C depletion trends within diamonds likely reflects ubiquitous precipitation from CH4- and CO2-bearing water-rich fluids, rather than diamond formation exclusively by carbonate-bearing and CH4-free oxidized fluids or melts.

Microbially mediated carbon cycling as a control on the δ 13C of sedimentary carbon in eutrophic Lake Mendota (USA): new models for interpreting isotopic excursions in the sedimentary record

NASA Astrophysics Data System (ADS)

Hollander, David J.; Smith, Michael A.

2001-12-01

An isotopic study of various carbon phases in eutrophic Lake Mendota (Wisconsin, USA) indicates that the δ13C composition of sedimentary organic and inorganic carbon has become more negative in response to increasing microbially mediated carbon cycling and processes associated with the intensification of seasonal and long-term eutrophication. Progressive increases in the contributions of isotopically depleted chemoautotrophic and methanotrophic biomass (reflected in the -40 to -90‰ values of hopanols and FAMES), attributed to seasonal and long-term increases in production and expansion of the anaerobic water mass, accounts for carbon isotopic trends towards depleted δ13C values observed in both seasonal varves and over the past 100 years. Changes in the intensities of certain microbial processes are also evident in the sedimentary geochemical record. During the period of most intense cultural eutrophication, when the oxic-anoxic interface was located close to the surface, methanogenesis/methanotrophy and the oxidation of biogenic methane increased to the extent that significant quantities of 13C-depleted CO2 were added into the epilimnion. This depleted CO2 was subsequently utilized by phytoplankton and incorporated into CaCO3 during biogenically induced calcite precipitation. A comparative study between eutrophic Lakes Mendota and Greifen, further indicate that the extent of nutrient loading in the epilimnion determines whether the δ13C record of sedimentary organic carbon reflects intensification of microbial processes in the hypolimnion and sediments, or changes in the primary productivity in the photic zone. From this comparison, a series of eutrophication models are developed to describe progressive transitions through thresholds of microbial and eukaryotic productivity and their influence on the δ13C record of sedimentary carbon. With increasing eutrophication, the models initially predict a negative and then a subsequent positive carbon isotopic excursion reflecting the changing influence of 13C-deleted microbial biomass relative to 13C-enriched photoautrophic biomass. These eutrophication models provide a framework to evaluate carbon cycling processes in modern environments and have significant implications for interpreting carbon isotopic excursions in the sedimentary record.

Ca cycling and isotopic fluxes in forested ecosystems in Hawaii

USGS Publications Warehouse

Wiegand, B.A.; Chadwick, O.A.; Vitousek, P.M.; Wooden, J.L.

2005-01-01

Biogeochemical processes fractionate Ca isotopes in plants and soils along a 4 million year developmental sequence in the Hawaiian Islands. We observed that plants preferentially take up 40Ca relative to 44Ca, and that biological fractionation and changes in the relative contributions from volcanic and marine sources produce a significant increase in 44Ca in soil exchangeable pools. Our results imply moderate fluxes enriched in 44Ca from strongly nutrient-depleted old soils, in contrast with high 40Ca fluxes in young and little weathered environments. In addition, biological fractionation controls divergent geochemical pathways of Ca and Sr in the plant-soil system. While Ca depletes progressively with increasing soil age, Sr/Ca ratios increase systematically. Sr isotope ratios provide a valuable tracer for provenance studies of alkaline earth elements in forested ecosystems, but its usefulness is limited when deciphering biogeochemical processes involved in the terrestrial Ca cycle. Ca isotopes in combination with Sr/ Ca ratios reveal more complex processes involved in the biogeochemistry of Ca and Sr. Copyright 2005 by the American Geophysical Union.

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.

Progress in the Use of Isotopes: The Atomic Triad - Reactors, Radioisotopes and Radiation

DOE R&D Accomplishments Database

Libby, W. F.

1958-08-04

Recent years have seen a substantial growth in the use of isotopes in medicine, agriculture, and industry: up to the minute information on the production and use of isotopes in the U.S. is presented. The application of radioisotopes to industrial processes and manufacturing operations has expanded more rapidly than any one except its most ardent advocates expected. New uses and new users are numerous. The adoption by industry of low level counting techniques which make possible the use of carbon-14 and tritium in the control of industrial processes and in certain exploratory and research problems is perhaps most promising of current developments. The latest information on savings to industry will be presented. The medical application of isotopes has continued to develop at a rapid pace. The current trend appears to be in the direction of improvements in technique and the substitution of more effective isotopes for those presently in use. Potential and actual benefits accruing from the use of isotopes in agriculture are reviewed. The various methods of production of radioisotopes are discussed. Not only the present methods but also interesting new possibilities are covered. Although isotopes are but one of the many peaceful uses of the atom, it is the first to pay its way. (auth)

Antimony isotopic composition in river waters affected by ancient mining activity.

PubMed

Resongles, Eléonore; Freydier, Rémi; Casiot, Corinne; Viers, Jérôme; Chmeleff, Jérôme; Elbaz-Poulichet, Françoise

2015-11-01

In this study, antimony (Sb) isotopic composition was determined in natural water samples collected along two hydrosystems impacted by historical mining activities: the upper Orb River and the Gardon River watershed (SE, France). Antimony isotope ratio was measured by HG-MC-ICP-MS (Hydride Generation Multi-Collector Inductively Coupled Plasma Mass Spectrometer) after a preconcentration and purification step using a new thiol-cellulose powder (TCP) procedure. The external reproducibility obtained for δ(123)Sb measurements of our in-house Sb isotopic standard solution and a certified reference freshwater was 0.06‰ (2σ). Significant isotopic variations were evident in surface waters from the upper Orb River (-0.06‰≤δ(123)Sb≤+0.11‰) and from the Gardon River watershed (+0.27‰≤δ(123)Sb≤+0.83‰). In particular, streams that drained different former mining sites exploited for Sb or Pb-Zn exhibited contrasted Sb isotopic signature, that may be related to various biogeochemical processes occurring during Sb transfer from rocks, mine wastes and sediments to the water compartment. Nevertheless, Sb isotopic composition appeared to be stable along the Gardon River, which might be attributed to the conservative transport of Sb at distance from mine-impacted streams, due to the relative mobile behavior of Sb(V) in natural oxic waters. This study suggests that Sb isotopic composition could be a useful tool to track pollution sources and/or biogeochemical processes in hydrologic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

New techniques for positron emission tomography in the study of human neurological disorders. Progress report, June 1990--June 1993

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

Kuhl, D.E.

1993-06-01

This progress report describes accomplishments of four programs. The four programs are entitled (1) Faster,simpler processing of positron-computing precursors: New physicochemical approaches, (2) Novel solid phase reagents and methods to improve radiosynthesis and isotope production, (3) Quantitative evaluation of the extraction of information from PET images, and (4) Optimization of tracer kinetic methods for radioligand studies in PET.

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

PubMed

Kaufmann, A; Walker, S; Mol, G

2016-04-15

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

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

NASA Astrophysics Data System (ADS)

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

2010-07-01

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

Using MASHA+TIMEPIX Setup for Registration Beta Decay Isotopes Produced in Heavy Ion Induced Reactions

NASA Astrophysics Data System (ADS)

Rodin, A. M.; Belozerov, A. V.; Chernysheva, E. V.; Dmitriev, S. N.; Gulyaev, A. V.; Gulyaeva, A. V.; Itkis, M. G.; Novoselov, A. S.; Oganessian, Yu. Ts.; Salamatin, V. S.; Stepantsov, S. V.; Vedeneev, V. Yu.; Yukhimchuk, S. A.; Krupa, L.; Granja, C.; Pospisil, S.; Kliman, J.; Motycak, S.; Sivacek, I.

2015-06-01

Radon and mercury isotopes were produced in multi nucleon transfer (48Ca + 232Th) and complete fusion (48Ca + naturalNd) reactions, respectively. The isotopes with given masses were detected using two detectors: a multi-strip detector of the well-type (made in CANBERRA) and a position-sensitive quantum counting hybrid pixel detector of the TIMEPIX type. The isotopes implanted into the detectors then emit alpha- and betaparticles until reaching the long lived isotopes. The position of the isotopes, the tracks, the time and energy of beta-particles were measured and analyzed. A new software for the particle recognition and data analysis of experimental results was developed and used. It was shown that MASHA+ TIMEPIX setup is a powerful instrument for investigation of neutron-rich isotopes far from stability limits.

The mercury isotope composition of Arctic coastal seawater

NASA Astrophysics Data System (ADS)

Štrok, Marko; Baya, Pascale Anabelle; Hintelmann, Holger

2015-11-01

For the first time, Hg isotope composition of seawater in the Canadian Arctic Archipelago is reported. Hg was pre-concentrated from large volumes of seawater sampling using anion exchange resins onboard the research vessel immediately after collection. Elution of Hg was performed in laboratory followed by isotope composition determination by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For comparison, seawater from two stations was shipped to the laboratory and processed within it. Results showed negative mass-dependent fractionation in the range from -2.85 to -1.10‰ for δ202Hg, as well as slightly positive mass-independent fractionation of odd Hg isotopes. Positive mass-independent fractionation of 200Hg was also observed. Samples that were pre-concentrated in the laboratory showed different Hg isotope signatures and this is most probably due to the abiotic reduction of Hg in the dark by organic matter during storage and shipment after sampling. This emphasizes the need for immediate onboard pre-concentration.

Magnesium Isotopes in the Earth, Moon, Mars, and Pallasite Parent Body: High-Precision Analysis of Olivine by Laser-Ablation Multi-Collector ICPMS

NASA Technical Reports Server (NTRS)

Norman, M.; McCulloch, M.; ONeill, H.; Brandon, A.

2004-01-01

Magnesium isotopes potentially offer new insights into a diverse range of processes including evaporation and condensation in the solar nebula, melting and metasomatism in planetary interiors, and hydrothermal alteration [1,2,3,4]. Volatility-related Mg isotopic variations of up to 10 per mil/amu relative to a terrestrial standard have been found in early nebular phases interpreted as evaporation residues [1], and relatively large variations (up to 3 per mil/amu) in the terrestrial mantle have been reported recently [4]. In order to investigate possible differences in the nebular history of material contributing to the terrestrial planets, and to search for evidence of a high-temperature origin of the Moon, we have measured the magnesium isotopic composition of primitive olivines from the Earth, Moon, Mars, and pallasite parent body using laser-ablation multicollector ICPMS.

A Bat's-Eye View of Holocene Climate Change in the Southwest: Resolving Ambiguities in Cave Isotopic Records

NASA Astrophysics Data System (ADS)

Cole, J. E.; Truebe, S. A.; Harrington, M. D.; Woodhead, J. D.; Overpeck, J. T.; Hlohowskyj, S.; Henderson, G. M.

2015-12-01

In dry environments, speleothems provide an outstanding archive of information on past climate change, particularly since lakes are typically absent or intermittent. Speleothem stable isotopes are widely used for climate reconstruction, but the isotope-climate relationship is complex in arid-region precipitation, and within-cave processes further complicate climate interpretations. Our isotope results from 3 southeastern Arizona caves, spanning the past 3.5-12 kyr, collectively indicate a weakening monsoon from 7kyr to present. These records exhibit substantial multidecadal-multicentury variability that is sometimes shared, and sometimes independent among caves. Strategies to overcome ambiguities in isotope records include long-term monitoring of cave dripwaters, multi-site comparisons, and multiproxy measurements. Monthly dripwater measurements from two caves spanning several years highlight substantial seasonal biases that create distinct differences in the climate sensitivity of individual cave records. These biases can lead to lack of correlation between records, but also creates opportunities for seasonally specific moisture reconstructions. New preliminary analyses suggest that elemental data can help to unravel the multivariate signal contained in speleothem oxygen isotope records.

Tracking multi-generational colonization of the breeding grounds by monarch butterflies in eastern North America

PubMed Central

Flockhart, D. T. Tyler; Wassenaar, Leonard I.; Martin, Tara G.; Hobson, Keith A.; Wunder, Michael B.; Norris, D. Ryan

2013-01-01

Insect migration may involve movements over multiple breeding generations at continental scales, resulting in formidable challenges to their conservation and management. Using distribution models generated from citizen scientist occurrence data and stable-carbon and -hydrogen isotope measurements, we tracked multi-generational colonization of the breeding grounds of monarch butterflies (Danaus plexippus) in eastern North America. We found that monarch breeding occurrence was best modelled with geographical and climatic variables resulting in an annual breeding distribution of greater than 12 million km2 that encompassed 99% occurrence probability. Combining occurrence models with stable isotope measurements to estimate natal origin, we show that butterflies which overwintered in Mexico came from a wide breeding distribution, including southern portions of the range. There was a clear northward progression of monarchs over successive generations from May until August when reproductive butterflies began to change direction and moved south. Fifth-generation individuals breeding in Texas in the late summer/autumn tended to originate from northern breeding areas rather than regions further south. Although the Midwest was the most productive area during the breeding season, monarchs that re-colonized the Midwest were produced largely in Texas, suggesting that conserving breeding habitat in the Midwest alone is insufficient to ensure long-term persistence of the monarch butterfly population in eastern North America. PMID:23926146

Earth Processes: Reading the Isotopic Code

NASA Astrophysics Data System (ADS)

Basu, Asish; Hart, Stan

Publication of this monograph will coincide, to a precision of a few per mil, with the centenary of Henri Becquerel's discovery of "radiations actives" (C. R. Acad. Sci., Feb. 24, 1896). In 1896 the Earth was only 40 million years old according to Lord Kelvin. Eleven years later, Boltwood had pushed the Earth's age past 2000 million years, based on the first U/Pb chemical dating results. In exciting progression came discovery of isotopes by J. J. Thomson in 1912, invention of the mass spectrometer by Dempster (1918) and Aston (1919), the first measurement of the isotopic composition of Pb (Aston, 1927) and the final approach, using Pb-Pb isotopic dating, to the correct age of the Earth: close—2.9 Ga (Gerling, 1942), closer—3.0 Ga (Holmes, 1949) and closest—4.50 Ga (Patterson, Tilton and Inghram, 1953).

Development of a Dynamically Configurable, Object-Oriented Framework for Distributed, Multi-modal Computational Aerospace Systems Simulation

NASA Technical Reports Server (NTRS)

Afjeh, Abdollah A.; Reed, John A.

2003-01-01

The following reports are presented on this project:A first year progress report on: Development of a Dynamically Configurable,Object-Oriented Framework for Distributed, Multi-modal Computational Aerospace Systems Simulation; A second year progress report on: Development of a Dynamically Configurable, Object-Oriented Framework for Distributed, Multi-modal Computational Aerospace Systems Simulation; An Extensible, Interchangeable and Sharable Database Model for Improving Multidisciplinary Aircraft Design; Interactive, Secure Web-enabled Aircraft Engine Simulation Using XML Databinding Integration; and Improving the Aircraft Design Process Using Web-based Modeling and Simulation.

Progress in centralised ethics review processes: Implications for multi-site health evaluations.

PubMed

Prosser, Brenton; Davey, Rachel; Gibson, Diane

2015-04-01

Increasingly, public sector programmes respond to complex social problems that intersect specific fields and individual disciplines. Such responses result in multi-site initiatives that can span nations, jurisdictions, sectors and organisations. The rigorous evaluation of public sector programmes is now a baseline expectation. For evaluations of large and complex multi-site programme initiatives, the processes of ethics review can present a significant challenge. However in recent years, there have been new developments in centralised ethics review processes in many nations. This paper provides the case study of an evaluation of a national, inter-jurisdictional, cross-sector, aged care health initiative and its encounters with Australian centralised ethics review processes. Specifically, the paper considers progress against the key themes of a previous five-year, five nation study (Fitzgerald and Phillips, 2006), which found that centralised ethics review processes would save time, money and effort, as well as contribute to more equitable workloads for researchers and evaluators. The paper concludes with insights for those charged with refining centralised ethics review processes, as well as recommendations for future evaluators of complex multi-site programme initiatives. Copyright © 2015 Elsevier Ltd. All rights reserved.

Zinc stable isotope fractionation upon accelerated oxidative weathering of sulfidic mine waste.

PubMed

Matthies, R; Krahé, L; Blowes, D W

2014-07-15

Accelerated oxidative weathering in a reaction cell (ASTM D 5744 standard protocol) was performed over a 33 week period on well characterized, sulfidic mine waste from the Kidd Creek Cu-Zn volcanogenic massive sulfide deposit, Canada. The cell leachate was monitored for physicochemical parameters, ion concentrations and stable isotope ratios of zinc. Filtered zinc concentrations (<0.45 μm) in the leachate ranged between 4.5 mg L(-1) and 1.9 g L(-1)-potentially controlled by pH, mineral solubility kinetics and (de)sorption processes. The zinc stable isotope ratios varied mass-dependently within +0.1 and +0.52‰ relative to IRMM 3702, and were strongly dependent on the pH (rpH-d66Zn=0.65, p<0.005, n=31). At a pH below 5, zinc mobilization was governed by sphalerite oxidation and hydroxide dissolution-pointing to the isotope signature of sphalerite (+0.1 to +0.16‰). Desorption processes resulted in enrichment of (66)Zn in the leachate reaching a maximum offset of +0.32‰ compared to the proposed sphalerite isotope signature. Over a period characterized by pH=6.1 ± 0.6, isotope ratios were significantly more enriched in (66)Zn with an offset of ≈ 0.23‰ compared to sphalerite, suggesting that zinc release may have been derived from a second zinc source, such as carbonate minerals, which compose 8 wt.% of the tailings. This preliminary study confirms the benefit of applying zinc isotopes alongside standard monitoring parameters to track principal zinc sources and weathering processes in complex multi-phase matrices. Copyright © 2014 Elsevier B.V. All rights reserved.

Spatially controlled Fe and Si isotope variations: an alternative view on the formation of the Torres del Paine pluton

NASA Astrophysics Data System (ADS)

Gajos, Norbert A.; Lundstrom, Craig C.; Taylor, Alexander H.

2016-11-01

We present new Fe and Si isotope ratio data for the Torres del Paine igneous complex in southern Chile. The multi-composition pluton consists of an approximately 1 km vertical exposure of homogenous granite overlying a contemporaneous 250-m-thick mafic gabbro suite. This first-of-its-kind spatially dependent Fe and Si isotope investigation of a convergent margin-related pluton aims to understand the nature of granite and silicic igneous rock formation. Results collected by MC-ICP-MS show a trend of increasing δ56Fe and δ30Si with increasing silica content as well as a systematic increase in δ56Fe away from the mafic base of the pluton. The marginal Torres del Paine granites have heavier Fe isotope signatures (δ56Fe = +0.25 ± 0.02 2se) compared to granites found in the interior pluton (δ56Fe = +0.17 ± 0.02 2se). Cerro Toro country rock values are isotopically light in both Fe and Si isotopic systems (δ56Fe = +0.05 ± 0.02 ‰; δ30Si = -0.38 ± 0.07 ‰). The variations in the Fe and Si isotopic data cannot be accounted for by local assimilation of the wall rocks, in situ fractional crystallization, late-stage fluid exsolution or some combination of these processes. Instead, we conclude that thermal diffusion or source magma variation is the most likely process producing Fe isotope ratio variations in the Torres del Paine pluton.

Modelling stable water isotopes during "high-precipitation" events at Dome C, Antarctica

NASA Astrophysics Data System (ADS)

Schlosser, Elisabeth; Masson-Delmotte, Valérie; Risi, Camille; Stenni, Barbara; Valt, Mauro; Powers, Jordan G.; Manning, Kevin W.; Duda, Michael G.; Cagnati, Anselmo

2014-05-01

For a correct paleoclimatologic interpretation of stable water isotopes from ice cores both pre- and post-depositional processes and their role for isotope fractionation have to be better understood. Our study focusses on "pre-depositional processes", namely the atmospheric processes that determine moisture transport and precipitation formation. At the deep ice core drilling site "Dome C", East Antarctica, fresh snow samples have been taken since 2006. These samples have been analysed crystallographically, which enables us to clearly distinguish between blowing snow, diamond dust, and "synoptic precipitation". Also the stable oxygen/hydrogen isotope ratios of the snow samples were measured, including measurements of 17-O. This is the first and only multi-year fresh-snow data series from an Antarctic deep drilling site. The Antarctic Mesoscale Prediction System (AMPS) employs Polar WRF for aviation weather forecasts in Antarctica. The data are archived and can be used for scientific purposes. The mesoscale atmospheric model was adapted especially for polar regions. The horizontal resolution for the domain that covers the Antarctic continent is 10 km. It was shown that precipitation at Dome C is temporally dominated by diamond dust. However, comparatively large amounts of precipitation are observed during several "high-precipitation" events per year, caused by synoptic activity in the circumpolar trough and related advection of relatively warm and moist air from lower latitudes to the interior of Antarctica. AMPS archive data are used to investigate the synoptic situations that lead to "high-precipitation" events at Dome C; in particular, possible moisture sources are determined using back-trajectories. With this meteorological information, the isotope ratios are calculated using two different isotope models, the Mixed Cloud Isotope Model, a simple Rayleigh-type model, and the LMDZ-iso (Laboratoire de Météorologie Dynamic Zoom), a General Circulation Model (GCM) with implementation of stable isotopes. The results are compared to the measured stable isotope ratios of the fresh snow samples.

A review of isotopic composition as an indicator of the natural and anthropogenic behavior of mercury

USGS Publications Warehouse

Ridley, W.I.; Stetson, S.J.

2006-01-01

There are seven stable isotopes of Hg that can be fractionated as a result of inorganic and organic interactions. Important inorganic reactions involve speciation changes resulting from variations in environmental redox conditions, and phase changes resulting from variations in temperature and/or atmospheric pressure. Important organic reactions include methylation and demethylation, reactions that are bacterially mediated, and complexing with organic anions in soils. The measurement of Hg isotopes by multi-collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS) is now sufficiently precise and sensitive that it is potentially possible to develop the systematics of Hg isotopic fractionation. This provides an opportunity to evaluate the utility of Hg isotopes in identifying source processes, transport mechanisms, and sinks. New values are provided for, 201Hg/198Hg, 200Hg/198Hg, 199Hg/198Hg for three standard materials (IRMM-AE639, SRM 1641c, SRM 3133) that can be used to make inter-laboratory data comparisons, and these values are tabulated with published isotopic information. Overall, the isotopic data for these standards agree to approximately 0.2???. The paper reviews Hg isotope studies that deal with hydrothermal ore deposits, sediments, coal and organic complexing. ?? 2006 Elsevier Ltd. All rights reserved.

Non-traditional isotopes in analytical ecogeochemistry assessed by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Prohaska, Thomas; Irrgeher, Johanna; Horsky, Monika; Hanousek, Ondřej; Zitek, Andreas

2014-05-01

Analytical ecogeochemistry deals with the development and application of tools of analytical chemistry to study dynamic biological and ecological processes within ecosystems and across ecosystem boundaries in time. It can be best described as a linkage between modern analytical chemistry and a holistic understanding of ecosystems ('The total human ecosystem') within the frame of transdisciplinary research. One focus of analytical ecogeochemistry is the advanced analysis of elements and isotopes in abiotic and biotic matrices and the application of the results to basic questions in different research fields like ecology, environmental science, climatology, anthropology, forensics, archaeometry and provenancing. With continuous instrumental developments, new isotopic systems have been recognized for their potential to study natural processes and well established systems could be analyzed with improved techniques, especially using multi collector inductively coupled plasma mass spectrometry (MC-ICP-MS). For example, in case of S, isotope ratio measurements at high mass resolution could be achieved at much lower S concentrations with ICP-MS as compared to IRMS, still keeping suitable uncertainty. Almost 50 different isotope systems have been investigated by ICP-MS, so far, with - besides Sr, Pb and U - Ca, Mg, Cd, Li, Hg, Si, Ge and B being the most prominent and considerably pushing the limits of plasma based mass spectrometry also by applying high mass resolution. The use of laser ablation in combination with MC-ICP-MS offers the possibility to achieve isotopic information on high spatial (µm-range) and temporal scale (in case of incrementally growing structures). The information gained with these analytical techniques can be linked between different hierarchical scales in ecosystems, offering means to better understand ecosystem processes. The presentation will highlight the use of different isotopic systems in ecosystem studies accomplished by ICP-MS. Selected examples on combining isotopic systems for the study of ecosystem processes on different spatial scales will underpin the great opportunities substantiated by the field of analytical ecogeochemistry. Moreover, recent developments in plasma mass spectrometry and the application of new isotopic systems require sound metrological approaches in order to prevent scientific conclusions drawn from analytical artifacts.

Tracking niche variation over millennial timescales in sympatric killer whale lineages

PubMed Central

Foote, Andrew D.; Newton, Jason; Ávila-Arcos, María C.; Kampmann, Marie-Louise; Samaniego, Jose A.; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S.; Gilbert, M. Thomas P.

2013-01-01

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish. PMID:23945688

Tracking niche variation over millennial timescales in sympatric killer whale lineages.

PubMed

Foote, Andrew D; Newton, Jason; Ávila-Arcos, María C; Kampmann, Marie-Louise; Samaniego, Jose A; Post, Klaas; Rosing-Asvid, Aqqalu; Sinding, Mikkel-Holger S; Gilbert, M Thomas P

2013-10-07

Niche variation owing to individual differences in ecology has been hypothesized to be an early stage of sympatric speciation. Yet to date, no study has tracked niche width over more than a few generations. In this study, we show the presence of isotopic niche variation over millennial timescales and investigate the evolutionary outcomes. Isotopic ratios were measured from tissue samples of sympatric killer whale Orcinus orca lineages from the North Sea, spanning over 10 000 years. Isotopic ratios spanned a range similar to the difference in isotopic values of two known prey items, herring Clupea harengus and harbour seal Phoca vitulina. Two proxies of the stage of speciation, lineage sorting of mitogenomes and genotypic clustering, were both weak to intermediate indicating that speciation has made little progress. Thus, our study confirms that even with the necessary ecological conditions, i.e. among-individual variation in ecology, it is difficult for sympatric speciation to progress in the face of gene flow. In contrast to some theoretical models, our empirical results suggest that sympatric speciation driven by among-individual differences in ecological niche is a slow process and may not reach completion. We argue that sympatric speciation is constrained in this system owing to the plastic nature of the behavioural traits under selection when hunting either mammals or fish.

Forensic Stable Isotope Biogeochemistry

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

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.

Advances in Multicollector ICPMS for precise and accurate isotope ratio measurements of Uranium isotopes

NASA Astrophysics Data System (ADS)

Bouman, C.; Lloyd, N. S.; Schwieters, J.

2011-12-01

The accurate and precise determination of uranium isotopes is challenging, because of the large dynamic range posed by the U isotope abundances and the limited available sample material. Various mass spectrometric techniques are used for the measurement of U isotopes, where TIMS is the most accepted and accurate one. Multicollector inductively coupled plasma mass spectrometry (MC-ICPMS) can offer higher productivity compared to TIMS, but is traditionally limited by low efficiency of sample utilisation. This contribution will discuss progress in MC-ICPMS for detecting 234U, 235U, 236U and 238U in various uranium reference materials from IRMM and NBL. The Thermo Scientific NEPTUNE Plus with Jet Interface offers a modified dry plasma ICP interface using a large interface pump combined with a special set of sample and skimmer cones giving ultimate sensitivity for all elements across the mass range. For uranium, an ion yield of > 3 % was reported previously [1]. The NEPTUNE Plus also offers Multi Ion Counting using discrete dynode electron multipliers as well as two high abundance-sensitivity filters to discriminate against peak tailing effects on 234U and 236U originating from the major uranium beams. These improvements in sensitivity and dynamic range allow accurate measurements of 234U, 235U and 236U abundances on very small samples and at low concentration. In our approach, minor U isotopes 234U and 236U were detected on ion counters with high abundance sensitivity filters, whereas 235U and 238U were detected on Faraday Cups using a high gain current amplifier (10e12 Ohm) for 235U. Precisions and accuracies for 234U and 236U were down to ~1%. For 235U, subpermil levels were reached.

Intrinsic W nucleosynthetic isotope variations in carbonaceous chondrites: Implications for W nucleosynthesis and nebular vs. parent body processing of presolar materials

NASA Astrophysics Data System (ADS)

Burkhardt, Christoph; Schönbächler, Maria

2015-09-01

The progressive dissolution of the carbonaceous chondrites Orgueil (CI1), Murchison (CM2) and Allende (CV3) with acids of increasing strength reveals correlated W isotope variations ranging from 3.5 ε182W and 6.5 ε183W in the initial leachate (acetic acid) to -60 ε182W and -40 ε183W in the leachate residue. The observed variations are readily explained by variable mixing of s-process depleted and s-process enriched components. One W s-process carrier is SiC, however, the observed anomaly patterns and mass-balance considerations require at least on additional s-process carrier, possibly a silicate or sulfide. The data reveal well-defined correlations, which provide a test for s-process nucleosynthesis models. The correlations demonstrate that current models need to be revised and highlight the need for more precise W isotope data of SiC grains. Furthermore the correlations provide a mean to disentangle nucleosynthetic and radiogenic contributions to 182W (ε182Wcorrected = ε182Wmeasured - (1.41 ± 0.05) × ε183Wmeasured; ε182Wcorrected = ε182Wmeasured - (-0.12 ± 0.06) × ε184Wmeasured), a prerequisite for the successful application of the Hf-W chronometer to samples with nucleosynthetic anomalies. The overall magnitude of the W isotope variations decreases in the order CI1 > CM2 > CV3. This can be interpreted as the progressive thermal destruction of an initially homogeneous mixture of presolar grains by parent-body processing. However, not only the magnitude but also the W anomaly patterns of the three chondrites are different. In particular leach step 2, that employs nitric acid, reveals a s-deficit signature for Murchison, but a s-excess for Orgueil and Allende. This could be the result of redistribution of anomalous W into a new phase by parent-body alteration, or, the fingerprint of dust processing in the solar nebula. Given that the thermal and aqueous alteration of Murchison is between the CI and CV3 chondrites, parent-body processing is probably not the sole cause for creating the different pattern. Small-scale nebular redistribution of anomalous W may have played a role as well. Similar nebular processes possibly acted differently on specific carrier phases and elements, resulting in the diverse nucleosynthetic signatures observed in planetary materials today.

Validation of Electrochemically Modulated Separations Performed On-Line with MC-ICP-MS for Uranium and Plutonium Isotopic Analyses

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

Liezers, Martin; Olsen, Khris B.; Mitroshkov, Alexandre V.

2010-08-11

The most time consuming process in uranium or plutonium isotopic analyses is performing the requisite chromatographic separation of the actinides. Filament preparation for thermal ionization (TIMS) adds further delays, but is generally accepted due to the unmatched performance in trace isotopic analyses. Advances in Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) are beginning to rival the performance of TIMS. Methods, such as Electrochemically Modulated Separations (EMS) can efficiently pre-concentrate U or Pu quite selectively from small solution volumes in a matrix of 0.5 M nitric acid. When performed in-line with ICP-MS, the rapid analyte release from the electrode is fast,more » and large transient analyte signal enhancements of >100 fold can be achieved as compared to more conventional continuous nebulization of the original starting solution. This makes the approach ideal for very low level isotope ratio measurements. In this paper, some aspects of EMS performance are described. These include low level Pu isotope ratio behavior versus concentration by MC-ICP-MS and uranium rejection characteristics that are also important for reliable low level Pu isotope ratio determinations.« less

Design study of 10 kW direct fission target for RISP project

NASA Astrophysics Data System (ADS)

Tshoo, K.; Jang, D. Y.; Woo, H. J.; Kang, B. H.; Kim, G. D.; Hwang, W.; Kim, Y. K.

2014-03-01

We are developing Isotope Separation On-Line (ISOL) target system, which consists of 1.3 mm-thick uranium-carbide multi-disks and cylindrical tantalum heater, to be installed in new facility for Rare Isotope Science Project in Korea. The intense neutron-rich nuclei are produced via the fission process using the uranium carbide targets with a 70 MeV proton beam. The fission rate was estimated to be ˜1.5 × 1013/sec for 10 kW proton beam. The target system has been designed to be operated at a temperature of ˜2000 °C so as to improve the release effciency.

Testing the Limits to Accurate Comminution Dates: A Progress Report

NASA Astrophysics Data System (ADS)

Piccione, G.; Blackburn, T.; Edwards, G. H.

2017-12-01

The ability to resolve the timing of fine particle production holds potential for contributing to several Earth Science sub-disciplines including glaciology, eolian and fluvial geomorphology, soil production, and fault dynamics. A relatively new geochronologic tool, U-series comminution dating, has shown potential to directly date the timing of particle comminution. This system's sensitivity to particle size arises from a physical disequilibrium in the 238U decay chain generated by the ejected loss of intermediate daughter products (e.g. 234U). It is the goal of this ongoing study to develop and test analytical procedures to improve the accuracy of comminution dating. In the geologic settings explored by previous studies, comminution dates integrate both the time of particle transport and time since deposition. To better test the accuracy of comminution dates, our study focuses on settings where silt has experienced little to no transport time, specifically, glacial moraines in the Eastern Sierras and Rock Avalanches in the San Gabriel Mountains, both locations with existing independent geochronologic constraints. Previous studies demonstrate the dependency of U-series comminution date on grain size and shape. Here we show that mineralogy of samples also plays a role, possibly controlled by the uranium content and crystal bond strength. To separate samples by size and mineralogy, we use dry sonic-sieving, density and magnetic separation. Non-detrital materials deposited on the rim of comminuted grains have an isotopic composition that is unrelated to the isotopic evolution since comminution and therefore must be removed through a multi-step leaching procedure. Leaching is complicated by the fact that areas within the comminuted crystal that have experienced physical fractionation are contained within damaged zones and are prone to being leached themselves, which removes areas of interest from the crystal. We present progress made on a sample processing method developed to alleviate complications that affect comminution age measurements. Initial 234U/238U measurements for untreated silt from an 800ka Sierran glacial till are up to 6% above secular equilibrium, while samples processed with this method have measured ratios as low as 3% below secular equilibrium.

Calcium Isotope Systematics During Development of the Domestic Chicken (Gallus gallus)

NASA Astrophysics Data System (ADS)

Wheatley, P. V.

2003-12-01

Calcium isotope distributions have been recognized as showing systematic and predictable fractionation in nature. However, most of the observed calcium isotope fractionation to date is due to biological processes. The presence of abundant amounts of calcium in mineralized tissues makes the isotopic system of calcium particularly valuable in biological and paleobiological questions involving biomineralization. In order to apply calcium isotope systematics to paleobiological questions the changes in the calcium isotope signatures of mineralized tissue in modern animals should be studied. My study observed the domestic chicken (Gallus gallus) through embryologic ontogeny. This was accomplished by obtaining fertilized eggs staged in a growth series from day 12 to day 20. The eggs were dissected and shell, embryonic bone, albumen, and yolk were analyzed in order to characterize the calcium isotopic composition of the individual components over the course of the growth series. Several systematic changes in the isotopic signatures of various tissues were observed during the course of the development of the embryos. In general, mineralization in biological systems preferentially partitions the lighter isotopes of calcium into hard parts. As a result of this fractionation during mineralization, partitioning of light isotopes of calcium into the mineralized tissues may result in residual tissues being enriched in the heavier isotopes as ontogeny progresses. Better understanding of the behavior of calcium in modern biological systems will improve its application to fossils and expand the number of paleobiological and evolutionary questions that can be addressed using calcium isotopic data.

Multi-scale study of the isotope effect in ISTTOK

NASA Astrophysics Data System (ADS)

Liu, B.; Silva, C.; Figueiredo, H.; Pedrosa, M. A.; van Milligen, B. Ph.; Pereira, T.; Losada, U.; Hidalgo, C.

2016-05-01

The isotope effect, namely the isotope dependence of plasma confinement, is still one of the principal scientific conundrums facing the magnetic fusion community. We have investigated the impact of isotope mass on multi-scale mechanisms, including the characterization of radial correlation lengths (\\boldsymbol{L}{r} ) and long-range correlations (LRC) of plasma fluctuations using multi-array Langmuir probe system, in hydrogen (H) and deuterium (D) plasmas in the ISTTOK tokamak. We found that when changing plasma composition from the H dominated to D dominated, the LRC amplitude increased markedly (10-30%) and the \\boldsymbol{L}{r} increased slightly (~10%). The particle confinement also improved by about 50%. The changes of LRC and \\boldsymbol{L}{r} are congruent with previous findings in the TEXTOR tokamak (Xu et al 2013 Phys. Rev. Lett. 110 265005). In addition, using biorthogonal decomposition, both geodesic acoustic modes and very low frequency (<5 kHz) coherent modes were found to be contributing to LRC.

Multi-element compound specific stable isotope analysis of volatile organic compounds at trace levels in groundwater samples

NASA Astrophysics Data System (ADS)

Herrero-Martín, Sara; Nijenhuis, Ivonne; Schmidt, Marie; Wolfram, Diana; Richnow, Hans. H.; Gehre, Matthias

2013-04-01

Groundwater pollution remains one of the major environmental and health concerns. A thorough understanding of sources, sinks and transformation processes of groundwater contaminants is needed to improve risk management evaluation, and to design efficient remediation and water treatment strategies. Isotopic tools provide unique information for an in-depth understanding of the fate of organic chemicals in the environment. During the last decades compound specific isotope analysis (CSIA) of complex mixtures, using gas chromatography-isotope ratio mass spectrometry (GC-IRMS), has gained popularity for the characterization and risk assessment of hazardous waste sites and for isotope forensics of organic contaminants. Multi-element isotope fingerprinting of organic substances provides a more robust framework for interpretation than the isotope analysis of only one element. One major challenge for application of CSIA is the analysis of trace levels of organic compounds in environmental matrices. It is necessary to inject 1 nmol carbon or 8 nmol hydrogen on column, to obtain an accurate and precise measurement of the isotope ratios, which is between two and three orders of magnitude larger than the amount of compound needed for conventional analysis of compound concentrations. Therefore, efficient extraction and pre-concentration techniques have to be integrated with GC-IRMS. Further research is urgently needed in this field, to evaluate the potential of novel and environmental-friendly sample pre-treatment techniques for CSIA to lower the detection limits and extending environmental applications. In this study, the novel coupling of a headspace autosampler (HS) with a programmed temperature vaporizer (PTV), allowing large volume injection of headspace samples, is proposed to improve the sensitivity of CSIA. This automatic, fast and solvent free strategy provides a significant increase on the sensitivity of GC-based methods maintaining the simple headspace instrumentation. The method was developed for the multi-element isotope analysis (carbon and hydrogen) of priority volatile organic groundwater pollutants (methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene and o-xylene (BTEX)), and for carbon isotope analysis of chlorinated benzenes and ethenes. The extraction and injection conditions were optimized in terms of maximum sensitivity and minimum isotope effects. During the injection of the headspace sample, the liner is maintained at a low temperature, such that the compounds are retained in a hydrophobic insert packing while the water vapor is eliminated through the split line. With the optimized conditions, it was possible to inject up to 5mL headspace sample with no significant carbon or hydrogen isotopic effects except for the most hydrophobic substance (MTBE), which was subject to a small and reproducible isotope fractionation for hydrogen. The increment on method sensitivity was at least 20 fold in comparison with conventional static headspace analysis. The environmental applicability of the HS-PTV-GC-IRMS method was evaluated by the analysis of groundwater samples from different contaminated field sites, containing BTEX and chlorinated volatile organic contaminants in the low µg/L range. The results obtained demonstrate that this pre-concentration technique is highly promising to enhance the limits of detection of current CSIA methods and broaden its possibilities.

Solid State Division progress report for period ending March 31, 1992

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

Green, P.H.; Hinton, L.W.

1992-09-01

During this period, the division conducted a broad, interdisciplinary materials research program with emphasis on theoretical solid state physics, superconductivity, neutron scattering, synthesis and characterization of materials, ion beam and laser processing, and the structure of solids and surfaces. The High Flux Isotope Reactor was returned to full operation.

Fundamental studies in isotope chemistry. Progress report, 1 August 1982-1 August 1983

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

Bigeleisen, J.

1983-01-01

Interest in a search for superheavy elements present in nature as a remnant of the big bang or through continuous production by cosmic rays has prompted us to study the isotope chemistry of superheavy elements. Calculations of the fractionation factors of superheavy elements of masses 10, 100, 1000, and in the form of isotopes of hydrogen, carbon, selenium and uranium against the light naturally occurring isotope of the element show that the superheavy isotope, even of infinite mass, will not be sufficiently fractionated in single stage natural processes to obscure its chemistry. Calculations have been made of the elementary separationmore » factors of superheavy isotopes of carbon and oxygen by fractional distillation of CO at 80/sup 0/K. The fractionation factors are discussed in terms of a model for liquid CO in good agreement with experimental data on /sup 13/C/sup 16/O and /sup 12/C/sup 18/O. Calculations for very heavy isotopic forms of CO reveal for the first time the coupling effect between translation and internal vibration in the liquid. It is shown that a 1ow temperature distillation plant, such as the Los Alamos COLA plant, has a significant potential for enrichment of superheavy isotopes of carbon. The maximum enrichment factor is 10/sup 55/.« less

β-decay spectroscopy of r-process nuclei with N = 126 at KISS

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

Hirayama, Y.; Watanabe, Y. X.; Imai, N.

2014-05-02

The β-decay properties of nuclei with N = 126, which are believed to act as progenitors in the rapid neutron capture (r-) process path forming the third peak (A ∼ 195) in the observed r-abundance element distribution, are considered critical for understanding the production of heavy elements such as gold and platinum at astrophysical sites. We have constructed the KEK Isotope Separation System (KISS), which consists of a gas cell based laser ion source (atomic number selection) and an isotope separation on-line (ISOL) (mass number selection), to produce pure low-energy beams of neutron-rich isotopes around N = 126 and tomore » study their β-decay properties, which are also of interest for astrophysics. The isotopes of interest will be produced by multi-nucleon transfer reactions in heavy ion collisions (e.g. {sup 136}Xe projectile on {sup 198}Pt target). KISS will allow us to study unknown isotopes produced in weak reaction channels under low background conditions. We successfully extracted the stable {sup 56}Fe beam from KISS at the last commissioning on-line experiment with the extraction efficiency of 0.25% and beam purity of more than 98%. We can access the nuclei with N = 126 and measure their half-lives using the KISS in the case of the extraction efficiency of 0.1%.« less

IMPACT OF LEAD ACID BATTERIES AND CADMIUM STABILIZERS ON INCINERATOR EMISSIONS

EPA Science Inventory

The Waste Analysis Sampling, Testing and Evaluation (WASTE) Program is a multi-year, multi-disciplinary program designed to elicit the source and fate of environmentally significant trace materials as a solid waste progresses through management processes. s part of the WASTE Prog...

Late Cretaceous (Late Campanian-Maastrichtian) sea surface temperature record of the Boreal Chalk Sea

NASA Astrophysics Data System (ADS)

Thibault, N.; Harlou, R.; Schovsbo, N. H.; Stemmerik, L.; Surlyk, F.

2015-11-01

The last 8 Myr of the Cretaceous greenhouse interval were characterized by a progressive global cooling with superimposed cool/warm fluctuations. The mechanisms responsible for these climatic fluctuations remain a source of debate that can only be resolved through multi-disciplinary studies and better time constraints. For the first time, we present a record of very high-resolution (ca. 4.5 kyr) sea-surface temperature (SST) changes from the Boreal epicontinental Chalk Sea (Stevns-1 core, Denmark), tied to an astronomical time scale of the late Campanian-Maastrichtian (74 to 66 Myr). Well-preserved bulk stable isotope trends and calcareous nannofossil palaeoecological patterns from the fully cored Stevns-1 borehole show marked changes in SSTs. These variations correlate with deep-water records of climate change from the tropical South Atlantic and Pacific oceans but differ greatly from the climate variations of the North Atlantic. We demonstrate that the onset and end of the early Maastrichtian cooling and of the large negative Campanian-Maastrichtian boundary carbon isotope excursion are coincident in the Chalk Sea. The direct link between SSTs and δ13C variations in the Chalk Sea reassesses long-term glacio-eustasy as the potential driver of carbon isotope and climatic variations in the Maastrichtian.

Late Cretaceous (late Campanian-Maastrichtian) sea-surface temperature record of the Boreal Chalk Sea

NASA Astrophysics Data System (ADS)

Thibault, Nicolas; Harlou, Rikke; Schovsbo, Niels H.; Stemmerik, Lars; Surlyk, Finn

2016-02-01

The last 8 Myr of the Cretaceous greenhouse interval were characterized by a progressive global cooling with superimposed cool/warm fluctuations. The mechanisms responsible for these climatic fluctuations remain a source of debate that can only be resolved through multi-disciplinary studies and better time constraints. For the first time, we present a record of very high-resolution (ca. 4.5 kyr) sea-surface temperature (SST) changes from the Boreal epicontinental Chalk Sea (Stevns-1 core, Denmark), tied to an astronomical timescale of the late Campanian-Maastrichtian (74 to 66 Ma). Well-preserved bulk stable isotope trends and calcareous nannofossil palaeoecological patterns from the fully cored Stevns-1 borehole show marked changes in SSTs. These variations correlate with deep-water records of climate change from the tropical South Atlantic and Pacific oceans but differ greatly from the climate variations of the North Atlantic. We demonstrate that the onset and end of the early Maastrichtian cooling and of the large negative Campanian-Maastrichtian boundary carbon isotope excursion are coincident in the Chalk Sea. The direct link between SSTs and δ13C variations in the Chalk Sea reassesses long-term glacio-eustasy as the potential driver of carbon isotope and climatic variations in the Maastrichtian.

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2014-09-10

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, probably the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs while processes within leaves or during phloem loading may contribute to the overall autotrophic – heterotrophic difference in carbon isotope compositions.« less

Nitrogen control of 13C enrichment in heterotrophic organs relative to leaves in a landscape-building desert plant species

DOE PAGES

Zhang, J.; Gu, L.; Bao, F.; ...

2015-01-01

A longstanding puzzle in isotope studies of C 3 plant species is that heterotrophic plant organs (e.g., stems, roots, seeds, and fruits) tend to be enriched in 13C compared to the autotrophic organ (leaves) that provides them with photosynthate. Our inability to explain this puzzle suggests key deficiencies in understanding post-photosynthetic metabolic processes. It also limits the effectiveness of applications of stable carbon isotope analyses in a variety of scientific disciplines ranging from plant physiology to global carbon cycle studies. To gain insight into this puzzle, we excavated whole plant architectures of Nitraria tangutorum Bobrov, a C 3 species thatmore » has an exceptional capability of fixing sands and building sand dunes, in two deserts in northwestern China. We systematically and simultaneously measured carbon isotope ratios and nitrogen and phosphorous contents of different parts of the excavated plants. We also determined the seasonal variations in leaf carbon isotope ratios on nearby intact plants of N. tangutorum. We found, for the first time, that higher nitrogen contents in heterotrophic organs were significantly correlated with increased heterotrophic 13C enrichment compared to leaves. However, phosphorous contents had no effect on the enrichment. In addition, new leaves had carbon isotope ratios similar to roots but were progressively depleted in 13C as they matured. We concluded that a nitrogen-mediated process, hypothesized to be the refixation of respiratory CO 2 by phosphoenolpyruvate (PEP) carboxylase, was responsible for the differences in 13C enrichment among different heterotrophic organs, while processes such as fractionating foliar metabolism and preferentially loading into phloem of 13C-enriched sugars may contribute to the overall autotrophic–heterotrophic difference in carbon isotope compositions.« less

Hydrogen Isotope Fractionation during the Biodegradation of 1,2-Dichloroethane: Potential for Pathway Identification Using a Multi-element (C, Cl, and H) Isotope Approach.

PubMed

Palau, Jordi; Shouakar-Stash, Orfan; Hatijah Mortan, Siti; Yu, Rong; Rosell, Monica; Marco-Urrea, Ernest; Freedman, David L; Aravena, Ramon; Soler, Albert; Hunkeler, Daniel

2017-09-19

Even though multi-element isotope fractionation patterns provide crucial information with which to identify contaminant degradation pathways in the field, those involving hydrogen are still lacking for many halogenated groundwater contaminants and degradation pathways. This study investigates for the first time hydrogen isotope fractionation during both aerobic and anaerobic biodegradation of 1,2-dichloroethane (1,2-DCA) using five microbial cultures. Transformation-associated isotope fractionation values (ε bulk H ) were -115 ± 18‰ (aerobic C-H bond oxidation), -34 ± 4‰ and -38 ± 4‰ (aerobic C-Cl bond cleavage via hydrolytic dehalogenation), and -57 ± 3‰ and -77 ± 9‰ (anaerobic C-Cl bond cleavage via reductive dihaloelimination). The dual-element C-H isotope approach (Λ C-H = Δδ 2 H/Δδ 13 C ≈ ε bulk H /ε bulk C , where Δδ 2 H and Δδ 13 C are changes in isotope ratios during degradation) resulted in clearly different Λ C-H values: 28 ± 4 (oxidation), 0.7 ± 0.1 and 0.9 ± 0.1 (hydrolytic dehalogenation), and 1.76 ± 0.05 and 3.5 ± 0.1 (dihaloelimination). This result highlights the potential of this approach to identify 1,2-DCA degradation pathways in the field. In addition, distinct trends were also observed in a multi- (i.e., Δδ 2 H versus Δδ 37 Cl versus Δδ 13 C) isotope plot, which opens further possibilities for pathway identification in future field studies. This is crucial information to understand the mechanisms controlling natural attenuation of 1,2-DCA and to design appropriate strategies to enhance biodegradation.

Isotopic Resonance Hypothesis: Experimental Verification by Escherichia coli Growth Measurements

NASA Astrophysics Data System (ADS)

Xie, Xueshu; Zubarev, Roman A.

2015-03-01

Isotopic composition of reactants affects the rates of chemical and biochemical reactions. As a rule, enrichment of heavy stable isotopes leads to progressively slower reactions. But the recent isotopic resonance hypothesis suggests that the dependence of the reaction rate upon the enrichment degree is not monotonous. Instead, at some ``resonance'' isotopic compositions, the kinetics increases, while at ``off-resonance'' compositions the same reactions progress slower. To test the predictions of this hypothesis for the elements C, H, N and O, we designed a precise (standard error +/-0.05%) experiment that measures the parameters of bacterial growth in minimal media with varying isotopic composition. A number of predicted resonance conditions were tested, with significant enhancements in kinetics discovered at these conditions. The combined statistics extremely strongly supports the validity of the isotopic resonance phenomenon (p << 10-15). This phenomenon has numerous implications for the origin of life studies and astrobiology, and possible applications in agriculture, biotechnology, medicine, chemistry and other areas.

New Hafnium Isotope and Trace Element Constraints on the Role of a Plume in Genesis of the Eastern Snake River Plain Basalts, Idaho

NASA Astrophysics Data System (ADS)

Taylor, R. D.; Reid, M. R.; Blichert-Toft, J.

2009-12-01

Bimodal volcanism associated with the eastern Snake River Plain (ESRP)-Yellowstone Plateau province has persisted since approximately 16 Ma. A time-transgressive track of rhyolitic eruptions which young progressively to the east and parallel the motion of the North American plate are overlain by younger basalts with no age progression. Interpretations for the origin of these basalts range from a thermo-chemical mantle plume to incipient melting of the shallow upper mantle, and remain controversial. The enigmatic ESRP basalts are characterized by high 3He/4He, diagnostic of a plume source, but also by lithophile radiogenic isotope signatures that are more enriched than expected for plume-derived OIBs. These features could possibly be caused by isotopic decoupling associated with shallow melting of a hybridized upper mantle, or derivation from an atypical mantle plume, or both by way of mixing. New Hf isotope and trace element data further constrain potential sources for the ESRP basalts. Their Hf isotopic signatures (ɛHf = +0.1 to -5.8) are moderately enriched and consistently fall above or in the upper part of the field of OIBs, with similar Nd isotope signatures (ɛNd = -2.0 to -5.8), indicating a source with high time-integrated Lu/Hf compared with Sm/Nd. The isotopic compositions of the basalts lie between those of Archean SCML and a more depleted end-member source, suggestive of contributions from at least two sources. The grouping of isotopic characteristics is compact compared to other regional volcanism, implying that the hybridization process is highly reproducible within the ESRP. Minor localized differences in isotopic composition may signify local variations in the relative proportions of the end-members. Trace element patterns also support genesis of the ESRP basalts from an enriched source. Our data detect evidence of deeper contributions derived from the garnet-stability field, and a greater affinity of the trace element signatures to plume sources than to sources in the mantle lithosphere. The Hf isotope and trace element characteristics of the ESRP basalts thus support a model of derivation from a deep mantle plume with additional melt contributions and isotopic overprinting from SCML.

Constraints of costal aquifer functioning in a deeply antropized area through a multi-isotope fingerprinting (Recife, Brazil)

NASA Astrophysics Data System (ADS)

Petelet-Giraud, Emmanuelle; Cary, Lise; Bertrand, Guillaume; Hirata, Ricardo; Martins, Veridiana; Montenegro, Suzana; Pauwels, Hélène; Kloppmann, Wolfram; Aquilina, Luc

2014-05-01

The Metropolitan Region of Recife (RMR) went through large changes of water and land uses over the last decades due to an increasing demographic pressure (1.5 M of inhabitants). These evolutions gave rise to numerous environmental consequences, such as a dramatic decline of the water levels, groundwater salinization and contamination. This degradation of natural resources is linked to the increase of water demand that is also punctually amplified by drought periods, inducing the construction of thousands of private wells. Recife city was built on an estuarine area, at the geological limits of the two sedimentary basins of Pernambuco (north of the city) and Paraíba (south of the city) separated by a famous shear zone (the Pernambuco lineament). Tectonic and sedimentary events involved in the genesis and evolution of these basins were mainly controlled by the opening of the Atlantic Ocean leading to the deposition of cretaceous sediments which now constitute the two main exploited aquifers, the Beberibe and Cabo aquifers. These two deep aquiferous formations are topped by the unconfined Boa Viagem aquifer of quaternary sediments. It is the most directly exposed to contamination, since it is connected to mangroves, rivers, estuaries and highly urbanized areas. Both the Beberibe and Cabo aquifers contain large clay levels and are separated by a rather continuous clayed formation which seems to play a consistent role of screen and to interfere in the hydraulic connections between the three aquifers. Previous isotopic studies have shown that recharge processes are similar in the aquifers, suggesting that exchanges may occur and may be modified or amplified by overexploitation. This very complex aquifer system is studied through more than 60 water samples, including some surface water samples from the main rivers. A methodology based on multi-isotopes fingerprinting is applied, including stable isotopes of the water molecule, strontium isotopes, boron isotopes, sulfur and oxygen isotopes of sulfates, together with major and trace elements. The main objectives are to better constrain (1) the recharge processes and connections between aquifers, and (2) the water quality degradation by exploring the salinization processes with direct seawater intrusion, paleo-seawater and/or recharge with salty water in the mangrove area, and also contamination due to urban activities. The first results highlighted the complexity of salinity sources and processes in the system. An important compartmentalization between aquifers and within the same aquifer units was observed with very distinct water signatures (87Sr/86Sr, d11B) at the same depth for wells located in the same street block. Groundwater residence time seems to indicate that some groundwaters were recharged under a colder climate, i.e 10-15 ky, with locally a very limited modern recharge. This point is of primary importance in terms of groundwater management of this strategic and fragile resource.

Groundwater Recharge and Flow Regime revealed by multi-tracers approach in a headwater, North China Plain

NASA Astrophysics Data System (ADS)

Sakakibara, Koichi; Tsujimura, Maki; Song, Xianfang; Zhang, Jie

2014-05-01

Groundwater recharge is a crucial hydrological process for effective water management especially in arid/ semi-arid regions. However, the insufficient number of specific research regarding groundwater recharge process has been reported previously. Intensive field surveys were conducted during rainy season, mid dry season, and end of dry season, in order to clarify comprehensive groundwater recharge and flow regime of Wangkuai watershed in a headwater, which is a main recharge zone of North China Plain. The groundwater, spring, stream water and lake water were sampled, and inorganic solute constituents and stable isotopes of oxygen 18 and deuterium were determined on all water samples. Also the stream flow rate was observed. The solute ion concentrations and stable isotopic compositions show that the most water of this region can be characterized by Ca-HCO3 type and the main water source is precipitation which is affected by altitude effect of stable isotopes. In addition, the river and reservoir of the area seem to recharge the groundwater during rainy season, whereas interaction between surface water and groundwater does not become dominant gradually after the rainy season. The inversion analysis applied in Wangkuai watershed using simple mixing model represents an existing multi-flow systems which shows a distinctive tracer signal and flow rate. In summary, the groundwater recharged at different locations in the upper stream of Wangkuai reservoir flows downward to alluvial fan with a certain amount of mixing together, also the surface water recharges certainly the groundwater in alluvial plain in the rainy season.

Land-Sea relationships of climate-related records: example of the Holocene in the eastern Canadian Arctic and Greenland

NASA Astrophysics Data System (ADS)

de Vernal, Anne; Fréchette, Bianca; Hillaire-Marcel, Claude

2017-04-01

Anne de Vernal, Bianca Fréchette, Claude Hillaire-Marcel Important progresses have been made to reconstruct climate and ocean changes through time. However, there is often a hiatus between the land-based climate reconstructions and paleoceanographical data. The reconstructed parameters are not the same (e.g. surface air temperature vs. sea-surface temperature). Moreover, the spatial (local to regional) and temporal dimensions (seasonal, annual to multi-decadal) of proxy-data are often inconsistent, thus preventing direct correlation of time series and often leading to uncertainties in multi-site, multi-proxy compilations. Here, we address the issue of land-sea relationships in the eastern Canadian Arctic-Baffin Bay-Labrador Sea-western Greenland based on the examination of different climate-related information from marine cores (dinocysts) collected nearshore vs. offshore, ice cores (isotopes), fjord and lake data (pollen). The combined information tends to indicate that "climate" changes are not easily neither adequately captured by temperature and temperature shifts. However, the seasonal contrast of temperatures seems to be a key parameter. Whereas it is often attenuated offshore, it is generally easy to reconstruct nearshore, where water stratification is usually stronger. The confrontation of data also shows a relationship between ice core data and sea-ice cover and/or sea-surface salinity, suggesting that air-sea exchanges in basins surrounding ice sheets play a significant role with respect to their isotopic composition. On the whole, combined onshore-offshore data consistently suggest a two-step shift towards optimal summer and winter conditions the circum Baffin Bay and northern Labrador Sea at 7.5 and 6 ka BP. These delayed optimal conditions seem to result from ice-meltwater discharges maintaining low salinity conditions in marine surface waters and thus a strong seasonality.

Multi-element, multi-compound isotope profiling as a means to distinguish the geographical and varietal origin of fermented cocoa (Theobroma cacao L.) beans.

PubMed

Diomande, Didier; Antheaume, Ingrid; Leroux, Maël; Lalande, Julie; Balayssac, Stéphane; Remaud, Gérald S; Tea, Illa

2015-12-01

Multi-element stable isotope ratios have been assessed as a means to distinguish between fermented cocoa beans from different geographical and varietal origins. Isotope ratios and percentage composition for C and N were measured in different tissues (cotyledons, shells) and extracts (pure theobromine, defatted cocoa solids, protein, lipids) obtained from fermented cocoa bean samples. Sixty-one samples from 24 different geographical origins covering all four continental areas producing cocoa were analyzed. Treatment of the data with unsupervised (Principal Component Analysis) and supervised (Partial Least Squares Discriminant Analysis) multiparametric statistical methods allowed the cocoa beans from different origins to be distinguished. The most discriminant variables identified as responsible for geographical and varietal differences were the δ(15)N and δ(13)C values of cocoa beans and some extracts and tissues. It can be shown that the isotope ratios are correlated with the altitude and precipitation conditions found in the different cocoa-growing regions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Multi-purpose hydrogen isotopes separation plant design

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

Boniface, H.A.; Gnanapragasam, N.V.; Ryland, D.K.

2015-03-15

There is a potential interest at AECL's Chalk River Laboratories to remove tritium from moderately tritiated light water and to reclaim tritiated, downgraded heavy water. With only a few limitations, a single CECE (Combined Electrolysis and Catalytic Exchange) process configuration can be designed to remove tritium from heavy water or light water and upgrade heavy water. Such a design would have some restrictions on the nature of the feed-stock and tritium product, but could produce essentially tritium-free light or heavy water that is chemically pure. The extracted tritium is produced as a small quantity of tritiated heavy water. The overallmore » plant capacity is fixed by the total amount of electrolysis and volume of catalyst. In this proposal, with 60 kA of electrolysis a throughput of 15 kg*h{sup -1} light water for detritiation, about 4 kg*h{sup -1} of heavy water for detritiation and about 27 kg*h{sup -1} of 98% heavy water for upgrading can be processed. Such a plant requires about 1,000 liters of AECL isotope exchange catalyst. The general design features and details of this multi-purpose CECE process are described in this paper, based on some practical choices of design criteria. In addition, we outline the small differences that must be accommodated and some compromises that must be made to make the plant capable of such flexible operation. (authors)« less

Assessing the role of clay authigenesis in the seawater potassium cycle: A paired K and Mg isotope study of deep-sea pore fluids

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

In situ formation of clays (clay authigenesis) in marine sediments and altered oceanic crust is an important sink of a number of seawater cations. In particular, clay authigenesis is a major, and yet unconstrained, flux in the global seawater potassium cycle. Potassium is the fourth most abundant cation in the ocean, which constitutes an isotopically enriched K reservoir (δ41K 0‰) compared to the solid Earth (δ41K -0.5‰). Understanding what processes control this isotopic offset is the main goal of this study. Here we use a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) to measure the K and Mg isotope ratios (41K/39K and 26Mg/24Mg) of deep-sea pore fluids in order to assess the effects of clay formation in the K isotope composition of seawater. Mg isotopes are used as an independent proxy for clay formation, since marine authigenic clays are isotopically distinct from their detrital counterpart, an abundant component of marine sediments. Our study sites (ODP/IODP 1052, U1378, U1395, U1403) vary in location, lithology, age and sedimentation rates; however, pore-fluids from all sites show decreasing K concentrations with depth, suggesting potassium uptake into the sediments. We find that although K concentration trends are similar across all sites, measured δ41K values vary significantly. Results from 1-D diffusion-advection-reaction models suggest that these differences in isotopic profiles arise from a complex interplay between sedimentation rate and K isotopic fractionation during clay formation, aqueous K diffusion and ion exchange reactions. Further, model simulations yield fractionation factors between 0.9980 and 1.0000 for clay formation in deep-sea sediments. Despite the minor contribution of these deep-sea pore-fluids as sinks of seawater K, the processes responsible for K isotope fractionation in our study sites (clay formation and aqueous K diffusion) are also observed at shallow marine systems (major K sinks) and are thus likely responsible for setting the K isotopic composition of seawater.

Insights into Mechanistic Models for Evaporation of Organic Liquids in the Environment Obtained by Position-Specific Carbon Isotope Analysis.

PubMed

Julien, Maxime; Nun, Pierrick; Robins, Richard J; Remaud, Gérald S; Parinet, Julien; Höhener, Patrick

2015-11-03

Position-specific isotope effects (PSIEs) have been measured by isotope ratio monitoring (13)C nuclear magnetic resonance spectrometry during the evaporation of 10 liquids of different polarities under 4 evaporation modes (passive evaporation, air-vented evaporation, low pressure evaporation, distillation). The observed effects are used to assess the validity of the Craig-Gordon isotope model for organic liquids. For seven liquids the overall isotope effect (IE) includes a vapor-liquid contribution that is strongly position-specific in polar compounds but less so in apolar compounds and a diffusive IE that is not position-specific, except in the alcohols, ethanol and propan-1-ol. The diffusive IE is diminished under forced evaporation. The position-specific isotope pattern created by liquid-vapor IEs is manifest in five liquids, which have an air-side limitation for volatilization. For the alcohols, undefined processes in the liquid phase create additional PSIEs. Three other liquids with limitations on the liquid side have a lower, highly position-specific, bulk diffusive IE. It is concluded that evaporation of organic pollutants creates unique position-specific isotope patterns that may be used to assess the progress of remediation or natural attenuation of pollution and that the Craig-Gordon isotope model is valid for the volatilization of nonpolar organic liquids with air-side limitation of the volatilization rate.

[Progress in stable isotope labeled quantitative proteomics methods].

PubMed

Zhou, Yuan; Shan, Yichu; Zhang, Lihua; Zhang, Yukui

2013-06-01

Quantitative proteomics is an important research field in post-genomics era. There are two strategies for proteome quantification: label-free methods and stable isotope labeling methods which have become the most important strategy for quantitative proteomics at present. In the past few years, a number of quantitative methods have been developed, which support the fast development in biology research. In this work, we discuss the progress in the stable isotope labeling methods for quantitative proteomics including relative and absolute quantitative proteomics, and then give our opinions on the outlook of proteome quantification methods.

Identification of the geographical place of origin of an unidentified individual by multi-isotope analysis.

PubMed

Font, Laura; van der Peijl, Gerard; van Leuwen, Carina; van Wetten, Isis; Davies, Gareth R

2015-01-01

A multi-isotope investigation (Sr and Pb isotopes and δ18O, δ13C and δ15N) was applied to bone and teeth from an unidentified male found drowned in the"IJ" Ruyterkade in Amsterdam, The Netherlands in March of 1999. The individual remained unidentified until mid 2013, after the isotope study was completed. Coupled δ13C and δ15N values in bone collagen recovered from rib and femur are consistent with an omnivore living in a region where C3-type diet dominates (i.e. Europe). Integrated Sr and Pb isotopes and δ18O values in canine and third molar teeth and femur and rib bone data exclude extended residence in north-west Europe and particularly The Netherlands. Characteristic Pb isotope ratios coupled with inferred δ18O values of drinking water argue for a most probable place of origin for the unidentified individual in west and south Poland, south-east Slovakia and the region of Ukraine-Romania-Bulgaria, specifically the region associated with the Carpathian Mountains. Independent of the isotope study, the Cold Case Team made a positive identification with an individual from south-west Poland, validating the results of the multiple-isotopic approach. Copyright © 2014 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Multi-element isotope fractionation concepts to characterize the biodegradation of hydrocarbons - from enzymes to the environment.

PubMed

Vogt, Carsten; Dorer, Conrad; Musat, Florin; Richnow, Hans-Hermann

2016-10-01

Multi-element compound-specific isotope fractionation (ME-CSIA) has become a state-of-the-art approach for identifying biotransformation reactions. In the last decade, several studies focused on the combined analysis of carbon and hydrogen stable isotopes upon biodegradation of hydrocarbons due to its widespread environmental occurrence as contaminants, often in high concentrations. Most known initial transformation reactions of hydrocarbons have been isotopically characterized in laboratory experiments using model cultures. The data suggest that several of these reactions - especially those occurring under anoxic conditions - can be identified by ME-CSIA, although a number of constraints have been realized which may lead to wrong ME-CSIA data interpretations in field studies. Generally, the applicability of ME-CSIA regarding hydrocarbon biodegradation needs to be corroborated in future field studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Lithium and carbon isotopes in river catchment: combined tracers to constrain chemical weathering processes

NASA Astrophysics Data System (ADS)

Rad, S.; Rive, K.; Assayag, N.; Dictor, M.; Garcin, M.

2012-12-01

Water-rock interactions produced in river catchment are accompanied by fractionation or changes in stable isotopes such as H, Li, C and O during chemical weathering processes. Li is a fluid-mobile element that tends to preferentially partition into the fluid phase during water-rock interaction. The relative mass difference between the two isotopes is considerable, generating large mass dependent fractionation during chemical weathering processes. The CO2 dissolves into the water providing the main acid that attack the rock during chemical weathering. Carbon stable isotopes and concentration of Dissolved Inorganic Carbon (DIC) in the river catchment can be used to determine the origin and consumption rates of CO2. In the present work, stable isotopes were analyzed in Allier River, one of the major river basins of France. The lithology is dominated by granite rocks within current upstream, while it is mainly basaltic and Oligocene sediments in the downstream with hydrothermal manifestations. We propose a new isotopic approach by combining δ7Li and δ13CDIC analyses in river catchment waters. A first method has been applied to volcanic tropical environments with Li concentrations correlated to δ13CDIC (Rad et al., 2011). Here, we have completed this approach by lithium isotopes. Water samples were collected during several field trips. Our results show a large variation in Li isotopes and C isotopes within the catchment from 3.3 ‰ to 30.3 ‰ and from -17.9‰ to -3.5‰, respectively. Chemical weathering rates linearly increase from upstream to downstream over 400km distance, whereas Li isotope signatures decrease and global C signature increases. This is due to low water-rock interaction dominated in upstream, whereas the downstream is punctually impacted by hydrothermalism. From Li and C isotopes, our results show 4 groups reflecting different chemical weathering processes: the first group with high fractionation of Li and C, for Li, the heavy lithium partitioned into surface waters, leaving lighter lithium behind in the weathered products, the signature of C is mainly due to organic matter or partially due to biochemical interaction with assimilation of CO2 by microorganism. The second group involves atmospheric equilibrium with CO2 degassing with organic origin or "cold" CO2 degassing with important fraction of Li. The third group present high fractionation of C, reflecting presence of superficial C with organic origin, with low fractionation of Li underling the hydrothermalism impact. Finally a fourth group with low fractionation mainly due to high temperature water-rock interaction. Therefore, the combination of the two tracers, Li and C isotopes, offers a powerful tool to discriminate chemical weathering processes from sources of alteration during water-rock interactions under multi-lithology terrains. Reference: Rad, S., Rivé, K., Allègre, C.J., 2011. Weathering regime associated with subsurface circulation on volcanic islands. Aquat. Geochem. 17, 3, 221-241.

Heavy Ion Fragmentation Experiments at the Bevatron

NASA Technical Reports Server (NTRS)

Heckman, H. H.

1975-01-01

Fragmentation processes of heavy nuclei in matter using the heavy-ion capability of the Bevatron were studied. The purpose was to obtain the single particle inclusive spectra of secondary nuclei produced at 0 deg by the fragmentation of heavy ion beam projectiles. The process being examined is B+T yields F + anything, where B is the beam nucleus, T is the target nucleus, and F is the detected fragment. The fragments F are isotopically identified by experimental procedures involving magnetic analysis, energy loss and time-of-flight measurements. Attempts were also made to: (1) measure the total and partial production cross section for all isotopes, (2) test the applicability of high-energy multi-particle interaction theory to nuclear fragmentation, (3) apply the cross-section data and fragmentation probabilities to cosmic ray transport theory, and (4) search for systematic behavior of fragment production as a means to improve existing semi-empirical theories of cross sections.

Mechanism of Aromatic Hydrocarbon Induced Mammary Tumorigenesis

DTIC Science & Technology

1999-07-01

the de-differentiation process of one form of cancer. These studies have been reported (Ashba and Traish, 1999; cf enclosed manuscript). SPECIFIC...be a multi-stage process . The progression of this disease is associated with cellular and molecular changes. Thus, initiation and progression may be...9,10,17-21). Whole aqueous extracts, decaffeinated extracts and purified components of tea have been found effective to varying degrees in the different

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.

Characterization Of Nuclear Materials Using Time-Of-Flight ICP-MS

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

Buerger, Stefan; Riciputi, Lee R; Bostick, Debra A

2006-01-01

The investigation of illicit trafficking of nuclear materials, nuclear safeguards analysis, and non-proliferation control requires sensitive and isotope-selective detection methods to gain crucial nuclear forensic information like isotope 'fingerprints' and multi-element signatures. The advantage of time-of-flight (TOF) mass spectrometry - quasi-simultaneous multi-mass analysis - combined with an inductively coupled plasma (ICP) ion source provides an analytical instrument with multi-element and multi-isotope capability and good detection limits. A TOF-ICP-MS system thus appears to be an advantageous choice for the investigation and characterization of nuclear materials. We present here results using a GBC OptiMass 8000 time-of-flight ICP-MS for the isotope screening ofmore » solid samples by laser ablation and the multi-element determination of impurities in uranium ore concentrates using matrix matched standards. A laser ablation system (New Wave Research, UP 213) coupled to the TOF-ICP-MS instrument has been used to optimize the system for analysis of non-radioactive metal samples of natural isotopic composition for a variety of elements including Cu, Sr, Zr, Mo, Cd, In, Ba, Ta, W, Re, Pt, and Pb in pure metals, alloys, and glasses to explore precision, accuracy, and detection limits. Similar methods were then applied to measure uranium. When the laser system is optimized, no mass bias correction is required. Precision and accuracy for the determination of the isotopic composition is typically 1 - 3% for elemental concentrations of as little as 50 ppm in the matrix, with no requirement for sample preparation. The laser ablation precision and accuracy are within ~10x of the instrumental limits for liquid analysis (0.1%). We have investigated the capabilities of the TOF-ICP-MS for the analysis of impurities in uranium matrices. Matrix matching has been used to develop calibration curves for a range of impurities (alkaline, earth-alkaline, transition metals, and rare earth elements). These calibration curves have been used to measure impurities in a number of uranium samples. The results from the TOF-ICP-MS will be compared with other mass spectrometric methods.« less

Abiogenic formation of alkanes in the Earth's crust as a minor source for global hydrocarbon reservoirs.

PubMed

Sherwood Lollar, B; Westgate, T D; Ward, J A; Slater, G F; Lacrampe-Couloume, G

2002-04-04

Natural hydrocarbons are largely formed by the thermal decomposition of organic matter (thermogenesis) or by microbial processes (bacteriogenesis). But the discovery of methane at an East Pacific Rise hydrothermal vent and in other crustal fluids supports the occurrence of an abiogenic source of hydrocarbons. These abiogenic hydrocarbons are generally formed by the reduction of carbon dioxide, a process which is thought to occur during magma cooling and-more commonly-in hydrothermal systems during water-rock interactions, for example involving Fischer-Tropsch reactions and the serpentinization of ultramafic rocks. Suggestions that abiogenic hydrocarbons make a significant contribution to economic hydrocarbon reservoirs have been difficult to resolve, in part owing to uncertainty in the carbon isotopic signatures for abiogenic versus thermogenic hydrocarbons. Here, using carbon and hydrogen isotope analyses of abiogenic methane and higher hydrocarbons in crystalline rocks of the Canadian shield, we show a clear distinction between abiogenic and thermogenic hydrocarbons. The progressive isotopic trends for the series of C1-C4 alkanes indicate that hydrocarbon formation occurs by way of polymerization of methane precursors. Given that these trends are not observed in the isotopic signatures of economic gas reservoirs, we can now rule out the presence of a globally significant abiogenic source of hydrocarbons.

Neutron-rich isotope production using the uranium carbide multi-foil SPES target prototype

NASA Astrophysics Data System (ADS)

Scarpa, D.; Biasetto, L.; Corradetti, S.; Manzolaro, M.; Andrighetto, A.; Carturan, S.; Prete, G.; Zanonato, P.; Stracener, D. W.

2011-03-01

In the framework of the R&D program for the SPES (Selective Production of Exotic Species) project of the Istituto Nazionale di Fisica Nucleare (INFN), production yields of neutron-rich isotopes have been measured at the Holifield Radioactive Ion Beam Facility (HRIBF, Oak Ridge National Laboratory, USA). This experiment makes use of the multi-foil SPES target prototype composed of 7 uranium carbide discs, with excess of graphite (ratio C/ U = 4 . 77 isotopes of medium mass (between 72 and 141amu), produced via proton-induced fission of uranium using a 40MeV proton beam, have been collected and analyzed for the target heated at 2000 ° C target temperature.

Transient signal isotope analysis: validation of the method for isotope signal synchronization with the determination of amplifier first-order time constants.

PubMed

Gourgiotis, Alkiviadis; Manhès, Gérard; Louvat, Pascale; Moureau, Julien; Gaillardet, Jérôme

2015-09-30

During transient signal acquisition by Multi-Collection Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS), an isotope ratio increase or decrease (isotopic drift hereafter) is often observed which is related to the different time responses of the amplifiers involved in multi-collection. This isotopic drift affects the quality of the isotopic data and, in a recent study, a method of internal amplifier signal synchronization for isotope drift correction was proposed. In this work the determination of the amplifier time constants was investigated in order to validate the method of internal amplifier signal synchronization for isotope ratio drift correction. Two different MC-ICPMS instruments, the Neptune and the Neptune Plus, were used, and both the lead transient signals and the signal decay curves of the amplifiers were investigated. Our results show that the first part of the amplifier signal decay curve is characterized by a pure exponential decay. This part of the signal decay was used for the effective calculation of the amplifier first-order time constants. The small differences between these time constants were compared with time lag values obtained from the method of isotope signal synchronization and were found to be in good agreement. This work proposes a way of determining amplifier first-order time constants. We show that isotopic drift is directly related to the amplifier first-order time constants and the method of internal amplifier signal synchronization for isotope ratio drift correction is validated. Copyright © 2015 John Wiley & Sons, Ltd.

Plutonium isotopic signatures in soils and their variation (2011-2014) in sediment transiting a coastal river in the Fukushima Prefecture, Japan.

PubMed

Jaegler, Hugo; Pointurier, Fabien; Onda, Yuichi; Hubert, Amélie; Laceby, J Patrick; Cirella, Maëva; Evrard, Olivier

2018-05-04

The Fukushima Daiichi Nuclear Power Plant (FDNPP) accident resulted in a significant release of radionuclides that were deposited on soils in Northeastern Japan. Plutonium was detected at trace levels in soils and sediments collected around the FDNPP. However, little is known regarding the spatial-temporal variation of plutonium in sediment transiting rivers in the region. In this study, plutonium isotopic compositions were first measured in soils (n = 5) in order to investigate the initial plutonium deposition. Then, plutonium isotopic compositions were measured on flood sediment deposits (n = 12) collected after major typhoon events in 2011, 2013 and 2014. After a thorough radiochemical purification, isotopic ratios ( 240 Pu/ 239 Pu, 241 Pu/ 239 Pu and 242 Pu/ 239 Pu) were measured with a Multi-Collector Inductively Coupled Mass Spectrometer (MC ICP-MS), providing discrimination between plutonium derived from global fallout, from atmospheric nuclear weapon tests, and plutonium derived from the FDNPP accident. Results demonstrate that soils with the most Fukushima-derived plutonium were in the main radiocaesium plume and that there was a variable mixture of plutonium sources in the flood sediment samples. Plutonium concentrations and isotopic ratios generally decreased between 2011 and 2014, reflecting the progressive erosion and transport of contaminated sediment in this coastal river during flood events. Exceptions to this general trend were attributed to the occurrence of decontamination works or the remobilisation of contaminated material during typhoons. The different plutonium concentrations and isotopic ratios obtained on three aliquots of a single sample suggest that the Fukushima-derived plutonium was likely borne by discrete plutonium-containing particles. In the future, these particles should be isolated and further characterized in order to better understand the fate of this long-lived radionuclide in the environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dual Si and O Isotope Measurement of Lunar Samples Using IRMS

NASA Astrophysics Data System (ADS)

Banerjee, N.; Hill, P. J. A.; Osinski, G. R.

2016-12-01

The use of isotopic systems and their associated theoretical models have become an increasingly sophisticated tool for investigating the origin of planetary bodies in the solar system. It was originally hypothesized that evidence for the impact origin of Moon would manifest itself as an isotopic heterogeneity between lunar and terrestrial samples; however, most isotope systems show no difference between the bulk Earth and Moon. The stable isotopes of both silicon (Si) and oxygen (O) have been essential in further understanding planetary processes including core formation. Historically the analysis of the Si and O isotope ratios in terrestrial and extraterrestrial material has primarily been measured independent of each other through three main techniques: isotope ratio mass spectrometry (IRMS), secondary ion mass spectrometry (SIMS), and multi-collector inductively coupled plasma mass-spectrometry (MC-ICPMS). Each technique has its own strength and weakness in regards to resolution and precision; however, one of the main limiting factors in all three of these techniques rests on the requirement of multiple aliquots. As most literature focuses on the measurement of oxygen or silicon isotopes, this unique line allows for the precise analysis of Si and O isotopes from the same aliquot of bulk sample, which cannot be done with SIMS or ICP-MS analysis. To deal with this problem a unique laser line system has been developed in the Laboratory for Stable Isotope Science at Western University, Canada, that simultaneously extracts SiF4 and O2 from the same 1-2 mg aliquot. We present the application of analyzing both isotopic systems from the sample aliquot to Apollo, meteoritic, and terrestrial samples and its implication for the formation of the Moon. Preliminary results from this line suggest that although the O isotopes ratios are consistent with a homogenous Moon-Earth system, a difference is observed in Si isotopes between Apollo and terrestrial samples compared to previous studies.

Developing a Multi-Year Learning Progression for Carbon Cycling in Socio-Ecological Systems

ERIC Educational Resources Information Center

Mohan, Lindsey; Chen, Jing; Anderson, Charles W.

2009-01-01

This study reports on our steps toward achieving a conceptually coherent and empirically validated learning progression for carbon cycling in socio-ecological systems. It describes an iterative process of designing and analyzing assessment and interview data from students in upper elementary through high school. The product of our development…

Lead isotope studies of the Guerrero composite terrane, west-central Mexico: implications for ore genesis

NASA Astrophysics Data System (ADS)

Potra, Adriana; Macfarlane, Andrew W.

2014-01-01

New thermal ionization mass spectrometry and multi-collector inductively coupled plasma mass spectrometry Pb isotope analyses of three Cenozoic ores from the La Verde porphyry copper deposit located in the Zihuatanejo-Huetamo subterrane of the Guerrero composite terrane are presented and the metal sources are evaluated. Lead isotope ratios of 3 Cenozoic ores from the El Malacate and La Esmeralda porphyry copper deposits located in the Zihuatanejo-Huetamo subterrane and of 14 ores from the Zimapan and La Negra skarn deposits from the adjoining Sierra Madre terrane are also presented to look for systematic differences in the lead isotope trends and ore metal sources among the proposed exotic tectonostratigraphic terranes of southern Mexico. Comparison among the isotopic signatures of ores from the Sierra Madre terrane and distinct subterranes of the Guerrero terrane supports the idea that there is no direct correlation between the distinct suspect terranes of Mexico and the isotopic signatures of the associated Cenozoic ores. Rather, these Pb isotope patterns are interpreted to reflect increasing crustal contribution to mantle-derived magmas as the arc advanced eastward onto a progressively thicker continental crust. The lead isotope trend observed in Cenozoic ores is not recognized in the ores from Mesozoic volcanogenic massive sulfide and sedimentary exhalative deposits. The Mesozoic ores formed prior to the amalgamation of the Guerrero composite terrane to the continental margin, which took place during the Late Cretaceous, in intraoceanic island arc and intracontinental marginal basin settings, while the Tertiary deposits formed after this event in a continental arc setting. Lead isotope ratios of the Mesozoic and Cenozoic ores appear to reflect these differences in tectonic setting of ore formation. Most Pb isotope values of ores from the La Verde deposit (206Pb/204Pb = 18.674-18.719) are less radiogenic than those of the host igneous rocks, but plot within the field defined by the Huetamo Sequence, suggesting that these ores may also contain metals from the sedimentary rocks. The Pb isotope ratios of ore samples from the Zimapan deposit (206Pb/204Pb = 18.771-18.848) are substantially higher than the whole-rock Pb isotope compositions of the basement rocks. The similarity of ore Pb to igneous rock Pb in the Zimapan district (206Pb/204Pb = 18.800-18.968) may indicate that the proximal source of ore metals in the hydrothermal system was the igneous activity.

Direct uranium isotope ratio analysis of single micrometer-sized glass particles

PubMed Central

Kappel, Stefanie; Boulyga, Sergei F.; Prohaska, Thomas

2012-01-01

We present the application of nanosecond laser ablation (LA) coupled to a ‘Nu Plasma HR’ multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10–20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant 236U/238U isotope ratios (i.e. 10−5). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for 234U/238U and 235U/238U ratios. Experimental results obtained for 236U/238U isotope ratios deviated by less than −2.5% from the certified values. Expanded relative total combined standard uncertainties Uc (k = 2) of 2.6%, 1.4% and 5.8% were calculated for 234U/238U, 235U/238U and 236U/238U, respectively. PMID:22595724

Direct uranium isotope ratio analysis of single micrometer-sized glass particles.

PubMed

Kappel, Stefanie; Boulyga, Sergei F; Prohaska, Thomas

2012-11-01

We present the application of nanosecond laser ablation (LA) coupled to a 'Nu Plasma HR' multi collector inductively coupled plasma mass spectrometer (MC-ICP-MS) for the direct analysis of U isotope ratios in single, 10-20 μm-sized, U-doped glass particles. Method development included studies with respect to (1) external correction of the measured U isotope ratios in glass particles, (2) the applied laser ablation carrier gas (i.e. Ar versus He) and (3) the accurate determination of lower abundant (236)U/(238)U isotope ratios (i.e. 10(-5)). In addition, a data processing procedure was developed for evaluation of transient signals, which is of potential use for routine application of the developed method. We demonstrate that the developed method is reliable and well suited for determining U isotope ratios of individual particles. Analyses of twenty-eight S1 glass particles, measured under optimized conditions, yielded average biases of less than 0.6% from the certified values for (234)U/(238)U and (235)U/(238)U ratios. Experimental results obtained for (236)U/(238)U isotope ratios deviated by less than -2.5% from the certified values. Expanded relative total combined standard uncertainties U(c) (k = 2) of 2.6%, 1.4% and 5.8% were calculated for (234)U/(238)U, (235)U/(238)U and (236)U/(238)U, respectively. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermal equilibration of iron meteorite and pallasite parent bodies recorded at the mineral scale by Fe and Ni isotope systematics

NASA Astrophysics Data System (ADS)

Chernonozhkin, Stepan M.; Weyrauch, Mona; Goderis, Steven; Oeser, Martin; McKibbin, Seann J.; Horn, Ingo; Hecht, Lutz; Weyer, Stefan; Claeys, Philippe; Vanhaecke, Frank

2017-11-01

In this work, a femtosecond laser ablation (LA) system coupled to a multi-collector inductively coupled plasma-mass spectrometer (fs-LA-MC-ICP-MS) was used to obtain laterally resolved (30-80 μm), high-precision combined Ni and Fe stable isotope ratio data for a variety of mineral phases (olivine, kamacite, taenite, schreibersite and troilite) composing main group pallasites (PMG) and iron meteorites. The stable isotopic signatures of Fe and Ni at the mineral scale, in combination with the factors governing the kinetic or equilibrium isotope fractionation processes, are used to interpret the thermal histories of small differentiated asteroidal bodies. As Fe isotopic zoning is only barely resolvable within the internal precision level of the isotope ratio measurements within a single olivine in Esquel PMG, the isotopically lighter olivine core relative to the rim (Δ56/54Ferim-core = 0.059‰) suggests that the olivines were largely thermally equilibrated. The observed hint of an isotopic and concentration gradient for Fe of crudely similar width is interpreted here to reflect Fe loss from olivine in the process of partial reduction of the olivine rim. The ranges of the determined Fe and Ni isotopic signatures of troilite (δ56/54Fe of -0.66 to -0.09‰) and schreibersite (δ56/54Fe of -0.48 to -0.09‰, and δ62/60Ni of -0.64 to +0.29‰) may result from thermal equilibration. Schreibersite and troilite likely remained in equilibrium with their enclosing metal to temperatures significantly below their point of crystallization. The Ni isotopic signatures of bulk metal and schreibersite correlate negatively, with isotopically lighter Ni in the metal of PMGs and isotopically heavier Ni in the metal of the iron meteorites analyzed. As such, the light Ni isotopic signatures previously observed in PMG metal relative to chondrites may not result from heterogeneity in the Solar Nebula, but rather reflect fractionation in the metal-schreibersite system. Comparison between the isotope ratio profiles of Fe and Ni determined across kamacite-taenite interfaces (Δ56/54Fekam-tae = -0.51 to -0.69‰ and Δ62/60Nikam-tae = +1.59 to +2.50‰) and theoretical taenite sub-solidus diffusive isotopic zoning broadly constrain the cooling rates of Esquel, CMS 04071 PMGs and Udei Station IAB to between ∼25 and 500 °C/Myr.

Cross-Calibration of Secondary Electron Multiplier in Noble Gas Analysis

NASA Astrophysics Data System (ADS)

Santato, Alessandro; Hamilton, Doug; Deerberg, Michael; Wijbrans, Jan; Kuiper, Klaudia; Bouman, Claudia

2015-04-01

The latest generation of multi-collector noble gas mass spectrometers has decisively improved the precision in isotopic ratio analysis [1, 2] and helped the scientific community to address new questions [3]. Measuring numerous isotopes simultaneously has two significant advantages: firstly, any fluctuations in signal intensity have no effect on the isotope ratio and secondly, the analysis time is reduced. This particular point becomes very important in static vacuum mass spectrometry where during the analysis, the signal intensity decays and at the same time the background increases. However, when multi-collector analysis is utilized, it is necessary to pay special attention to the cross calibration of the detectors. This is a key point in order to have accurate and reproducible isotopic ratios. In isotope ratio mass spectrometry, with regard to the type of detector (i.e. Faraday or Secondary Electron Multiplier, SEM), analytical technique (TIMS, MC-ICP-MS or IRMS) and isotope system of interest, several techniques are currently applied to cross-calibrate the detectors. Specifically, the gain of the Faraday cups is generally stable and only the associated amplifier must be calibrated. For example, on the Thermo Scientific instrument control systems, the 1011 and 1012 ohm amplifiers can easily be calibrated through a fully software controlled procedure by inputting a constant electric signal to each amplifier sequentially [4]. On the other hand, the yield of the SEMs can drift up to 0.2% / hour and other techniques such as peak hopping, standard-sample bracketing and multi-dynamic measurement must be used. Peak hopping allows the detectors to be calibrated by measuring an ion beam of constant intensity across the detectors whereas standard-sample bracketing corrects the drift of the detectors through the analysis of a reference standard of a known isotopic ratio. If at least one isotopic pair of the sample is known, multi-dynamic measurement can be used; in this case the known isotopic ratio is measured on different pairs of detectors and the true value of the isotopic ratio of interest can be determined by a specific equation. In noble gas analysis, due to the decay of the ion beam during the measurement as well as the special isotopic systematic of the gases themselves, the cross-calibration of the SEM using these techniques becomes more complex and other methods should be investigated. In this work we present a comparison between different approaches to cross-calibrate multiple SEM's in noble gas analysis in order to evaluate the most suitable and reliable method. References: [1] Mark et al. (2009) Geochem. Geophys. Geosyst. 10, 1-9. [2] Mark et al. (2011) Geochim. Cosmochim. 75, 7494-7501. [3] Phillips and Matchan (2013) Geochimica et Cosmochimica Acta 121, 229-239. [4] Koornneef et al. (2014) Journal of Analytical Atomic Spectrometry 28, 749-754.

Integrating Stomach Content and Stable Isotope Analyses to Quantify the Diets of Pygoscelid Penguins

PubMed Central

Polito, Michael J.; Trivelpiece, Wayne Z.; Karnovsky, Nina J.; Ng, Elizabeth; Patterson, William P.; Emslie, Steven D.

2011-01-01

Stomach content analysis (SCA) and more recently stable isotope analysis (SIA) integrated with isotopic mixing models have become common methods for dietary studies and provide insight into the foraging ecology of seabirds. However, both methods have drawbacks and biases that may result in difficulties in quantifying inter-annual and species-specific differences in diets. We used these two methods to simultaneously quantify the chick-rearing diet of Chinstrap (Pygoscelis antarctica) and Gentoo (P. papua) penguins and highlight methods of integrating SCA data to increase accuracy of diet composition estimates using SIA. SCA biomass estimates were highly variable and underestimated the importance of soft-bodied prey such as fish. Two-source, isotopic mixing model predictions were less variable and identified inter-annual and species-specific differences in the relative amounts of fish and krill in penguin diets not readily apparent using SCA. In contrast, multi-source isotopic mixing models had difficulty estimating the dietary contribution of fish species occupying similar trophic levels without refinement using SCA-derived otolith data. Overall, our ability to track inter-annual and species-specific differences in penguin diets using SIA was enhanced by integrating SCA data to isotopic mixing modes in three ways: 1) selecting appropriate prey sources, 2) weighting combinations of isotopically similar prey in two-source mixing models and 3) refining predicted contributions of isotopically similar prey in multi-source models. PMID:22053199

Fractionation of 238U/235U by reduction during low temperature uranium mineralisation processes

NASA Astrophysics Data System (ADS)

Murphy, Melissa J.; Stirling, Claudine H.; Kaltenbach, Angela; Turner, Simon P.; Schaefer, Bruce F.

2014-02-01

Investigations of ‘stable’ uranium isotope fractionation during low temperature, redox transformations may provide new insights into the usefulness of the 238U/235U isotope system as a tracer of palaeoredox processes. Sandstone-hosted uranium deposits accumulate at an oxidation/reduction interface within an aquifer from the low temperature reduction of soluble U(VI) complexes in groundwaters, forming insoluble U(IV) minerals. This setting provides an ideal environment in which to investigate the effects of redox transformations on 238U/235U fractionation. Here we present the first coupled measurements of 238U/235U isotopic compositions and U concentrations for groundwaters and mineralised sediment samples from the same redox system in the vicinity of the high-grade Pepegoona sandstone-hosted uranium deposit, Australia. The mineralised sediment samples display extremely variable 238U/235U ratios (herein expressed as δUCRM145238, the per-mil deviation from the international NBL standard CRM145). The majority of mineralised sediment samples have δUCRM145238 values between -1.30±0.05 and 0.55±0.12‰, spanning a ca. 2‰ range. However, one sample has an unusually light isotopic composition of -4.13±0.05‰, which suggests a total range of U isotopic variability of up to ca. 5‰, the largest variation found thus far in a single natural redox system. The 238U/235U isotopic signature of the mineralised sediments becomes progressively heavier (enriched in 238U) along the groundwater flow path. The groundwaters show a greater than 2‰ variation in their 238U/235U ratios, ranging from δUCRM145238 values of -2.39±0.07 to -0.71±0.05‰. The majority of the groundwater data exhibit a clear systematic relationship between 238U/235U isotopic composition and U concentration; samples with the lowest U concentrations have the lowest 238U/235U ratios. The preferential incorporation of 238U during reduction of U(VI) to U(IV) and precipitation of uranium minerals leaves the groundwaters enriched in 235U, resulting in a progressive shift in 238U/235U towards lighter values in the aqueous phase as U is removed. These data can be modelled by a closed system Rayleigh fractionation model, with a fractionation factor (α, representing the 238U/235U composition of the groundwater relative to the solid uranium minerals) ranging from ∼0.9996 to 1.0000, with the majority of datapoints ranging from α values of 0.9998 to 0.9999. The sense and magnitude of the results of this study imply that 238U/235U fractionation is likely to be controlled by volume-dependent nuclear field shift effects during the reduction of U(VI) to U(IV) during mineralisation processes. These findings support the use of the 238U/235U isotopic system as a tracer to constrain the nature and timing of palaeoredox conditions.

Geochemistry and the Understanding of Groundwater Systems

NASA Astrophysics Data System (ADS)

Glynn, P. D.; Plummer, L. N.; Weissmann, G. S.; Stute, M.

2009-12-01

Geochemical techniques and concepts have made major contributions to the understanding of groundwater systems. Advances continue to be made through (1) development of measurement and characterization techniques, (2) improvements in computer technology, networks and numerical modeling, (3) investigation of coupled geologic, hydrologic, geochemical and biologic processes, and (4) scaling of individual observations, processes or subsystem models into larger coherent model frameworks. Many applications benefit from progress in these areas, such as: (1) understanding paleoenvironments, in particular paleoclimate, through the use of groundwater archives, (2) assessing the sustainability (recharge and depletion) of groundwater resources, and (3) their vulnerability to contamination, (4) evaluating the capacity and consequences of subsurface waste isolation (e.g. geologic carbon sequestration, nuclear and chemical waste disposal), (5) assessing the potential for mitigation/transformation of anthropogenic contaminants in groundwater systems, and (6) understanding the effect of groundwater lag times in ecosystem-scale responses to natural events, land-use changes, human impacts, and remediation efforts. Obtaining “representative” groundwater samples is difficult and progress in obtaining “representative” samples, or interpreting them, requires new techniques in characterizing groundwater system heterogeneity. Better characterization and simulation of groundwater system heterogeneity (both physical and geochemical) is critical to interpreting the meaning of groundwater “ages”; to understanding and predicting groundwater flow, solute transport, and geochemical evolution; and to quantifying groundwater recharge and discharge processes. Research advances will also come from greater use and progress (1) in the application of environmental tracers to ground water dating and in the analysis of new geochemical tracers (e.g. compound specific isotopic analyses, noble gas isotopes, analyses of natural organic tracers), (2) in inverse geochemical and hydrological modeling, (3) in the understanding and simulation of coupled biological, geological, geochemical and hydrological processes, and (4) in the description and quantification of processes occurring at the boundaries of groundwater systems (e.g. unsaturated zone processes, groundwater/surface water interactions, impacts of changing geomorphology and vegetation). Improvements are needed in the integration of widely diverse information. Better techniques are needed to construct coherent conceptual frameworks from individual observations, simulated or reconstructed information, process models, and intermediate scale models. Iterating between data collection, interpretation, and the application of forward, inverse, and statistical modeling tools is likely to provide progress in this area. Quantifying groundwater system processes by using an open-system thermodynamic approach in a common mass- and energy-flow framework will also facilitate comparison and understanding of diverse processes.

Isotope ratio measurements of pg-size plutonium samples using TIMS in combination with "multiple ion counting" and filament carburization

NASA Astrophysics Data System (ADS)

Jakopic, Rozle; Richter, Stephan; Kühn, Heinz; Benedik, Ljudmila; Pihlar, Boris; Aregbe, Yetunde

2009-01-01

A sample preparation procedure for isotopic measurements using thermal ionization mass spectrometry (TIMS) was developed which employs the technique of carburization of rhenium filaments. Carburized filaments were prepared in a special vacuum chamber in which the filaments were exposed to benzene vapour as a carbon supply and carburized electrothermally. To find the optimal conditions for the carburization and isotopic measurements using TIMS, the influence of various parameters such as benzene pressure, carburization current and the exposure time were tested. As a result, carburization of the filaments improved the overall efficiency by one order of magnitude. Additionally, a new "multi-dynamic" measurement technique was developed for Pu isotope ratio measurements using a "multiple ion counting" (MIC) system. This technique was combined with filament carburization and applied to the NBL-137 isotopic standard and samples of the NUSIMEP 5 inter-laboratory comparison campaign, which included certified plutonium materials at the ppt-level. The multi-dynamic measurement technique for plutonium, in combination with filament carburization, has been shown to significantly improve the precision and accuracy for isotopic analysis of environmental samples with low-levels of plutonium.

Uranium Isotope Fractionation during Oxidation of Dissolved U(iv) and Synthetic Solid UO2

NASA Astrophysics Data System (ADS)

Wang, X.; Johnson, T. M.; Lundstrom, C. C.

2013-12-01

U isotopes (238U/235U) show promise as a tool for environmental monitoring of U contamination as well as a proxy for paleo-redox conditions. However, the isotopic fractionation mechanisms of U are still poorly understood. In groundwater systems, U(VI), a mobile contaminant, can be reduced to immobile U(IV) and thus remediated. Previous work shows that 238U/235U of the remaining U(VI) changes with the extent of reduction. Therefore, U(VI) isotope composition in groundwater can potentially be used to detect and perhaps quantify the extent of reduction. However, knowing if isotopic fractionation occurs during U(IV) oxidation is equally important. First, the reduced U(IV) (either solid or as dissolved organic complexes) potentially can be reoxidized to U(VI). If isotope fractionation occurs during oxidation, it would complicate the use of U isotope composition as a monitoring technique. Further, in natural weathering processes, U(IV) minerals are oxidized to form dissolved U(VI), which is carried to rivers and eventually to the ocean and deposited in marine sediments. The weathering cycle is thus sensitive to redox conditions, meaning the sedimentary U isotope record may serve as a paleoredox indicator, provided U isotope fractionation during oxidation and reduction are well known. We conducted experiments oxidizing 2 different U(IV) species by O2 and measuring isotopic fractionation factors. In one experiment, dissolved U(IV) in 0.1 N HCl (pH 1) was oxidized by entrained air. As oxidation proceeds at pH 1, the remaining dissolved U(IV) becomes progressively enriched in 238U in a linear trend, while the product U(VI) paralleled, but was offset to 1.0‰ lighter in 238U/235U. This linear progression of both remaining reactant and product suggests equilibrium fractionation during oxidation of dissolved U(IV) by O2. A second experiment oxidized synthetic, solid UO2 (in 20 mM NaHCO3, pH 7) with entrained air. The oxidative fractionation is very weak in this case with product U(VI) ~0.1‰ heavier than the remaining UO2. We attribute the lack of strong fractionation during oxidation of solid UO2 to a 'rind effect', where the surface layer must be completely oxidized before the next layer is exposed to oxidant. Hence, nearly complete, congruent conversion of each layer of U(IV) to U(VI) results in minimal isotope fractionation. A small amount of transient fractionation probably occurs initially, but this is quickly negated as the surface becomes isotopically fractionated. Interestingly, our measured ~0.1‰ U isotope fractionation during oxidation of solid U(IV) agrees with the natural observation that 238U/235U ratios in river water (mainly U(VI)) are ~0.1‰ greater than those in fresh continental rocks (primarily U(IV) minerals). Application of these results to natural settings should be done with caution, however. Oxidation of natural uraninite in continental rocks is a much slower process. If the U(VI) product and the U(IV) reactant remain in contact for long periods of time (e.g., months), they may evolve toward isotopic equilibrium. Measurements of 238U/235U in various natural weathering environments should be undertaken to examine this idea.

New techniques for positron emission tomography in the study of human neurological disorders

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

Kuhl, D.E.

1993-01-01

This progress report describes accomplishments of four programs. The four programs are entitled (1) Faster,simpler processing of positron-computing precursors: New physicochemical approaches, (2) Novel solid phase reagents and methods to improve radiosynthesis and isotope production, (3) Quantitative evaluation of the extraction of information from PET images, and (4) Optimization of tracer kinetic methods for radioligand studies in PET.

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis

PubMed Central

Valentine, Benjamin; Kamenov, George D.; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people’s movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape. PMID:25923705

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis.

PubMed

Valentine, Benjamin; Kamenov, George D; Kenoyer, Jonathan Mark; Shinde, Vasant; Mushrif-Tripathy, Veena; Otarola-Castillo, Erik; Krigbaum, John

2015-01-01

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people's movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape.

Disentangling the complexity of nitrous oxide cycling in coastal sediments: Results from a novel multi-isotope approach

NASA Astrophysics Data System (ADS)

Wankel, S. D.; Buchwald, C.; Charoenpong, C.; Ziebis, W.

2014-12-01

Although marine environments contribute approximately 30% of the global atmospheric nitrous oxide (N2O) flux, coastal systems appear to comprise a disproportionately large majority of the ocean-atmosphere flux. However, there exists a wide range of estimates and future projections of N2O production and emission are confounded by spatial and temporal variability of biological sources and sinks. As N2O is produced as an intermediate in both oxidative and reductive microbial processes and can also be consumed as an electron acceptor, a mechanistic understanding of the regulation of these pathways remains poorly understood. To improve our understanding of N2O dynamics in coastal sediments, we conducted a series of intact flow-through sediment core incubations (Sylt, Germany), while manipulating both the O2 and NO3- concentrations in the overlying water. Steady-state natural abundance isotope fluxes (δ15N and δ18O) of nitrate, nitrite, ammonium and nitrous oxide were monitored throughout the experiments. We also measured both the isotopomer composition (site preference (SP) of the 15N in N2O) as well as the Δ17O composition in experiments conducted with the addition of NO3- with an elevated Δ17O composition (19.5‰), which provide complementary information about the processes producing and consuming N2O. Results indicate positive N2O fluxes (to the water column) across all conditions and sediment types. Decreasing dissolved O2 to 30% saturation resulted in reduced N2O fluxes (5.9 ± 6.5 μmol m2 d-1) compared to controls (17.8 ± 6.5 μmol m-2 d-1), while the addition of 100 μM NO3- yielded higher N2O fluxes (49.0 ± 18.5 μmol m-2 d-1). In all NO3- addition experiments, the Δ17O signal from the NO3- was clearly observed in the N2O efflux implicating denitrification as a large source of N2O. However, Δ17O values were always lower (1.9 to 8.6‰) than the starting NO3- indicating an important role for nitrification-based N2O production and/or O isotope exchange with water in influencing the O isotope composition of N2O from the sediment-water interface. A steady-state multi-isotope flux model will help to constraining rates and isotope effects of these processes and improve our understanding of the dynamics and pathways of N2O production and emission under varying scenarios of environmental change.

Landbird migration in the American West: Recent progress and future research directions

USGS Publications Warehouse

Carlisle, J.D.; Skagen, S.K.; Kus, B.E.; van Riper, Charles; Paxton, K.L.; Kelly, J.F.

2009-01-01

Our knowledge of avian behaviors during the nonbreeding period still lags behind that of the breeding season, but the last decade has witnessed a proliferation in research that has yielded significant progress in understanding migration patterns of North American birds. And, although historically the great majority of migration research has been conducted in the eastern half of the continent, there has been much recent progress on aspects of avian migration in the West. In particular, expanded use of techniques such as radar, plasma metabolites, mist-netting, count surveys, stable isotopes, genetic data, and animal tracking, coupled with an increase in multi-investigator collaborations, have all contributed to this growth of knowledge. There is increasing recognition that migration is likely the most limiting time of year for migratory birds, increasing the importance of continuing to decipher patterns of stopover ecology, identifying critical stopover habitats, and documenting migration routes in the diverse and changing landscapes of the American West. Here, we review and briefly synthesize the latest findings and advances in avian migration and consider research needs to guide future research on migration in the West. ?? 2009 by The Cooper Ornithological Society. All rights reserved.

Evaluating degradation of hexachlorcyclohexane (HCH) isomers within a contaminated aquifer using compound-specific stable carbon isotope analysis (CSIA).

PubMed

Bashir, Safdar; Hitzfeld, Kristina L; Gehre, Matthias; Richnow, Hans H; Fischer, Anko

2015-03-15

The applicability of compound-specific stable carbon isotope analysis (CSIA) for assessing biodegradation of hexachlorocyclohexane (HCH) isomers was investigated in a contaminated aquifer at a former pesticide processing facility. A CSIA method was developed and tested for efficacy in determining carbon isotope ratios of HCH isomers in groundwater samples using gas chromatography - isotope ratio mass spectrometry (GC-IRMS). The carbon isotope ratios of HCHs measured for samples taken from the field site confirmed contaminant source zones at former processing facilities, a storage depot and a waste dump site. The (13)C-enrichment in HCHs provided evidence for biodegradation of HCHs especially downstream of the contaminant source zones. CSIA from monitoring campaigns in 2008, 2009 and 2010 revealed temporal trends in HCH biodegradation. Thus, the impact and progress of natural attenuation processes could be evaluated within the investigated aquifer. Calculations based on the Rayleigh-equation approach yielded levels of HCH biodegradation ranging from 30 to 86 %. Moreover, time- and distance-dependent in situ first-order biodegradation rate constants were estimated with maximal values of 3 × 10(-3) d(-1) and 10 × 10(-3) m(-1) for α-HCH, 11 × 10(-3) d(-1) and 37 × 10(-3) m(-1) for β-HCH, and 6 × 10(-3) d(-1) and 19 × 10(-3) m(-1) for δ-HCH, respectively. This study highlights the applicability of CSIA for the assessment of HCH biodegradation within contaminated aquifers. Copyright © 2015 Elsevier Ltd. All rights reserved.

ISONITRATE demonstration project: How isotopic monitoring can improve management of nitrate pollution in water

NASA Astrophysics Data System (ADS)

Widory, D.

2008-12-01

Nitrate is one of the major pollutants of drinking water resources worldwide. Recent European directives reduced inputs from intensive agriculture, but in most places NO3 levels are approaching the potable limit of 50 mg.l-1 in groundwater. Determining the source(s) of contamination in groundwater is an important first step for improving its quality by emission control. It is with this aim that we review here the benefit of using a multi-isotope approach (d15N, d180, d11B), in addition to conventional hydrogeological analysis, to constrain the the origin of NO3 pollution in water. The isotopic composition of the dissolved nitrogen species has been used extensively to better constrain the sources and fate of nitrate in groundwater. The possibility of quantifying both origin and secondary processes affecting N concentrations by means of a single tracer appears more limited however. Nitrogen cannot be considered conservative because it is biologically modified through nitrification and denitrification reactions, both during infiltration of the water and in the groundwater body, causing isotopic fractionation that modifies the d15N signatures of the dissolved N species. Discriminating multiple NO3 sources by their N isotopic composition alone becomes impossible whenever heterogenic or autogenic denitrification occurs, thus arising the need for establishing co-migrating discriminators of NO3 sources: addition of the d180 from NO3 and of the d11B. This presentation will strongly rely on our current European Life ISONITRATE project, which aims at showing policy makers how management of nitrate pollution in water can be greatly improved by the incorporation of the multi-isotope monitoring. The pilot site is located in the Alsace region (France and border Germany), part of the Upper Rhine basin, a groundwater body considered as one of the most important drinking water reservoirs in Europe. The demonstration of the multi-isotope approach is based on 4 distinct scenarios: 1. Natural case: corresponds to the natural nitrification of the soil and represents the reference end-member. Samples with NO3 concentration levels higher than this end-member are considered as polluted. 2. Denitrification case: groundwater samples are selected along an identified denitrification gradient in the "Appenweier-Rheinau" region (Germany): the uppermost samples being contaminated by mineral fertilizers used in vineyards (but not denitrified), and the downstream sample being (almost) totally denitrified. 3. Simple case: chosen as being under the influence of a sole type of nitrate pollution source: mineral fertilisation from the "Orschwihr- Bergholtz vineyards". 4. Complex case: where nitrates correspond to a mixing of different pollution sources (mineral and organic fertilisers), located within the "Dietwiller area".

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

MIMO signal progressing with RLSCMA algorithm for multi-mode multi-core optical transmission system

NASA Astrophysics Data System (ADS)

Bi, Yuan; Liu, Bo; Zhang, Li-jia; Xin, Xiang-jun; Zhang, Qi; Wang, Yong-jun; Tian, Qing-hua; Tian, Feng; Mao, Ya-ya

2018-01-01

In the process of transmitting signals of multi-mode multi-core fiber, there will be mode coupling between modes. The mode dispersion will also occur because each mode has different transmission speed in the link. Mode coupling and mode dispersion will cause damage to the useful signal in the transmission link, so the receiver needs to deal received signal with digital signal processing, and compensate the damage in the link. We first analyzes the influence of mode coupling and mode dispersion in the process of transmitting signals of multi-mode multi-core fiber, then presents the relationship between the coupling coefficient and dispersion coefficient. Then we carry out adaptive signal processing with MIMO equalizers based on recursive least squares constant modulus algorithm (RLSCMA). The MIMO equalization algorithm offers adaptive equalization taps according to the degree of crosstalk in cores or modes, which eliminates the interference among different modes and cores in space division multiplexing(SDM) transmission system. The simulation results show that the distorted signals are restored efficiently with fast convergence speed.

Kinetic Isotope Effects as a Probe of Hydrogen Transfers to and from Common Enzymatic Cofactors

PubMed Central

Roston, Daniel; Islam, Zahidul; Kohen, Amnon

2013-01-01

Enzymes use a number of common cofactors as sources of hydrogen to drive biological processes, but the physics of the hydrogen transfers to and from these cofactors is not fully understood. Researchers study the mechanistically important contributions from quantum tunneling and enzyme dynamics and connect those processes to the catalytic power of enzymes that use these cofactors. Here we describe some progress that has been made in studying these reactions, particularly through the use of kinetic isotope effects (KIEs). We first discuss the general theoretical framework necessary to interpret experimental KIEs, and then describe practical uses for KIEs in the context of two case studies. The first example is alcohol dehydrogenase, which uses a nicotinamide cofactor to catalyze a hydride transfer, and the second example is thymidylate synthase, which uses a folate cofactor to catalyze both a hydride and a proton transfer. PMID:24161942

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.

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.

Iron isotope fractionation among magnetite, pyrrhotite, chalcopyrite, rhyolite melt and aqueous fluid at magmatic-hydrothermal conditions

NASA Astrophysics Data System (ADS)

Bilenker, L. D.; Simon, A.; Lundstrom, C.; Gajos, N.

2012-12-01

Fractionation of non-traditional stable isotopes (NTSI) such as Fe in magmatic systems is a relatively understudied subject. The fractionation of Fe stable isotopes has been quantified in some natural igneous samples, but there is a paucity of experimental data that could provide further insight into the causative processes of the observed fractionation. Substantial experimental work has been performed at higher temperatures pertaining to the formation of chondrites and the Earth's core, but only a handful of studies have addressed crustal rocks. To fill this knowledge gap, we performed isothermal, isobaric experiments containing mineral (e.g., magnetite, Fe-sulfides) and fluid, or mineral, rhyolite melt, and fluid assemblages to quantify equilibrium fractionation factors (α). These data, to our knowledge, are the first data that quantify the effect of a fluid phase on iron isotope fractionation at conditions appropriate for evolving magmatic systems. Charges were run inside gold capsules held in a René-41 cold seal vessel, and heated to 400, 600, or 800°C at 150 MPa for mineral-fluid, and 800°C and 100 MPa for mineral-melt-fluid runs. Use of the René vessel fixed the fO2 at the NNO buffer, an oxidation state consistent with arc magmas. The isotopic compositions of the starting and quenched phases were obtained by using a Multi-Collector Plasma Mass Spectrometer (MC-ICP-MS). Equilibrium was assessed by performing time-series runs and the three-isotope method, used only once before in a similar Fe isotope study. Correlation between Fe isotope mass and oxidation state is also being explored. Magnetite-fluid results indicate enrichment of heavy Fe isotopes in the mineral relative to the fluid, consistent with measurements of felsic igneous rocks. Magnetite-melt-fluid relationships are also consistent with measurements of natural samples. In the latter assemblage, over the course of the run, the rhyolite melt becomes heavy relative to the fluid while magnetite takes on a heavier Fe isotope signature than the starting value. These data corroborate the hypothesis that fluid exsolution caused the isotopic patterns observed in highly-differentiated igneous rocks. Further, owing to the ubiquitous importance of melt degassing as a critical process for the formation of magmatic-hydrothermal ore deposits, these data may be potentially serve as an exploration tool. This work contributes to our overall understanding of igneous processes by elucidating the Fe isotope fingerprints observed in the field as well as develop the laboratory techniques needed to study NTSI fractionation in magmatic systems and build a reliable dataset for interpretation of natural systems.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

NASA Astrophysics Data System (ADS)

Yuan, Honglin; Liu, Xu; Chen, Lu; Bao, Zhian; Chen, Kaiyun; Zong, Chunlei; Li, Xiao-Chun; Qiu, Johnson Wenhong

2018-04-01

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100-3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.

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.

Zn and C isotopic evidence of climatic change during the Marinoan

NASA Astrophysics Data System (ADS)

Thiemens, M. M.; Moynier, F.; Koeberl, C.; Thiemens, M. H.; Shaheen, R.; Gyollai, I.; Popp, F.; Chong, K.

2011-12-01

The "Snowball Earth" events of the Cryogenian period are renowned for their remarkable chemical and isotopic signatures left in the geological record. Through analysis of post Marinoan glaciation cap carbonates from Namibia, specifically from Fransfontein, the Khowarib Valley, and Naraachamspos, a multi isotopic study was undertaken. We analyzed the δ 13C of chemically isolated calcite and dolomite. A moderate depletion of 13C in calcite (δ 13C<0% V-PDB) associated with global glaciations was observed, confirming the event. Associated dolomites also show a 13C depletion, but at a much lower magnitude. Zinc is a trace element that is necessary for all forms of life. Zn does not undergo redox cycling under normal environmental conditions, and biological uptake is one of the few processes that produces isotopic fractionation. This fractionation is in the range of 0.1 permil for the 66Zn/64Zn ratio (δ 66Zn in permil deviation), however with the advent of multi-collection inductively-coupled plasma mass spectrometry (MC-ICP-MS) such variations have become resolvable. We also have measured the Zinc composition of multiple species of lab cultured archaea, and found that the cells are enriched in the light isotopes of Zn compared to the culture medium. By measuring Zn levels in the Cap Carbonates, we seek corroboration for the carbon depletion we find during the glaciation. Zinc should undergo a similarly significant alteration at the mass extinction from climatic shifts inherent to a worldwide glaciation. We find the samples to be relatively consistent, with a δ 66Zn of approximately 0.30 to 0.40 in most places, with a δ 68Zn of double that, values typical of terrestrial rocks. Several sites have a much larger fractionation, with δ 66Zn of up to 0.90 in the Khowarib Valley, and up to 1.06 in the clays at the entrance to the South Valley. These isotopic compositions may be indicative of the massive climatic event leading to the formation of the cap carbonates.

On the longevity of silicic magma based on multi-isotope investigation of zircons and modeling their survivals destinies

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Wotzlaw, J. F.; Melnik, O. E.

2015-12-01

Large volumes of crystal poor, near-liquidus rhyolites are erupted worldwide as tuffs and lavas in rift and hot spots more common previously on early earth, creating temporally very high magma production rates. In this contribution we combine results of IDTIMS dating of zircons with numerical modeling of zircon crystallization. New investigation of zircons in major Yellowstone tuffs: Huckleberry Ridge (Members A,B,C), Mesa Falls, and Lava Creek (A,B) tuffs was done by a combination of in situ measurements of oxygen isotopes followed by ID-TIMS U-Pb dating, Hf isotopes and trace elemental investigation of single crystals. We discover that nearly all zircons are of eruption age, but display significant isotope (O,Hf) diversity and often show decoupled O and Hf isotope systematics. This record rapid (~103yrs) double or triple remelting and sequestration from diverse Archean crust and hydrothermally altered shallow-crustal rocks from previous eruptive cycles, followed by effective mixing of co-existing magma reservoirs with diverse zircons prior to eruptions. Similar results characterize other studied Snake River Plain rhyolites in pre-Yellowstone Heise complex. These results collectively suggest that zircons crystallize after reheating above saturation rejuvenation in isotopically-diverse areas of the crust in the magma plumbing system. Modeling of zircon and quartz dissolution and crystallization trajectories outline conditions of survival (inheritance) vs complete dissolution on conductive timescales, and when combined with a phase diagram, magma T-t paths can be computed. Zircon rejuvenation requires hot, >770-800°C peak temperatures lasting 10-102yrs. We speculate that near liquidus hot and dry Yellowstone rhyolites are kept alive in a multi-batch state by a series of interconnected pods and sills that can rapidly get thermomechanically assembled into large, shallow and eruptable supervolcanoic magma bodies. We suggest that overpressure and roof dynamics and rheology plays a more important role than magma buyoncy. The runaway batch assembly process creates temporally very high magma production rates, orders of magnitude higher than for arc volcanoes. Such views have implication for the state of the magma chamber under Yellowstone and similar supervolcanoes elsewhere.

Using isotopes to investigate hydrological flow pathways and sources in a remote Arctic catchment

NASA Astrophysics Data System (ADS)

Lessels, Jason; Tetzlaff, Doerthe; Dinsmore, Kerry; Street, Lorna; Billet, Mike; Baxter, Robert; Subke, Jens-Arne; Wookey, Phillip

2014-05-01

Stable water isotopes allow for the identification of flow paths and stream water sources. This ability is beneficial in improving the understanding in catchments with dynamic spatial and temporal sources. Arctic catchments are characterised with strong seasonality where the dominant flow paths change throughout the short summer season. Therefore, the identification of stream water sources through time and space is necessary in order to accurately quantify these dynamics. Stable isotope tracers are incredibly useful tools which integrate processes of time and space and therefore, particularly useful in identifying flow pathways and runoff sources at remote sites. This work presents stable isotope data collected from a small (1km2) catchment in Northwest Canada. The aims of this study are to 1) identify sources of stream water through time and space, 2) provide information which will be incorporated into hydrological and transit time models Sampling of snowmelt, surface runoff, ice-wedge polygons, stream and soil water was undertaken throughout the 2013 summer. The results of this sampling reveal the dominant flow paths in the catchment and the strong influence of aspect in controlling these processes. After the spring freshet, late lying snow packs on north facing slopes and thawing permafrost on south facing slopes are the dominant sources of stream water. Progressively through the season the thawing permafrost and precipitation become the largest contributing sources. The depth of the thawing aspect layer and consequently the contribution to the stream is heavily dependent on aspect. The collection of precipitation, soil and stream isotope samples throughout the summer period provide valuable information for transit time estimates. The combination of spatial and temporal sampling of stable isotopes has revealed clear differences between the main stream sources in the studied catchment and reinforced the importance of slope aspect in these catchments.

New bulk and in situ isotopic and elemental geochemistry of shallow drill core from Atlantis Massif: insights into the sources and paths of fluids and clasts

NASA Astrophysics Data System (ADS)

Bilenker, L.; Weis, D.; Scoates, J. S.

2017-12-01

We present stable Fe and radiogenic isotope and complementary trace element data for samples from Atlantis Massif. This oceanic core complex is located at 30°N where the Atlantis Transform Fault intersects the Mid-Atlantic Ridge (MAR) and is associated with the Lost City Hydrothermal Field (LCHF). It is a unique place to investigate the abiotic and biotic geochemical processes that play a role in the alteration of both crustal and mantle seafloor rocks. The samples analyzed represent a shallow (<15 m) survey of five drill sites (IODP Expedition 357) within Atlantis Massif, varying in distance from the LCHF and MAR. Analyses were performed on a sample set spanning a wide range in degree of alteration and lithology. Bulk measurements involved dissolving whole rock powders, whereas in situ analyses were performed on digested microdrilled samples or by laser ablation. Bulk rock Fe isotope values (n = 34) are correlated with loss-on-ignition (LOI) by sample lithology and location relative to LCHF. Using LOI as a proxy for degree of alteration, this observation indicates that the Fe isotope systematics of seafloor crustal and mantle rocks preserve indicators of fluid flow and source. The Hf and Nd isotope compositions for various lithologies form all analyzed sites are homogeneous, indicating minimal alteration of these isotopic systems. Bulk Sr values provide insight into elemental exchange between seawater and the surface of Atlantis Massif and bulk Pb isotopes allow for fingerprinting of the source of basalt breccias through comparison with published Pb isotope values of MAR basalts. The new results cluster around the Pb, Hf, Nd isotopic composition of mid-ocean ridge basalt from 30.68°N and do not match samples north or south of that location. In situ Fe isotope data within three altered samples reflect varying degrees of hydrothermal and seawater interaction, where the Fe isotope ratios within each sample are likely correlated with extent of exchange or redox. Laser trace element and Pb isotope data in progress will allow us to investigate this further. This study contributes to our understanding of element mobility and mass transfer during chemical reactions within the seafloor, provides insight into the source of the lithological units and fluid flow, and allows for quantification of alteration processes.

Application of multi-tone mask technology in photolithographic fabrication of color filter components in LCD

NASA Astrophysics Data System (ADS)

Takada, Yoshihiro; Fukui, Matoko; Sai, Tsunehiro

2008-11-01

Recent progresses in the photoresists and photolithography for LCD industry applications have been primarily driven by the following two factors: advancement in the material performances (high resolution, high contrast ratio, low dielectric constant) for higher display quality, and cost reduction in the fabrication process. Along with crucial demand for cost competitiveness by improving production efficiency, environmental consciousness has been a major priority at fabrication process design to minimize the amount of waste produced. Having said the above, integration of two or more fabrication processes into a single process by using multi-tone mask technology has been the interest of research, due to its obvious advantage of reducing fabrication processes and cost. For example, multi-tone mask technology application has been widely employed on the TFT side to reduce the different types of photomasks being used. Similar trend has been employed on the CF side as well, where application of multi-tone mask technology is being investigated to integrate fabrication of multiple CF micro-components into a single process. In this presentation, we demonstrate a new approach of fabricating photospacer and peripheral CF components (MVA protrusion, sub-photospacers) in a single integrated process through multi-tone mask technology.

A Nine-year Record of Groundwater Environmental Tracer Variations in a Weathered Sandstone Plateau Aquifer.

NASA Astrophysics Data System (ADS)

Cendon, D. I.; Hankin, S. I.; Hughes, C. E.; Meredith, K.; Peterson, M.; Scheiber, L.; Shimizu, Y.

2016-12-01

Most groundwater isotopic studies are limited to one snapshot in time due to high costs associated with sampling and analytical procedures. The timing of sampling within long-term seasonal climatic cycles may affect interpretations, particularly in unconfined or semi-confined aquifer systems. To test the potential influence of decadal climatic trends, particularly on groundwater residence time, we have combined results from a multi-year sampling programme. Hydrogeochemistry and isotopic tracer analysis including H2O stable isotopes, δ13CDIC, 3H, 14CDIC for all samples and 87Sr/86Sr and NO3-δ15N, have been applied to groundwater recovered from the Kulnura - Mangrove Mountain aquifer hosted by a weathered sandstone plateau within the Sydney Basin (Australia). In general, the study area is characterised by alternating dry and wet periods that can be prolonged as they are linked to wider climatic events such as El Niño, La Niña and modulated by the Indian Ocean Dipole. The region experienced above average rainfall from 1985-1990 followed by generally drier conditions (1991-2007) and slightly wetter conditions to 2015. Groundwater results from the first years (2006-2010), under generally dry conditions resulted in lower groundwater levels, revealed important inter-annual variations. These are interpreted to be locally driven by groundwater extraction, resulting in a progressive influx of modern groundwater. The progressive input of modern water has exposed deeper parts of the aquifer to increased NO3- concentrations of anthropogenic origin. The change in chemistry of the groundwater, particularly the lowering of groundwater pH, has accelerated the dissolution of carbonate mineral phases that in turn affects 14C residence time assessments. Subsequent sampling results (2012-2015), under higher rainfall conditions, suggest modern recharge in areas previously without measurable tritium activities. The complex interplay between recharge, anthropogenic influences and climate may be further complicated by the local irregularities in the sandstone weathering profile and the transition to preferential groundwater fracture-flow with depth.

Comparative performance study of different sample introduction techniques for rapid and precise selenium isotope ratio determination using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS).

PubMed

Elwaer, Nagmeddin; Hintelmann, Holger

2007-11-01

The analytical performance of five sample introduction systems, a cross flow nebulizer spray chamber, two different solvent desolvation systems, a multi-mode sample introduction system (MSIS), and a hydride generation (LI2) system were compared for the determination of Se isotope ratio measurements using multi-collector inductively coupled plasma mass spectrometry (MC-ICP/MS). The optimal operating parameters for obtaining the highest Se signal-to-noise (S/N) ratios and isotope ratio precision for each sample introduction were determined. The hydride generation (LI2) system was identified as the most suitable sample introduction method yielding maximum sensitivity and precision for Se isotope ratio measurement. It provided five times higher S/N ratios for all Se isotopes compared to the MSIS, 20 times the S/N ratios of both desolvation units, and 100 times the S/N ratios produced by the conventional spray chamber sample introduction method. The internal precision achieved for the (78)Se/(82)Se ratio at 100 ng mL(-1) Se with the spray chamber, two desolvation, MSIS, and the LI2 systems coupled to MC-ICP/MS was 150, 125, 114, 13, and 7 ppm, respectively. Instrument mass bias factors (K) were calculated using an exponential law correction function. Among the five studied sample introduction systems the LI2 showed the lowest mass bias of -0.0265 and the desolvation system showed the largest bias with -0.0321.

Hadron Spectra, Decays and Scattering Properties Within Basis Light Front Quantization

NASA Astrophysics Data System (ADS)

Vary, James P.; Adhikari, Lekha; Chen, Guangyao; Jia, Shaoyang; Li, Meijian; Li, Yang; Maris, Pieter; Qian, Wenyang; Spence, John R.; Tang, Shuo; Tuchin, Kirill; Yu, Anji; Zhao, Xingbo

2018-07-01

We survey recent progress in calculating properties of the electron and hadrons within the basis light front quantization (BLFQ) approach. We include applications to electromagnetic and strong scattering processes in relativistic heavy ion collisions. We present an initial investigation into the glueball states by applying BLFQ with multigluon sectors, introducing future research possibilities on multi-quark and multi-gluon systems.

Nuclear data uncertainty propagation by the XSUSA method in the HELIOS2 lattice code

NASA Astrophysics Data System (ADS)

Wemple, Charles; Zwermann, Winfried

2017-09-01

Uncertainty quantification has been extensively applied to nuclear criticality analyses for many years and has recently begun to be applied to depletion calculations. However, regulatory bodies worldwide are trending toward requiring such analyses for reactor fuel cycle calculations, which also requires uncertainty propagation for isotopics and nuclear reaction rates. XSUSA is a proven methodology for cross section uncertainty propagation based on random sampling of the nuclear data according to covariance data in multi-group representation; HELIOS2 is a lattice code widely used for commercial and research reactor fuel cycle calculations. This work describes a technique to automatically propagate the nuclear data uncertainties via the XSUSA approach through fuel lattice calculations in HELIOS2. Application of the XSUSA methodology in HELIOS2 presented some unusual challenges because of the highly-processed multi-group cross section data used in commercial lattice codes. Currently, uncertainties based on the SCALE 6.1 covariance data file are being used, but the implementation can be adapted to other covariance data in multi-group structure. Pin-cell and assembly depletion calculations, based on models described in the UAM-LWR Phase I and II benchmarks, are performed and uncertainties in multiplication factor, reaction rates, isotope concentrations, and delayed-neutron data are calculated. With this extension, it will be possible for HELIOS2 users to propagate nuclear data uncertainties directly from the microscopic cross sections to subsequent core simulations.

High precision isotope ratio measurements of mercury isotopes in cinnabar ores using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Hintelmann, Holger; Lu, ShengYong

2003-06-01

Variations in Hg isotope ratios in cinnabar ores obtained from different countries were detected by high precision isotope ratio measurements using multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Values of delta198/202Hg varied from 0.0-1.3 percent per thousand relative to a NIST SRM 1641d Hg solution. The typical external uncertainty of the delta values was 0.06 to 0.26 percent per thousand. Hg was introduced into the plasma as elemental Hg after reduction by sodium borohydride. A significant fractionation of lead isotopes was observed during the simultaneous generation of lead hydride, preventing normalization of the Hg isotope ratios using the measured 208/206Pb ratio. Hg ratios were instead corrected employing the simultaneously measured 205/203T1 ratio. Using a 10 ng ml(-1) Hg solution and 10 min of sampling, introducing 60 ng of Hg, the internal precision of the isotope ratio measurements was as low as 14 ppm. Absolute Hg ratios deviated from the representative IUPAC values by approximately 0.2% per u. This observation is explained by the inadequacy of the exponential law to correct for mass bias in MC-ICP-MS measurements. In the absence of a precisely characterized Hg isotope ratio standard, we were not able to determine unambiguously the absolute Hg ratios of the ore samples, highlighting the urgent need for certified standard materials.

Update and evaluation of decay data for spent nuclear fuel analyses

NASA Astrophysics Data System (ADS)

Simeonov, Teodosi; Wemple, Charles

2017-09-01

Studsvik's approach to spent nuclear fuel analyses combines isotopic concentrations and multi-group cross-sections, calculated by the CASMO5 or HELIOS2 lattice transport codes, with core irradiation history data from the SIMULATE5 reactor core simulator and tabulated isotopic decay data. These data sources are used and processed by the code SNF to predict spent nuclear fuel characteristics. Recent advances in the generation procedure for the SNF decay data are presented. The SNF decay data includes basic data, such as decay constants, atomic masses and nuclide transmutation chains; radiation emission spectra for photons from radioactive decay, alpha-n reactions, bremsstrahlung, and spontaneous fission, electrons and alpha particles from radioactive decay, and neutrons from radioactive decay, spontaneous fission, and alpha-n reactions; decay heat production; and electro-atomic interaction data for bremsstrahlung production. These data are compiled from fundamental (ENDF, ENSDF, TENDL) and processed (ESTAR) sources for nearly 3700 nuclides. A rigorous evaluation procedure of internal consistency checks and comparisons to measurements and benchmarks, and code-to-code verifications is performed at the individual isotope level and using integral characteristics on a fuel assembly level (e.g., decay heat, radioactivity, neutron and gamma sources). Significant challenges are presented by the scope and complexity of the data processing, a dearth of relevant detailed measurements, and reliance on theoretical models for some data.

Alpine Holocene Tree Ring Isotope Records - A Synthesis of a Multi-Proxy Approach in Dendroclimatology

NASA Astrophysics Data System (ADS)

Ziehmer, Malin Michelle; Nicolussi, Kurt; Schlüchter, Christian; Leuenberger, Markus

2017-04-01

High-resolution climate reconstructions based on tree-ring proxies are often limited by the individual segment length of living trees selected at the defined sampling sites, which mostly results in relatively short multi-centennial proxy series. A potential extension of living wood records comprise the addition of subfossil and archeological wood remains resulting in chronologies and associated climate reconstructions which are able to cover a few millennia in central Europe (e.g. Büntgen et al., 2011). However, existing multi-millennial tree-ring width chronologies in central Europe rank among the longest continuous chronologies world-wide and span the entire Holocene (Becker et al., 1993; Nicolussi et al. 2009). So far, these chronologies have mainly been used for dating subfossil wood samples, floating chronologies and archeological artifacts, but only in parts for reconstructing climate. Finds of Holocene wood remains in glacier forefields, peat bogs and small lakes allow us not only to establish such long-term tree-ring width records; further they offer the possibility to establish multi-millennial proxy records for the entire Holocene by using a multi-proxy approach which includes both tree-ring width and triple stable isotope ratios. As temperature limits tree growth at the Alpine upper tree line, the existing tree-ring width records are currently limited to reconstruct a single environmental variable. In the framework of the project Alpine Holocene Tree Ring Isotope Records, we combine tree-ring width, cellulose content as well as carbon, oxygen and hydrogen isotope series in a multi-proxy approach which allows the reconstruction of past environments by combining both Holocene wood remains and recent tree samples from two Alpine tree-line species. For this purpose, α-cellulose is prepared from 5-year tree ring blocks following the procedure after Boettger et al. (2007) and subsequently crushed by ultrasonic homogenization (Laumer et al., 2009). The cellulose content is determined for each individual sample and carbon, oxygen and hydrogen isotopic ratios are measured simultaneously (Loader et al., 2015). The isotope records of carbon, oxygen and hydrogen show distinct low-frequency trends for the Early- and Mid-Holocene, but the individual series per proxy are often offset in their isotopic signature. As the sampling sites in our study are distributed along a SW-NE transect, the influence of the site conditions (latitude, longitude, elevation, exposition) and the tree species is tested and subsequently a correction is applied to the individual series. In addition, the tree-ring width records operate as a helpful tool in detecting and attributing the influence of larch budmoth outbreaks on the cellulose content and isotope records. We here present a synthesis of the applied multi-proxy approach and its ability to reconstruct Holocene climate variability for the time span from 9000 to 3500 years b2k covering the Early-Holocene (9000 to 7200 years b2k) and Mid-Holocene (7200 to 4200 years b2k) and the transition to the late Holocene (4200 to 3500 years b2k) as well as the recent 400 years including the modern warming. References Becker, B., & Kromer, B. Palaeogeogr. Palaeoclimatol. Palaeoecol., 1993, 103(1): 67-71 Boettger, T., et al. Anal. Chem., 2007, 79: 4603-4612 Büntgen, U. et al. Science, 2011, 331(6017): 578-582 Laumer, W., et al. Rapid Commun. Mass Spectrom., 2009, 23: 1934-1940 Loader, N.J., et al. Anal. Chem., 2015, 87: 376-380 Nicolussi K., et al. The Holocene, 2009, 19(6): 909-920

Lead-isotopic, sulphur-isotopic, and trace-element studies of galena from the Silesian-Cracow Zn-Pb ores, polymetallic veins from the Gory Swietokrzyskie MTS, and the Myszkow porphyry copper deposit, Poland

USGS Publications Warehouse

Church, S.E.; Vaughn, R.B.; Gent, C.A.; Hopkins, R.T.

1996-01-01

Lead-isotopic data on galena samples collected from a paragenetically constrained suite of samples from the Silesian-Cracow ore district show no regional or paragenetically controlled lead-isotopic trends within the analytical reproducibility of the measurements. Furthermore, the new lead-isotopic data agree with previously reported lead-isotopic results (R. E. Zartman et al., 1979). Sulfur-isotopic analyses of ores from the Silesian-Cracow district as well as from vein ore from the Gory Swietokrzyskie Mts. and the Myszkow porphyry copper deposit, when coupled with trace-element data from the galena samples, clearly discriminate different hydrothermal ore-forming events. Lead-isotopic data from the Permian and Miocene evaporite deposits in Poland indicate that neither of these evaporite deposits were a source of metals for the Silesian-Cracow district ores. Furthermore, lead-isotopic data from these evaporite deposits and the shale residues from the Miocene halite samples indicate that the crustal evolution of lead in the central and western European platform in southern Poland followed normal crustal lead-isotopic growth, and that the isotopic composition of crustal lead had progressed beyond the lead-isotopic composition of lead in the Silesian-Cracow ores by Permian time. Thus, Mesozoic and Tertiary sedimentary flysch rocks can be eliminated as viable source rocks for the metals in the Silesian-Cracow Mississippi Valley-type (MVT) deposits. The uniformity of the isotopic composition of lead in the Silesian-Cracow ores, when coupled with the geologic evidence that mineralization must post-date Late Jurassic faulting (E. Gorecka, 1991), constrains the geochemical nature of the source region. The source of the metals is probably a well-mixed, multi-cycle molasse sequence of sedimentary rocks that contains little if any Precambrian metamorphic or granitic clasts (S. E. Church, R. B. Vaughn, 1992). If ore deposition was post Late Jurassic (about 150 m. y.) or later as indicated by the geologic evidence, the source rocks probably contained elevated concentrations of Zn and Pb (75-100 ppm), and relatively low concentrations of U and Th (2 and 8 ppm or less, respectively). The Carboniferous coal-bearing molasse rocks of the Upper Silesian Coal Basin are a prime candidate for such a source region. The presence of ammonia and acetate in the fluid inclusions (Viets et al., 1996a) also indicate that the Carboniferous coal-bearing molasse sequence in the Upper Silesian Coal Basin may have been a suitable pathway for the MVT ore fluids. The lead-isotopic homogeneity, when coupled with the sulfur-isotopic heterogeneity of the ores suggests that mixing of a single metal-bearing fluid with waters from separate aquifers containing variable sulfur-isotopic compositions in karsts in the Muschelkalk Formation of Middle Triassic age may have been responsible for the precipitation of the ores of the Silesian-Cracow district.

Identifying calcium sources at an acid deposition-impacted spruce forest: A strontium isotope, alkaline earth element multi-tracer approach

USGS Publications Warehouse

Bullen, T.D.; Bailey, S.W.

2005-01-01

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources, but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration ratios of trees and soils to discern the record of Ca sources for red spruce at a base-poor, acid deposition-impacted watershed. We measured 87Sr/86Sr and chemical compositions of cross-sectional stemwood cores of red spruce, other spruce tissues and sequential extracts of co-located soil samples. 87Sr/86Sr and Sr/Ba ratios together provide a tracer of alkaline earth element sources that distinguishes the plant-available fraction of the shallow organic soils from those of deeper organic and mineral soils. Ca/Sr ratios proved less diagnostic, due to within-tree processes that fractionate these elements from each other. Over the growth period from 1870 to 1960, 87Sr/86Sr and Sr/Ba ratios of stemwood samples became progressively more variable and on average trended toward values that considered together are characteristic of the uppermost forest floor. In detail the stemwood chemistry revealed an episode of simultaneous enhanced uptake of all alkaline earth elements during the growth period from 1930 to 1960, coincident with reported local and regional increases in atmospheric inputs of inorganic acidity. We attribute the temporal trends in stemwood chemistry to progressive shallowing of the effective depth of alkaline earth element uptake by fine roots over this growth period, due to preferential concentration of fine roots in the upper forest floor coupled with reduced nutrient uptake by roots in the lower organic and upper mineral soils in response to acid-induced aluminum toxicity. Although both increased atmospheric deposition and selective weathering of Ca-rich minerals such as apatite provide possible alternative explanations of aspects of the observed trends, the chemical buffering capacity of the forest floor-biomass pool limits their effectiveness as causal mechanisms. ?? Springer 2005.

Coupling Meteorology, Metal Concentrations, and Pb Isotopes for Source Attribution in Archived Precipitation Samples

EPA Science Inventory

A technique that couples lead (Pb) isotopes and multi-element concentrations with meteorological analysis was used to assess source contributions to precipitation samples at the Bondville, Illinois USA National Trends Network (NTN) site. Precipitation samples collected over a 16 ...

The Power of Integrating Kinetic Isotope Effects into the Formalism of the Michaelis-Menten Equation

PubMed Central

Klinman, Judith P.

2014-01-01

The final arbiter of enzyme mechanism is the ability to establish and test a kinetic mechanism. Isotope effects play a major role in expanding the scope and insight derived from the Michaelis-Menten equation. The integration of isotope effects into the formalism of the Michaelis-Menten equation began in the 1970s and has continued to this day. This review discusses a family of eukaryotic copper proteins that includes dopamine β-monooxygenase, tyramine β-monooxygenase, and peptidylglycine α-amidating enzyme, responsible for the synthesis of the neuro-active compounds, norepinephrine, octopamine and C-terminally carboxamidated peptides, respectively. Highlighted are results that show how combining kinetic isotope effects with initial rate parameters permits an evaluation of: (i) the order of substrate binding to multi-substrate enzymes; (ii) the magnitude of individual rate constants in complex, multi-step reactions; (iii) the identification of chemical intermediates; and (iv) the role of non-classical (tunneling) behavior in C–H activation. PMID:23937475

Multi-factorial in vivo stable isotope fractionation: causes, correlations, consequences and applications.

PubMed

Schmidt, Hanns-Ludwig; Robins, Richard J; Werner, Roland A

2015-01-01

Many physical and chemical processes in living systems are accompanied by isotope fractionation on H, C, N, O and S. Although kinetic or thermodynamic isotope effects are always the basis, their in vivo manifestation is often modulated by secondary influences. These include metabolic branching events or metabolite channeling, metabolite pool sizes, reaction mechanisms, anatomical properties and compartmentation of plants and animals, and climatological or environmental conditions. In the present contribution, the fundamentals of isotope effects and their manifestation under in vivo conditions are outlined. The knowledge about and the understanding of these interferences provide a potent tool for the reconstruction of physiological events in plants and animals, their geographical origin, the history of bulk biomass and the biosynthesis of defined representatives. It allows the use of isotope characteristics of biomass for the elucidation of biochemical pathways and reaction mechanisms and for the reconstruction of climatic, physiological, ecological and environmental conditions during biosynthesis. Thus, it can be used for the origin and authenticity control of food, the study of ecosystems and animal physiology, the reconstruction of present and prehistoric nutrition chains and paleaoclimatological conditions. This is demonstrated by the outline of fundamental and application-orientated examples for all bio-elements. The aim of the review is to inform (advanced) students from various disciplines about the whole potential and the scope of stable isotope characteristics and fractionations and to provide them with a comprehensive introduction to the literature on fundamental aspects and applications.

Recent progress in the understanding of H transport and trapping in W

NASA Astrophysics Data System (ADS)

Schmid, K.; Bauer, J.; Schwarz-Selinger, T.; Markelj, S.; Toussaint, U. v.; Manhard, A.; Jacob, W.

2017-12-01

The retention of hydrogen isotopes (HIs) (H, D and T) in the first, plasma exposed wall is one of the key concerns for the operation of future long pulse fusion devices. It affects the particle-, momentum- and energy balance in the scrape off layer as well as the retention of HIs and their permeation into the coolant. The currently accepted picture that is used for interpreting current laboratory and tokamak experiments is that of diffusion hindered by trapping at lattice defects. This paper summarises recent results that show that this current picture of how HIs are transported and retained in W needs to be extended: the modification of the surface (e.g. blistering) can lead to the formation of fast loss channels for near surface HIs. Trapping at single occupancy traps with fixed de-trapping energy fails to explain isotope exchange experiments, instead a trapping model with multi occupancy traps and fill level dependent de-trapping energies is required. The presence of interstitial impurities like N or C may affect the transport of solute HI. The presence of HIs during damage creation by e.g. neutrons stabilises defects and reduces defect annealing at elevated temperatures.

Progress on Establishing the Feasibility of Lead Slowing Down Spectroscopy for Direct Measurement of Plutonium in Used Fuel

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

Kulisek, Jonathan A.; Anderson, Kevin K.; Bowyer, Sonya M.

2012-07-19

Developing a method for the accurate, direct, and independent assay of the fissile isotopes in bulk materials (such as used fuel) of next-generation domestic nuclear fuel cycles is a goal of the Office of Nuclear Energy, Fuel Cycle R&D, Material Protection and Control Technology (MPACT) Campaign. To meet this goal, MPACT continues to support a multi-institutional collaboration to address the feasibility of Lead Slowing Down Spectroscopy (LSDS) as an active nondestructive assay method that has the potential to provide independent, direct measurement of Pu and U isotopic masses in used fuel with an uncertainty considerably lower than the approximately 10%more » typical of today’s confirmatory assay methods. An LSDS is comprised of a stack of lead (typically 1-6 m3) in which materials to be measured are placed in the lead and a pulse of neutrons is injected. The neutrons in this pulse lose energy due to inelastic and (subsequently) elastic scattering and the average energy of the neutrons decreases as the time increases by a well-defined relationship. In the interrogation energy region (~0.1-1000 eV) the neutrons have little energy spread (~30%) about the average neutron energy. Due to this characteristic, the energy of the (assay) neutrons can then be determined by measuring the time elapsed since the neutron pulse. By measuring the induced fission neutrons emitted from the used fuel, it is possible to determine isotopic-mass content by unfolding the unique structure of isotopic resonances across the interrogation energy region. This paper will present efforts on the development of time-spectral analysis algorithms, fast neutron detector advances, and validation and testing measurements.« less

Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

NASA Astrophysics Data System (ADS)

Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

2016-09-01

The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and provide important mechanistic details about the overall TSR process.

High Precision Iron Isotope Compositions in Components From the Allende CV3 Meteorite by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Mullane, E.; Russell, S. S.; Weiss, D.; Mason, T. F.; Gounelle, M.

2001-12-01

Four chondrules and one matrix sample of Allende were examined for Fe-isotope frac-tionation, using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Iron is the most volatile major constituent of chondrules and a recent study [1] suggested that solar system Fe was initially isotopically homogeneous. Thus, any isotopic variation is likely due to mass fractionation during nebular process-ing. The chondrule samples were split. One portion was subject to a standard acid dis-solution whilst the other was polished, ena-bling textural and compositional characteri-zation. Fe, Cu and Zn are separated from the remaining matrix elements [2], removing potential interfering ions from the solution. 100 % elemental recovery (within error) is achieved, ensuring that chromatographic fractionation does not occur [2]. Hydrogen is bled into the collision cell, minimising Ar polyatomic species interferences. Typical precisions of 0.1‰ (2σ ) for 54Fe/56Fe ratios are achieved for 75 replicates. Instrumental mass bias is assessed using (1) sample-standard brack-eting and (2) doping with Cu. A variation of 0.8‰ /amu is observed, which is approximately 18 times the analyti-cal uncertainty at the 2σ level. Our high precision data show that: (1) Allende chondrules and matrix exhibit clear isotopic variation in iron. (2) δ 54Fe val-ues appear to be correlated to the bulk FeO content, with the more iron rich samples enriched in the lighter 54Fe isotope. (3) δ 54Fe values appear to be unre-lated to texture, and consequently to the temperature of chondrule formation. Bulk Fe-content may be a proxy for the amount of volatilisation experienced, and volatilisation of Fe in chondrule precursor material has resulted in a residue of the heavier Fe isotopes. Chondrules are known to have often experienced several heating events, and their texture primarily reflects the nature of the last event. Thus, the lack of correlation between the δ 54Fe value and chondrule texture suggests that Fe-isotope composi-tion was derived from chondrule precursor material. [1] Zhu et al. (2001) Nature 412, p.311 [2] Mullane et al. (2001) LPS XXXII, No.1545.

A Multi-layered Quantitative In Vivo Expression Atlas of the Podocyte Unravels Kidney Disease Candidate Genes.

PubMed

Rinschen, Markus M; Gödel, Markus; Grahammer, Florian; Zschiedrich, Stefan; Helmstädter, Martin; Kretz, Oliver; Zarei, Mostafa; Braun, Daniela A; Dittrich, Sebastian; Pahmeyer, Caroline; Schroder, Patricia; Teetzen, Carolin; Gee, HeonYung; Daouk, Ghaleb; Pohl, Martin; Kuhn, Elisa; Schermer, Bernhard; Küttner, Victoria; Boerries, Melanie; Busch, Hauke; Schiffer, Mario; Bergmann, Carsten; Krüger, Marcus; Hildebrandt, Friedhelm; Dengjel, Joern; Benzing, Thomas; Huber, Tobias B

2018-05-22

Damage to and loss of glomerular podocytes has been identified as the culprit lesion in progressive kidney diseases. Here, we combine mass spectrometry-based proteomics with mRNA sequencing, bioinformatics, and hypothesis-driven studies to provide a comprehensive and quantitative map of mammalian podocytes that identifies unanticipated signaling pathways. Comparison of the in vivo datasets with proteomics data from podocyte cell cultures showed a limited value of available cell culture models. Moreover, in vivo stable isotope labeling by amino acids uncovered surprisingly rapid synthesis of mitochondrial proteins under steady-state conditions that was perturbed under autophagy-deficient, disease-susceptible conditions. Integration of acquired omics dimensions suggested FARP1 as a candidate essential for podocyte function, which could be substantiated by genetic analysis in humans and knockdown experiments in zebrafish. This work exemplifies how the integration of multi-omics datasets can identify a framework of cell-type-specific features relevant for organ health and disease. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Particular geoscientific perspectives on stable isotope analysis in the arboreal system

NASA Astrophysics Data System (ADS)

Helle, Gerhard; Balting, Daniel; Pauly, Maren; Slotta, Franziska

2017-04-01

In geosciences stable isotopes of carbon, oxygen and hydrogen from the tree ring archive have been used for several decades to trace the course of past environmental and climatological fluctuations. In contrast to ice cores, the tree ring archive is of biological nature (like many other terrestrial archives), but provides the opportunity to establish site networks with very high resolution in space and time. Many of the basic physical mechanisms of isotope shifts are known, but biologically mediated processes may lead to isotope effects that are poorly understood. This implies that the many processes within the arboreal system leading to archived isotope ratios in wood material are governed by a multitude of environmental variables that are not only tied to the isotopic composition of atmospheric source values (precipitation, CO2), but also to seasonally changing metabolic flux rates and pool sizes of photosynthates within the trees. Consequently, the extraction of climate and environmental information is particularly challenging and reconstructions are still of rather qualitative nature. Over the last 10 years or so, monitoring studies have been implemented to investigate stable isotope, climate and environmental signal transfer within the arboreal system to develop transfer or response functions that can translate the relevant isotope values extracted from tree rings into climate or other environmental variables. To what extent have these efforts lead to a better understanding that helps improving the meaningfulness of tree ring isotope signals? For example, do monitoring studies help deciphering the causes for age-related trends in tree ring stable isotope sequences that are published in a growing number of papers. Are existing monitoring studies going into detail enough or is it already too much effort for the outcome? Based on what we know already particularly in mesic habitats, tree ring stable isotopes are much better climate proxies than other tree ring parameters. However, millennial or multi-millennial high quality reconstructions from tree ring isotopes are still rare. This is because of i) methodological constraints related to mass spectrometric analyses and ii) the nature of tree-ring chronologies that are put together by many trees of various individual ages. In view of this: What is the state-of-the-art in high throughput tree ring stable isotope analyses? Is it necessary to advance existing methodologies further to conserve the annual time resolution provided by the tree-ring archive? Other terrestrial archives, like lake sediments and speleothems rarely provide annually resolved stable isotope data. Furthermore, certain tree species from tropical or sub-tropical regions cannot be dated properly by dendrochronology and hence demand specific stable isotope measuring strategies, etc.. Although the points raised here do specifically apply for the tree ring archive, some of them are important for all proxy archives of organic origin.

Uncertainty evaluation in normalization of isotope delta measurement results against international reference materials.

PubMed

Meija, Juris; Chartrand, Michelle M G

2018-01-01

Isotope delta measurements are normalized against international reference standards. Although multi-point normalization is becoming a standard practice, the existing uncertainty evaluation practices are either undocumented or are incomplete. For multi-point normalization, we present errors-in-variables regression models for explicit accounting of the measurement uncertainty of the international standards along with the uncertainty that is attributed to their assigned values. This manuscript presents framework to account for the uncertainty that arises due to a small number of replicate measurements and discusses multi-laboratory data reduction while accounting for inevitable correlations between the laboratories due to the use of identical reference materials for calibration. Both frequentist and Bayesian methods of uncertainty analysis are discussed.

[Progress in omics research of Aspergillus niger].

PubMed

Sui, Yufei; Ouyang, Liming; Lu, Hongzhong; Zhuang, Yingping; Zhang, Siliang

2016-08-25

Aspergillus niger, as an important industrial fermentation strain, is widely applied in the production of organic acids and industrial enzymes. With the development of diverse omics technologies, the data of genome, transcriptome, proteome and metabolome of A. niger are increasing continuously, which declared the coming era of big data for the research in fermentation process of A. niger. The data analysis from single omics and the comparison of multi-omics, to the integrations of multi-omics based on the genome-scale metabolic network model largely extends the intensive and systematic understanding of the efficient production mechanism of A. niger. It also provides possibilities for the reasonable global optimization of strain performance by genetic modification and process regulation. We reviewed and summarized progress in omics research of A. niger, and proposed the development direction of omics research on this cell factory.

Isotopic values of the Amazon headwaters in Peru: comparison of the wet upper Río Madre de Dios watershed with the dry Urubamba-Apurimac river system.

PubMed

Lambs, L; Horwath, A; Otto, T; Julien, F; Antoine, P-O

2012-04-15

The Amazon River is a huge network of long tributaries, and little is known about the headwaters. Here we present a study of one wet tropical Amazon forest side, and one dry and cold Atiplano plateau, originating from the same cordillera. The aim is to see how this difference affects the water characteristics. Different kind of water (spring, lake, river, rainfall) were sampled to determine their stable isotopes ratios (oxygen 18/16 and hydrogen 2/1) by continuous flow isotope ratio mass spectrometry (IRMS). These ratios coupled with chemical analysis enabled us to determine the origin of the water, the evaporation process and the water recycling over the Amazon plain forest and montane cloud forest. Our study shows that the water flowing in the upper Madre de Dios basin comes mainly from the foothill humid forest, with a characteristic water recycling process signature, and not from higher glacier melt. On the contrary, the water flowing in the Altiplano Rivers is mainly from glacier melts, with a high evaporation process. This snow and glacier are fed mainly by Atlantic moisture which transits over the large Amazon forest. The Atlantic moisture and its recycling over this huge tropical forest display a progressive isotopic gradient, as a function of distance from the ocean. At the level of the montane cloud forest and on the altiplano, respectively, additional water recycling and evaporation occur, but they are insignificant in the total water discharge. Copyright © 2012 John Wiley & Sons, Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Practical experience using speleothem data in multi-proxy climate reconstructions

NASA Astrophysics Data System (ADS)

Graham, N.

2009-04-01

Speleothem records have clear potential to extend and sharpen our understanding of past climate change. Many speleothem records feature both high sample resolution and precision age models, characteristics generally available only in tree-ring records, among terrestrial climate proxies. Speleothem records also avoid some processes that add uncertainty to the interpretation of biological proxy records. At the same time, model results suggest that even if speleothems did provide long and perfect records of meteoric water isotope concentrations, it would not be always be obvious how to interpret the isotopic fluctuations unambiguously in terms of precipitation or temperature variability. Other uncertainties can arise from local hydrologic and speleothem growth processes, as well as sampling and calibration uncertainties. Similar comments apply to other sorts of speleothem-derived records, e.g., verve thickness. These issues of interpretation are especially important in cases where data availability makes calibration to local climate data problematic and when past climate conditions limit the relevance of such calibrations. The presentation will focus broadly on the use of speleothem records together with other sorts of proxy records either to get a general idea of climatic change during some period, or for more formal climate field reconstruction. Examples from few such efforts will be given. Results from simulations with models incorporating stable water isotopes will be discussed, with consideration of what the results imply about the climatic interpretation of speleothem isotope records. The views will be those a climate scientist trying to make better use of speleothem data, a perspective which will highlight 1) where climate researchers would benefit from better understanding of isotope and speleothem processes, and 2) what steps that speleothem researchers could take to tighten the physical interpretation of their records. Convergence on these points will allow us to take better take advantage of the precision and spatial distribution of speleothem records offer for the understanding of past climate.

Assessment of sources and fate of nitrate in shallow groundwater of an agricultural area by using a multi-tracer approach.

PubMed

Pastén-Zapata, Ernesto; Ledesma-Ruiz, Rogelio; Harter, Thomas; Ramírez, Aldo I; Mahlknecht, Jürgen

2014-02-01

Nitrate isotopic values are often used as a tool to understand sources of contamination in order to effectively manage groundwater quality. However, recent literature describes that biogeochemical reactions may modify these values. Therefore, data interpretation is difficult and often vague. We provide a discussion on this topic and complement the study using halides as comparative tracers assessing an aquifer underneath a sub-humid to humid region in NE Mexico. Hydrogeological information and stable water isotopes indicate that active groundwater recharge occurs in the 8000km(2) study area under present-day climatic and hydrologic conditions. Nitrate isotopes and halide ratios indicate a diverse mix of nitrate sources and transformations. Nitrate sources include organic waste and wastewater, synthetic fertilizers and soil processes. Animal manure and sewage from septic tanks were the causes of groundwater nitrate pollution within orchards and vegetable agriculture. Dairy activities within a radius of 1,000 m from a sampling point significantly contributed to nitrate pollution. Leachates from septic tanks caused nitrate pollution in residential areas. Soil nitrogen and animal waste were the sources of nitrate in groundwater under shrubland and grassland. Partial denitrification processes helped to attenuate nitrate concentration underneath agricultural lands and grassland, especially during summer months. © 2013. Published by Elsevier B.V. All rights reserved.

Multi-institutional tumor banking: lessons learned from a pancreatic cancer biospecimen repository.

PubMed

Demeure, Michael J; Sielaff, Timothy; Koep, Larry; Prinz, Richard; Moser, A James; Zeh, Herb; Hostetter, Galen; Black, Jodi; Decker, Ardis; Rosewell, Sandra; Bussey, Kimberly J; Von Hoff, Daniel

2010-10-01

Clinically annotated pancreatic cancer samples are needed for progress to be made toward developing more effective treatments for this deadly cancer. As part of a National Cancer Institute-funded program project, we established a biospecimen core to support the research efforts. This article summarizes the key hurdles encountered and solutions we found in the process of developing a successful multi-institution biospecimen repository.

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

NASA Astrophysics Data System (ADS)

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

2007-12-01

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

Applications of Ultra-Intense, Short Laser Pulses

NASA Astrophysics Data System (ADS)

Ledingham, Ken W. D.

The high intensity laser production of electron, proton, ion and photon beams is reviewed particularly with respect to the laser-plasma interaction which drives the acceleration process. A number of applications for these intense short pulse beams is discussed e.g. ion therapy, PET isotope production and laser driven transmutation studies. The future for laser driven nuclear physics at the huge new, multi-petawatt proposed laser installation ELI in Bucharest is described. Many people believe this will take European nuclear research to the next level.

Mesoscopic modeling of multi-physicochemical transport phenomena in porous media

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

Kang, Qinjin; Wang, Moran; Mukherjee, Partha P

2009-01-01

We present our recent progress on mesoscopic modeling of multi-physicochemical transport phenomena in porous media based on the lattice Boltzmann method. Simulation examples include injection of CO{sub 2} saturated brine into a limestone rock, two-phase behavior and flooding phenomena in polymer electrolyte fuel cells, and electroosmosis in homogeneously charged porous media. It is shown that the lattice Boltzmann method can account for multiple, coupled physicochemical processes in these systems and can shed some light on the underlying physics occuning at the fundamental scale. Therefore, it can be a potential powerful numerical tool to analyze multi-physicochemical processes in various energy, earth,more » and environmental systems.« less

In-situ Sr isotopic measurement of scheelite using fs-LA-MC-ICPMS

NASA Astrophysics Data System (ADS)

Li, Chao; Zhou, Limin; Zhao, Zheng; Zhang, Zhiyuan; Zhao, Hong; Li, Xinwei; Qu, Wenjun

2018-07-01

Scheelite is one of the main ore minerals in tungsten deposits, and Sr isotopic compositions of scheelite can be used to examine the petrogenesis of igneous rocks and fluid metasomatism in mineralization processes. Both thermal ionization mass spectrometer (TIMS) and femsecond laser ablation multi-collector inductively coupled plasma mass spectrometer (fs-LA-MC-ICP-MS) have been applied to analyze Sr isotopic compositions in scheelite. Here we describe a LA-MC-ICP-MS technique which can obtain in-situ, accurate, high precision 87Sr/86Sr ratios from 20 to 50 μm scheelite in line mode without requiring time-consuming mineral separation and pre-chemical procedures. We found that Ca dimers and Ca argides do not detectably affect the obtained 87Sr/86Sr ratios, and the adopted protocol overcomes interferences from Kr+, Rb+, Er2+ and Yb2+. The results of three MPI-DING reference glasses (KL2-G, ML3B-G and StHs6/80-G) are consistent with the recommended values. Here we show that the values of 87Sr/86Sr are relatively homogeneous for two scheelites from quartz veins, and are comparable to the values determined by a traditional solution method. Hence, these two scheelite samples have the potential to be reference materials for Sr isotopic determination by LA-MC-ICP-MS. To illustrate the utility of the technique, Sr isotopes of scheelites from three different types of tungsten deposits of South China are documented. The 87Sr/86Sr of scheelite from granite-related veinlet-disseminated and porphyry tungsten deposits varies systematically, showing a positive correlation between Sr content and 87Sr/86Sr ratios. These micrometer scale inhomogeneities could be explained by mixing of two components, reflecting intense fluid metasomatism during mineralization processes. High 87Sr/86Sr ratios were obtained for the scheelite samples from a quartz vein type tungsten deposit, indicating that the late stage ore-forming fluid was mainly derived from the surrounding strata. These examples show that in-situ Sr isotopic measurement of scheelite is a powerful tool to decipher the degree of fluid-rock interaction in ore-forming processes.

TIGRESS: TRIUMF-ISAC gamma-ray escape-suppressed spectrometer

NASA Astrophysics Data System (ADS)

Svensson, C. E.; Amaudruz, P.; Andreoiu, C.; Andreyev, A.; Austin, R. A. E.; Ball, G. C.; Bandyopadhyay, D.; Boston, A. J.; Chakrawarthy, R. S.; Chen, A. A.; Churchman, R.; Drake, T. E.; Finlay, P.; Garrett, P. E.; Grinyer, G. F.; Hackman, G.; Hyland, B.; Jones, B.; Kanungo, R.; Maharaj, R.; Martin, J. P.; Morris, D.; Morton, A. C.; Pearson, C. J.; Phillips, A. A.; Ressler, J. J.; Roy, R.; Sarazin, F.; Schumaker, M. A.; Scraggs, H. C.; Smith, M. B.; Starinsky, N.; Valiente-Dobón, J. J.; Waddington, J. C.; Watters, L. M.

2005-10-01

The TRIUMF-ISAC gamma-ray escape-suppressed spectrometer (TIGRESS) is a new γ-ray detector array being developed for use at TRIUMF's Isotope Separator and Accelerator (ISAC) radioactive ion beam facility. TIGRESS will comprise 12 32-fold segmented clover-type HPGe detectors coupled with 20-fold segmented modular Compton suppression shields and custom digital signal processing electronics. This paper provides an overview of the TIGRESS project and progress in its development to date.

Carbon Monoxide Isotopes: On the Trail of Galactic Chemical Evolution

NASA Technical Reports Server (NTRS)

Langer, W.

1995-01-01

From the early days of the discovery of radio emission from carbon monoxide it was realized that it offered unusual potential for under- standing the chemical evolution of the Galaxy and external galaxies through measurements of molecular isotopes. These results bear on stellar nucleosynthesis, star formation, and gases in the interstellar medium. Progress in isotopic radio measurements will be reviewed.

Combining wood anatomy and stable isotope variations in a 600-year multi-parameter climate reconstruction from Corsican black pine

NASA Astrophysics Data System (ADS)

Szymczak, Sonja; Hetzer, Timo; Bräuning, Achim; Joachimski, Michael M.; Leuschner, Hanns-Hubert; Kuhlemann, Joachim

2014-10-01

We present a new multi-parameter dataset from Corsican black pine growing on the island of Corsica in the Western Mediterranean basin covering the period AD 1410-2008. Wood parameters measured include tree-ring width, latewood width, earlywood width, cell lumen area, cell width, cell wall thickness, modelled wood density, as well as stable carbon and oxygen isotopes. We evaluated the relationships between different parameters and determined the value of the dataset for climate reconstructions. Correlation analyses revealed that carbon isotope ratios are influenced by cell parameters determining cell size, whereas oxygen isotope ratios are influenced by cell parameters determining the amount of transportable water in the xylem. A summer (June to August) precipitation reconstruction dating back to AD 1185 was established based on tree-ring width. No long-term trends or pronounced periods with extreme high/low precipitation are recorded in our reconstruction, indicating relatively stable moisture conditions over the entire time period. By comparing the precipitation reconstruction with a summer temperature reconstruction derived from the carbon isotope chronologies, we identified summers with extreme climate conditions, i.e. warm-dry, warm-wet, cold-dry and cold-wet. Extreme climate conditions during summer months were found to influence cell parameter characteristics. Cold-wet summers promote the production of broad latewood composed of wide and thin-walled tracheids, while warm-wet summers promote the production of latewood with small thick-walled cells. The presented dataset emphasizes the potential of multi-parameter wood analysis from one tree species over long time scales.

(n,{gamma}) Experiments on tin isotopes

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

Baramsai, B.; Mitchell, G. E.; Walker, C. L.

2013-04-19

Neutron capture experiments on highly enriched {sup 117,119}Sn isotopes were performed with the DANCE detector array located at the Los Alamos Neutron Science Center. The DANCE detector provides detailed information about the multi-step {gamma}-ray cascade following neutron capture. Analysis of the experimental data provides important information to improve understanding of the neutron capture reaction, including a test of the statistical model, the assignment of spins and parities of neutron resonances, and information concerning the Photon Strength Function (PSF) and Level Density (LD) below the neutron separation energy. Preliminary results for the (n,{gamma}) reaction on {sup 117,119}Sn are presented. Resonance spinsmore » of the odd-A tin isotopes were almost completely unknown. Resonance spins and parities have been assigned via analysis of the multi-step {gamma}-ray spectra and directional correlations.« less

Evidence of magmatic degassing in Archean komatiites: Insights from the Wannaway nickel-sulfide deposit, Western Australia

NASA Astrophysics Data System (ADS)

Caruso, Stefano; Fiorentini, Marco L.; Moroni, Marilena; Martin, Laure A. J.

2017-12-01

Magmatic degassing from komatiite lava flows potentially influenced the geochemical evolution of the Archean atmosphere and hydrosphere. We argue that the escape of SO2-rich volatiles from komatiites impacted on the mineralogical, geochemical and isotopic composition of associated nickel-sulfide mineralization leaving behind detectable and measurable footprints that can be best observed where the polarity of the magmatic sequence is clearly recognizable. Here we focus on the ore-bearing sequence of the Archean komatiite-hosted N01 nickel-sulfide orebody at Wannaway, Yilgarn Craton, Western Australia. This deposit displays a volcanic sequence with a well-defined succession of stratigraphically-correlated facies comprising a massive sulfide horizon at the base of the channelized komatiite flow, overlain by matrix and disseminated sulfide mineralization. Pyrrhotite is the dominant sulfide phase in the lower part of the ore profile. The amount of troilite gradually increases from the base of the matrix ore over several meters up-sequence, eventually becoming dominant at the expense of pyrrhotite. In the upper portion of the mineralized sequence troilite is associated with accessory Mn sulfide alabandite (MnS), which is usually reported in reduced terrestrial and extra-terrestrial environments. Such mineralogical and volcanological features are consistent with upwards decreasing in fS2 and fO2 away from the basal contact of the komatiite flow. After evaluating the possible role of metamorphism, the pyrrhotite-troilite-alabandite assemblage and the progressive up-sequence decrease of the pyrrhotite/troilite ratio across the upper part of the mineralized sequence are interpreted as magmatic and indicative of progressive loss of sulfur with concomitant establishment of reducing conditions within the sulfide melt ponding at the base of the komatiite lava. In this context, the investigation of spatially constrained sulfur isotopic signatures allows to isolate the multiple sulfur fractionation processes that impacted on sulfide mineralization and ultimately permits the identification of the isotopic shift associated with magmatic degassing. Following this approach we recognize two distinct sulfur isotope exchanges processes triggered by 1) assimilation of sulfidic shales during emplacement of the komatiite flow, and 2) equilibration between the sulfide melt and the sulfur dissolved in the silicate melt. We finally correlate the remaining δ34S depletion up-stratigraphy with the loss of heavy sulfur isotopes through magmatic degassing of SO2-rich volatiles from the ultramafic flow. The emission of SO2 upon emplacement and cooling of the magma flow would also explain the progressive reducing fO2 and fS2 conditions indicated by variations in mineral assemblages from the base of the komatiite upwards.

Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

PubMed

Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

2006-03-01

Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1.

Monitoring BTEX degradation by CSIA - chances and challenges

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Investigating Uranium Mobility Using Stable Isotope Partitioning of 238U/235U and a Reactive Transport Model

NASA Astrophysics Data System (ADS)

Bizjack, M.; Johnson, T. M.; Druhan, J. L.; Shiel, A. E.

2015-12-01

We report a numerical reactive transport model which explicitly incorporates the effectively stable isotopes of uranium (U) and the factors that influence their partitioning in bioactive systems. The model reproduces trends observed in U isotope ratios and concentration measurements from a field experiment, thereby improving interpretations of U isotope ratios as a tracer for U reactive transport. A major factor contributing to U storage and transport is its redox state, which is commonly influenced by the availability of organic carbon to support metal-reducing microbial communities. Both laboratory and field experiments have demonstrated that biogenic reduction of U(VI) fractionates the stable isotope ratio 238U/235U, producing an isotopically heavy solid U(IV) product. It has also been shown that other common reactive transport processes involving U do not fractionate isotopes to a consistently measurable level, which suggests the capacity to quantify the extent of bioreduction occurring in groundwater containing U using 238U/235U ratios. A recent study of a U bioremediation experiment at the Rifle IFRC site (Colorado, USA) applied Rayleigh distillation models to quantify U stable isotope fractionation observed during acetate amendment. The application of these simplified models were fit to the observations only by invoking a "memory-effect," or a constant source of low-concentration, unfractionated U(VI). In order to more accurately interpret the measured U isotope ratios, we present a multi-component reactive transport model using the CrunchTope software. This approach is capable of quantifying the cycling and partitioning of individual U isotopes through a realistic network of transport and reaction pathways including reduction, oxidation, and microbial growth. The model incorporates physical heterogeneity of the aquifer sediments through zones of decreased permeability, which replicate the observed bromide tracer, major ion chemistry, U concentration, and U isotope ratios. These results suggest that the rate-limited transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions in the modeling domain and that these zones are responsible for the suggested "memory" effect observed in previous U isotope studies at this site.

LabData database sub-systems for post-processing and quality control of stable isotope and gas chromatography measurements

NASA Astrophysics Data System (ADS)

Suckow, A. O.

2013-12-01

Measurements need post-processing to obtain results that are comparable between laboratories. Raw data may need to be corrected for blank, memory, drift (change of reference values with time), linearity (dependence of reference on signal height) and normalized to international reference materials. Post-processing parameters need to be stored for traceability of results. State of the art stable isotope correction schemes are available based on MS Excel (Geldern and Barth, 2012; Gröning, 2011) or MS Access (Coplen, 1998). These are specialized to stable isotope measurements only, often only to the post-processing of a special run. Embedding of algorithms into a multipurpose database system was missing. This is necessary to combine results of different tracers (3H, 3He, 2H, 18O, CFCs, SF6...) or geochronological tools (Sediment dating e.g. with 210Pb, 137Cs), to relate to attribute data (submitter, batch, project, geographical origin, depth in core, well information etc.) and for further interpretation tools (e.g. lumped parameter modelling). Database sub-systems to the LabData laboratory management system (Suckow and Dumke, 2001) are presented for stable isotopes and for gas chromatographic CFC and SF6 measurements. The sub-system for stable isotopes allows the following post-processing: 1. automated import from measurement software (Isodat, Picarro, LGR), 2. correction for sample-to sample memory, linearity, drift, and renormalization of the raw data. The sub-system for gas chromatography covers: 1. storage of all raw data 2. storage of peak integration parameters 3. correction for blank, efficiency and linearity The user interface allows interactive and graphical control of the post-processing and all corrections by export to and plot in MS Excel and is a valuable tool for quality control. The sub-databases are integrated into LabData, a multi-user client server architecture using MS SQL server as back-end and an MS Access front-end and installed in four laboratories to date. Attribute data storage (unique ID for each subsample, origin, project context etc.) and laboratory management features are included. Export routines to Excel (depth profiles, time series, all possible tracer-versus tracer plots...) and modelling capabilities are add-ons. The source code is public domain and available under the GNU general public licence agreement (GNU-GPL). References Coplen, T.B., 1998. A manual for a laboratory information management system (LIMS) for light stable isotopes. Version 7.0. USGS open file report 98-284. Geldern, R.v., Barth, J.A.C., 2012. Optimization of instrument setup and post-run corrections for oxygen and hydrogen stable isotope measurements of water by isotope ratio infrared spectroscopy (IRIS). Limnology and Oceanography: Methods 10, 1024-1036. Gröning, M., 2011. Improved water δ2H and δ18O calibration and calculation of measurement uncertainty using a simple software tool. Rapid Communications in Mass Spectrometry 25, 2711-2720. Suckow, A., Dumke, I., 2001. A database system for geochemical, isotope hydrological and geochronological laboratories. Radiocarbon 43, 325-337.

A multi-proxy isotope study (δ41K, δ26Mg, 87Sr/86Sr) of low-temperature oceanic crust alteration: the Troodos Ophiolite and Ocean Drilling Program Hole 801C

NASA Astrophysics Data System (ADS)

Santiago Ramos, D. P.; Higgins, J. A.

2017-12-01

Low-temperature alteration of oceanic crust plays an important role in a number of geochemical cycles, thus modulating the chemical composition of the oceans. In particular, it has been established that low-temperature (<150oC) alteration of basalt is a major sink of seawater potassium. However, little is known about the effects of this process on the potassium isotope composition of seawater, which is 0.5‰ enriched relative to bulk silicate Earth (δ41KBSE=-0.54‰). Here we measure a number of isotope systems (δ41K, δ26Mg, 87Sr/86Sr) in both host rock and vein material from the upper volcanic section of Cretaceous (Troodos Ophiolite) and Jurassic (ODP 801C) oceanic crust using a MC-ICP-MS. The goal is to estimate the K isotopic fractionation associated with basalt alteration in low-temperature conditions, and how it might affect the K isotope enrichment of seawater relative to BSE. We find that marine hydrothermal samples from Troodos and ODP site 801C are enriched in potassium relative to the unaltered glass compositions and have δ41K values both higher and lower than BSE, ranging from -0.45‰ to -0.69‰ (n = 9) and -0.32‰ to -0.71‰ (n = 5), respectively. The low measured δ41K values could represent 1) fractionation (α<1) of K isotopes during uptake from seawater (δ41KSW 0‰), or 2) remobilized mantle-sourced K (δ41KBSE=-0.54‰) from deeper within the ophiolite sequence. Measurements of δ26Mg (n=15) and 87Sr/86Sr (n=12) in these samples yield enriched values relative to bulk silicate Earth, suggesting that alteration of oceanic crust likely happened under high water-to-rock ratios in both Troodos and ODP 801C, and that the added potassium is seawater-sourced. We thus suggest that the isotopically light δ41K values measured in both sites are associated with the formation of secondary clays enriched in the 39K isotope. This light isotope enrichment could be intensified if seawater K sourcing is a diffusion-limited process, as aqueous potassium diffusion has been associated with K isotope fractionations between 0.9967 and 0.9984. Our results indicate that the uptake of potassium in altered oceanic crust could be responsible, in part, for the observed K isotope enrichment of seawater relative to bulk silicate Earth.

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.

Seasonal, synoptic and diurnal variation of atmospheric water-isotopologues in the boundary layer of Southwestern Germany caused by plant transpiration, cold-front passages and dewfall.

NASA Astrophysics Data System (ADS)

Christner, Emanuel; Dyroff, Christoph; Kohler, Martin; Zahn, Andreas; Gonzales, Yenny; Schneider, Matthias

2013-04-01

Atmospheric water is an enormously crucial trace gas. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010) and carries huge amounts of latent heat. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. As H216O, H218O and HDO differ in vapor pressure and mass, isotope fractionation occurs due to condensation, evaporation and diffusion processes. In contrast to that, plants are able to transpire water with almost no isotope fractionation. For that reason the ratio of isotopologue concentrations in the boundary layer (BL) provides, compared to humidity measurements alone, independent and additional constraints for quantifying the strength of evaporation and transpiration. Furthermore the isotope ratios contain information about transport history of an air mass and microphysical processes, that is not accessible by humidity measurements. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) a commercial Picarro Analyzer L2120-i is operated at Karlsruhe in Southwestern Germany, which is continuously measuring the isotopologues H216O, HDO and H218O of atmospheric water vapor since January 2012. A one year record of H216O, HDO and H218O shows clear seasonal, synoptic and diurnal characteristics and reveals the main driving processes affecting the isotopic composition of water vapor in the Middle European BL. Changes in continental plant transpiration and evaporation throughout the year lead to a slow seasonal HDO/H216O-variation, that cannot be explained by pure Rayleigh condensation. Furthermore, cold-front passages from NW lead to fast and pronounced depletion of the HDO/H216O-ratio within minutes. Superimposed to these variations are local diurnal processes like dewfall, which cause a diurnal pattern captured by the deuterium excess.

Application of zinc isotope tracer technology in tracing soil heavy metal pollution

NASA Astrophysics Data System (ADS)

Norbu, Namkha; Wang, Shuguang; Xu, Yan; Yang, Jianqiang; Liu, Qiang

2017-08-01

Recent years the soil heavy metal pollution has become increasingly serious, especially the zinc pollution. Due to the complexity of this problem, in order to prevent and treat the soil pollution, it's crucial to accurately and quickly find out the pollution sources and control them. With the development of stable isotope tracer technology, it's able to determine the composition of zinc isotope. Based on the theory of zinc isotope tracer technique, and by means of doing some latest domestic and overseas literature research about the zinc isotope multi-receiving cups of inductively coupled plasma mass spectrometer (MC-ICP-MS) testing technology, this paper summarized the latest research results about the pollution tracer of zinc isotope, and according to the deficiencies and existing problems of previous research, made outlooks of zinc isotope fractionation mechanism, repository establishment and tracer multiple solutions.

Micro- and nano-mechanics in China: A brief review of recent progress and perspectives

NASA Astrophysics Data System (ADS)

Xu, ZhiPing; Zheng, QuanShui

2018-07-01

The past three decades have witnessed the explosion of nanoscience and technology, where notable research efforts have been made in synthesizing nanomaterials and controlling nanostructures of bulk materials. The uncovered mechanical behaviors of structures and materials with reduced sizes and dimensions pose open questions to the community of mechanicians, which expand the framework of continuum mechanics by advancing the theory, as well as modeling and experimental tools. Researchers in China have been actively involved into this exciting area, making remarkable contributions to the understanding of nanoscale mechanical processes, the development of multi-scale, multi-field modeling and experimental techniques to resolve the processing-microstructures-properties relationship of materials, and the interdisciplinary studies that broaden the subjects of mechanics. This article reviews selected progress made by this community, with the aim to clarify the key concepts, methods and applications of micro- and nano-mechanics, and to outline the perspectives in this fast-evolving field.

College of DuPage Planning Process: College of DuPage Planning, the Foundation for Decision Making.

ERIC Educational Resources Information Center

College of DuPage, Glen Ellyn, IL. Office of Research and Planning.

At College of DuPage (CD), in Glen Ellyn, Illinois, institutional planning is a multi-level, on-going process involving continuous college-wide input. The nine schematic levels in the CD planning process are interconnected and progress from global and broad-based issues, answering such questions as why the college exists, to concrete levels…

Ramping up to the Biology Workbench: A Multi-Stage Approach to Bioinformatics Education

ERIC Educational Resources Information Center

Greene, Kathleen; Donovan, Sam

2005-01-01

In the process of designing and field-testing bioinformatics curriculum materials, we have adopted a three-stage, progressive model that emphasizes collaborative scientific inquiry. The elements of the model include: (1) context setting, (2) introduction to concepts, processes, and tools, and (3) development of competent use of technologically…

Solar Spectral Irradiance Reconstruction over 9 Millennia from a Composite 14C and 10Be Series

NASA Astrophysics Data System (ADS)

Wu, C. J.; Usoskin, I. G.; Krivova, N.; Kovaltsov, G.; Solanki, S. K.

2017-12-01

The Sun is the main external energy source to the Earth and thus the knowledge of solar variability on different time scales is important for understanding the solar influence on the terrestrial atmosphere and climate. The overall energy input and its spectral distribution are described by the total (TSI) and spectral (SSI) solar irradiance, respectively. Direct measurements of the solar irradiance provide information on solar variability on the decadal and shorter time scales, while the sunspot number record covers four centuries. On yet longer time scales only indirect proxies can be used, such as the concentrations of the cosmogenic isotopes 10Be and 14C in terrestrial archives. These isotopes are produced in the terrestrial atmosphere by impinging cosmic rays, whose flux is modulated by solar activity. Therefore the isotope data retrieved from various natural archives around the globe show a very high degree of similarity reflecting changes in the solar activity. Nevertheless, significant short-term deviations can be observed due to the different geochemical production processes and local climatic conditions. We will present the newest TSI/SSI reconstruction over the last 9000 years based on a new consistent composite multi-isotope proxy series. The solar irradiance reconstruction reveals the global and robust pattern of solar variability in the past.

A new approach for deciphering between single and multiple accumulation events using intra-tooth isotopic variations: Application to the Middle Pleistocene bone bed of Schöningen 13 II-4.

PubMed

Julien, Marie-Anne; Rivals, Florent; Serangeli, Jordi; Bocherens, Hervé; Conard, Nicholas J

2015-12-01

It is often difficult to differentiate between archaeological bonebeds formed by one event such as a mass kill of a single herd, and those formed by multiple events that occurred over a longer period of time. The application of high temporal resolution studies such as intra-tooth isotopic profiles on archaeological mammal cohorts offers new possibilities for exploring this issue, allowing investigators to decipher between single and multiple accumulation events. We examined (18)O and (13)C isotopic variations from the enamel carbonate of 23 horse third molars from the Middle Pleistocene archaeological site of Schöningen. We employed a new approach to investigate processes of fossil accumulation that uses both bulk and intra-tooth isotopic variations and takes into account animal behavior, age at death and dental development to test the degree of isotopic affinity of animals from the same fossil assemblage. Oxygen and carbon isotope bulk values indicate that the horses from Schöningen 13 II-4 experienced relatively similar climatic and dietary regimes. Inter-individual differences of the bulk values of the horses sampled in the current study present nevertheless inter-individual variability similar to individuals from multi-layered localities. In addition, the intra-tooth isotopic variation of specimens of the same age at death seems to indicate that the studied cohort corresponds to a mix of individuals that recorded both similar and different isotopic histories. Finally, the conditions recorded in the isotopic signal shortly before death (i.e., for teeth not fully mineralized) varied between sampled individuals, suggesting possible differences in the seasonality of death. Considering those results, we discuss the possibility that the horses from Schöningen 13 II-4 correspond to an accumulation of different death events. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dual isotopic approach for determining groundwater origin and water-rock interactions in over exploited watershed in India

NASA Astrophysics Data System (ADS)

Negrel, Philippe; Pauwels, Hélène; Millot, Romain; Roy, Stéphane; Guerrot, Catherine

2010-05-01

Groundwater flow and storage in hard rock areas is becoming a matter of great interest and importance to researchers and water managers either with regards to the quantity, quality of water as well as delimitation of resources and aquifers. Degradation of groundwater resources by abstraction, contamination, ... has been increasing in many areas and is of growing concern for few decades. In terms of hydrogeology, hard rocks represent a quite heterogeneous and anisotropic media with irregular distribution of pathways of groundwater flow, typically consisting of three vertical zones, upper weathered, middle fractured and lower massive bedrock. Aim of this work is dual and the Maheshwaram watershed (53 km2, Andhra Pradesh, India) representative of watersheds in southern India in terms of geology, overpumping of its hard-rock aquifer (more than 700 classical open end wells in use), its cropping pattern (rice dominating), and its rural socio-economy mainly based on traditional agriculture is investigated through stable isotopes of the water molecule and lead isotopes in groundwater. The overall objective is to incorporate isotopic- and chemical-tracing data and constraints into methods for evaluating groundwater circulation. It divides into fingerprinting the groundwater recharge processes (e.g. the input by the monsoon) and the water use in such agricultural watershed, which is of primary importance in such semi-arid context and investigating the processes of water-rock interactions (e.g. granite-water interaction). In the frame of delimitation of resources and aquifers and long-term sustainability, we monitored the input from monsoon-precipitation over 2 years, and measured spatial and temporal variations in δ18O and δ2H in the groundwater and in precipitation. Individual recharge from the two monsoon periods was identified. This led to identification of periods during which evaporation affects groundwater quality through a higher concentration of salts and stable isotopes in the return flow. In addition, such evaporation is further affected by land use, rice paddies having the strongest evapotranspiration. Lead concentrations span over one or two orders of magnitude up to approximately 20 ?g. L-1. Pb-isotopes, measured in water by MC-ICPMS using an improved new procedure, fluctuate largely as exemplified by the 206Pb/204Pb ratio, reaching values up to 25. Most of the lead in the groundwaters is of geogenic origin, and through the lead isotopic signature in groundwater we have traced and fingerprinted the processes of water-rock interactions considering the granite matrix. Combining a weathering model and field observations, we have defined a two step weathering process that includes a control on the Pb-isotopes ratios by accessory phases and by the main mineral from the granite in a second step of weathering. For future studies, multi-isotope approach will be necessary for the identification of possible flowpaths, in conjunction with the larger exploitation of the groundwater resources. This is also challenging for generalising the use of isotope tools (such as Nd, Sr, Pb and newly developed isotope systematics like Ca, Si...) in many other catchments that may face structural problems of groundwater overdraft.

Late Quaternary palaeoenvironmental reconstruction from Lake Ohrid using stable isotopes

NASA Astrophysics Data System (ADS)

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

2016-04-01

Lake Ohrid is a large, deep lake located on the Balkan Peninsula at the border between Macedonia and Albania, and is considered the oldest extant lake in Europe. An International Continental scientific Drilling Program (ICDP) deep drilling campaign was carried out in 2013 as part of the interdisciplinary Scientific Collaboration On Past Speciation Conditions in Lake Ohrid (SCOPSCO) project. Over 1500 m of sediment were recovered from six coring locations at the main target site in the central basin, where the maximum drill depth reached 569 m below the lake floor. Initial results indicate continuous lacustrine conditions over the past >1.2 Ma (Wagner et al., 2014). Here, we present oxygen and carbon isotope data (δ18O and δ13C) from carbonate from the upper 248 m of the SCOPSCO succession, which covers the last 640 ka, spanning marine isotope stages 15-1, according to an age model based on tephra and orbital tuning (Francke et al., 2015). Modern monitoring data show Lake Ohrid to be an evaporative system, where variations in δ18O of endogenic carbonate are primarily a function of changes in water balance, and δ13C largely reflects fluctuations in the amount of soil-derived CO2 and organic matter recycling. Our results indicate a trend from wetter to drier conditions through the Holocene, which is consistent with regional and hemispheric processes related to changes in insolation and progressive aridification. Over the last 640 ka, relatively stable climate conditions are inferred before ca. 450 ka, a transition to a wetter climate between ca. 400-250 ka, and a trend to drier climate after ca. 250 ka. Higher frequency, multi-millennial-scale oscillations observed during warm stages are most likely associated with regional climate change as a function of orbital forcing. This record is one of the most extensive and highly-resolved continental isotope records available, and emphasises the potential of Lake Ohrid as a valuable archive of long-term palaeoclimate and palaeoenvironmental change in the northern Mediterranean region. Francke, A., Wagner, B., Just, J., Leicher, N., Gromig, R., Baumgarten, H., Vogel, H., Lacey, J. H., Sadori, L., Wonik, T., Leng, M. J., Zanchetta, G., Sulpizio, R., and Giaccio, B. (2015). Sedimentological processes and environmental variability at Lake Ohrid (Macedonia, Albania) between 640 ka and present day. Biogeosciences Discussions 12, 15111-15156. Wagner, B., Wilke, T., Krastel, S., Zanchetta, G., Sulpizio, R., Reicherter, K., Leng, M. J., Grazhdani, A., Trajanovski, S., Francke, A., Lindhorst, K., Levkov, Z., Cvetkoska, A., Reed, J. M., Zhang, X., Lacey, J. H., Wonik, T., Baumgarten, H., and Vogel, H. (2014). The SCOPSCO drilling project recovers more than 1.2 million years of history from Lake Ohrid. Scientific Drilling 17, 19-29.

Carbon isotope fractionation during microbial methane oxidation

NASA Astrophysics Data System (ADS)

Barker, James F.; Fritz, Peter

1981-09-01

Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

Archean crustal evolution in the Southern São Francisco craton, Brazil: Constraints from U-Pb, Lu-Hf and O isotope analyses

NASA Astrophysics Data System (ADS)

Albert, Capucine; Farina, Federico; Lana, Cristiano; Stevens, Gary; Storey, Craig; Gerdes, Axel; Dopico, Carmen Martínez

2016-12-01

In this study we present U-Pb and Hf isotope data combined with O isotopes in zircon from Neoarchean granitoids and gneisses of the southern São Francisco craton in Brazil. The basement rocks record three distinct magmatic events: Rio das Velhas I (2920-2850 Ma), Rio das Velhas II (2800-2760 Ma) and Mamona (2750-2680 Ma). The three sampled metamorphic complexes (Bação, Bonfim and Belo Horizonte) have distinct εHf vs. time arrays, indicating that they grew as separate terranes. Paleoarchean crust is identified as a source which has been incorporated into younger magmatic rocks via melting and mixing with younger juvenile material, assimilation and/or source contamination processes. The continental crust in the southern São Francisco craton underwent a change in magmatic composition from medium- to high-K granitoids in the latest stages, indicating a progressive HFSE enrichment of the sources that underwent anatexis in the different stages and possibly shallowing of the melting depth. Oxygen isotope data shows a secular trend towards high δ18O (up to 7.79‰) indicating the involvement of metasediments in the petrogenesis of the high potassium granitoids during the Mamona event. In addition, low δ18O values (down to 2.50‰) throughout the Meso- and Neoarchean emphasize the importance of meteoritic fluids in intra-crustal magmatism. We used hafnium isotope modelling from a compilation of detrital zircon compositions to constrain crustal growth rates and geodynamics from 3.50 to 2.65 Ga. The modelling points to a change in geodynamic process in the southern São Francisco craton at 2.9 Ga, from a regime dominated by net crustal growth in the Paleoarchean to a Neoarchean regime marked by crustal reworking. The reworking processes account for the wide variety of granitoid magmatism and are attributed to the onset of continental collision.

NUCLEOSYNTHETIC TUNGSTEN ISOTOPE ANOMALIES IN ACID LEACHATES OF THE MURCHISON CHONDRITE: IMPLICATIONS FOR HAFNIUM-TUNGSTEN CHRONOMETRY

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

Burkhardt, Christoph; Wieler, Rainer; Kleine, Thorsten

Progressive dissolution of the Murchison carbonaceous chondrite with acids of increasing strengths reveals large internal W isotope variations that reflect a heterogeneous distribution of s- and r-process W isotopes among the components of primitive chondrites. At least two distinct carriers of nucleosynthetic W isotope anomalies must be present, which were produced in different nucleosynthetic environments. The co-variation of {sup 182}W/{sup 184}W and {sup 183}W/{sup 184}W in the leachates follows a linear trend that is consistent with a mixing line between terrestrial W and a presumed s-process-enriched component. The composition of the s-enriched component agrees reasonably well with that predicted bymore » the stellar model of s-process nucleosynthesis. The co-variation of {sup 182}W/{sup 184}W and {sup 183}W/{sup 184}W in the leachates provides a means for correcting the measured {sup 182}W/{sup 184}W and {sup 182}W/{sup 183}W of Ca-Al-rich inclusions (CAI) for nucleosynthetic anomalies using the isotopic variations in {sup 183}W/{sup 184}W. This new correction procedure is different from that used previously, and results in a downward shift of the initial {epsilon}{sup 182}W of CAI to -3.51 {+-} 0.10 (where {epsilon}{sup 182}W is the variation in 0.01% of the {sup 182}W/{sup 183}W ratio relative to Earth's mantle). This revision leads to Hf-W model ages of core formation in iron meteorite parent bodies that are {approx}2 Myr younger than previously calculated. The revised Hf-W model ages are consistent with CAI being the oldest solids formed in the solar system, and indicate that core formation in some planetesimals occurred within {approx}2 Myr of the beginning of the solar system.« less

Stable Isotopic Constraints on Abiogenic Hydrocarbon gas Contributions to Thermogenic Natural gas Resources in the Northern Appalachian Basin, USA

NASA Astrophysics Data System (ADS)

Burruss, R. C.; Laughrey, C. D.

2006-05-01

The generation of abiogenic methane by serpentinization or by graphite-water reactions in high-grade metamorphic rocks is well documented by isotopic, fluid inclusion, and petrographic studies. However, geochemical evidence is equivocal for abiogenic generation of higher hydrocarbon gases (ethane through pentane) in economic resources. Thermogenic hydrocarbon gases, generated by thermal cracking of sedimentary organic matter of biological origin, are progressively enriched in 13C as a function of increasing number of carbon atoms in the molecule. The isotopic composition is controlled by the kinetic isotope effect (KIE) during carbon-carbon bond breaking with the largest KIE for methane. Published work on gases in Precambrian rocks in Canada and South Africa suggest that some were generated by abiogenic Fischer-Tropsch type reactions that produced gases with carbon isotopic compositions that are reversed from the thermogenic trend. We have documented reversed isotopic compositions in natural gas accumulations in lower Paleozoic reservoirs of the Appalachian basin regionally from West Virginia and eastern Ohio through Pennsylvania to central New York. The regional accumulation in lower Silurian age strata shows progressive enhancement of the isotopic reversal with increasing depth in the basin. Multivariate analysis of the molecular and isotopic data define an end-member in the deep basin with an approximate composition of 98 mol % CH4, 1-2 mol % C2H6, << 1 mol % C3H8, and δ13C (CH4) = -27 ‰, δ13C (C2H6) = -40 ‰, δ13C (C3H8) = - 41‰. The nominal similarity of isotopic reversals in the gases from Precambrian rocks to those in the lower Paleozoic rocks of the Appalachian basin suggests that abiogenic F-T reactions may have generated some fraction of the gases in the deep basin. Comparison of molecular and hydrogen isotopic compositions show that the gases of putative abiogenic F-T origin are significantly different from Appalachian basin gases. All the Precambrian gases have extremely light hydrogen isotopic compositions of CH4 (δ2H < -300‰) and are depleted in CH4 (Canada gases C1/C2+ < 10, S. Africa gases C1/C2+ < 60) compared to gases in lower Paleozoic reservoirs of the Appalachian basin (δ2H (CH4) > -150‰, C1/C2+ up to 220). New isotopic studies of gas accumulations, gases in fluid inclusions, and of sedimentary organic matter in the Appalachian basin are in progress to constrain the possible contribution of abiogenic hydrocarbon generation to gas accumulations in this basin.

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.

A novel procedure for Rubidium separation and its isotope measurements on geological samples by MC-ICP-MS

NASA Astrophysics Data System (ADS)

Ma, J.; Zhang, Z.; Wei, G.; Zhang, L.

2017-12-01

A method including a novel column Rb separation procedure and high-precision Rb isotope measurement in geological materials by using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in standard-sample-bracketing (SSB) mode has been developed. Sr-Spec resin was employed, in which the distribution coefficients for Rb, K, Ba and Sr are different in nitric acid, to sequentially separate them from the matrix. The dissolved samples were loaded on the column in 3 M HNO3, the main matrix such as Al, Ca, Fe, Mg, Mn and Na were removed by rinsing with 4.5 mL HNO3, Rb and K were then sequentially eluted by 3 M HNO3 in different volumes. After that, Ba was eluted by 8 M HNO3, and Sr was finally eluted by Milli-Q water. This enable us to collect the pure Rb, K, Ba and Sr one by one with recovery close to 100% for their isotopic compositions measurement on MC-ICP-MS. We here focus on Rb isotope measurement. The measurement using MC-ICP-MS yielded an internal precision for δ87Rb of < ± 0.03‰ (2SE), and the external precision was generally better than ± 0.06‰ (2SD) based on the long-term results of the Rb standard solutions NIST SRM 984. A series of geological rock standards, were analyzed using this method, and the results indicate significant Rb isotope differences in different geologic materials. This will provide a powerful tool to investigate Rb isotope fractionation during geological processes.Based on this method, Rb isotope compositions from a basaltic weathering profile were carried out. The data show the lighter Rb (85Rb) isotope is preferentially leached from the weathering profile and remains heavy Rb isotope (87Rb) in the weathered residues during the incipient weathering stage. From the moderate to advanced weathering stage, the significant variations of Rb isotope were observed and multiple factors, such as leaching, adsorption, desorption, and precipitation, should play important role in fractionating Rb isotope.

Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Célia J.; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Bernard, Sophie; Kaiser, Jan; Levin, Ingeborg; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik S. W.; Röckmann, Thomas

2017-04-01

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol-1 in 1940 to (322 ± 1) nmol mol-1 in 2008, the isotopic composition of atmospheric N2O decreased by (-2.2 ± 0.2) ‰ for δ15Nav, (-1.0 ± 0.3) ‰ for δ18O, (-1.3 ± 0.6) ‰ for δ15Nα, and (-2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (-7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water - VSMOW) for δ18O, δ15Nα = (-3.0 ± 1.9) ‰ and δ15Nβ = (-11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα - δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

Identifying source and formation altitudes of nitrates in drinking water from Réunion Island, France, using a multi-isotopic approach.

PubMed

Rogers, Karyne M; Nicolini, Eric; Gauthier, Virginie

2012-09-01

Nitrate concentrations, water isotopes (δ(2)H and δ(18)O(water)) and associated nitrate isotopes (δ(15)N(nitrate) and δ(18)O(nitrate)) from 10 drinking water wells, 5 fresh water springs and the discharge from 3 wastewater treatment stations in Réunion Island, located in the Indian Ocean, were analysed. We used a multi isotopic approach to investigate the extent of nitrate contamination, nitrate formation altitude and source of nitrates in Réunion Island's principal aquifer. Water from these study sites contained between 0.1 and 85.3 mg/L nitrate. δ(15)N(nitrate) values between +6 and +14‰ suggested the main sources of contamination were animal and/or human waste, rather than inorganic (synthetic) fertilisers, infiltrating through the subsurface into the saturated zone, due to rainfall leaching of the unsaturated zone at various altitudes of precipitation. Based on δ(15)N(nitrate) values alone, it was not possible to distinguish between animal and human activities responsible for the contamination of each specific catchment. However, using a multi isotope approach (δ(18)O(water) and δ(15)N(nitrate)), it was possible to relate the average altitude of rainfall infiltration (δ(18)O(water)) associated with the nitrate contamination (δ(18)O(nitrate)). This relationship between land use, rainfall recharge altitude and isotopic composition (δ(15)N(nitrate) and δ(18)O(water)) discriminated between the influences of human waste at lower (below 600 m elevation) or animal derived contamination (at elevations between 600 and 1300 m). By further comparing the theoretical altitude of nitrate formation calculated by the δ(18)O(nitrate), it was possible to determine that only 5 out of 15 fresh water wells and springs followed the conservative nitrate formation mechanism of 2/3δ(18)O(water)+1/3δ(18)O(air), to give nitrate formation altitudes which corresponded to land use activities. Copyright © 2012 Elsevier B.V. All rights reserved.

Progressive transmission of road network

NASA Astrophysics Data System (ADS)

Ai, Bo; Ai, Tinghua; Tang, Xinming; Li, Zhen

2009-10-01

The progressive transmission of vector map data requires efficient multi-scale data model to process the data into hierarchical structure. This paper presents such a data structure of road network without redundancy of geometry for progressive transmission. For a given scale, the road network display has to settle two questions. One is which road objects to be represented and the other is what geometric details to be visualized for the selected roads. This paper combines the Töpfer law and the BLG-tree structure into a multi-scale representation matrix to answer simultaneously the above two questions. In the matrix, rows from top to bottom represent the roads in the sequence of descending classification of traffic and length, which can support the Töpfer law to retrieve the more important roads. In a row, columns record one road by a linear BLG-tree to provide good line graphics.

Rapid mitigation of carrier-induced degradation in commercial silicon solar cells

NASA Astrophysics Data System (ADS)

Hallam, Brett J.; Chan, Catherine E.; Chen, Ran; Wang, Sisi; Ji, Jingjia; Mai, Ly; Abbott, Malcolm D.; Payne, David N. R.; Kim, Moonyong; Chen, Daniel; Chong, CheeMun; Wenham, Stuart R.

2017-08-01

We report on the progress for the understanding of carrier-induced degradation (CID) in p-type mono and multi-crystalline silicon (mc-Si) solar cells, and methods of mitigation. Defect formation is a key aspect to mitigating CID. Illuminated annealing can be used for both mono and mc-Si solar cells to reduce CID. The latest results of an 8-s UNSW advanced hydrogenation process applied to industrial p-type Czochralski PERC solar cells are shown with average efficiency enhancements of 1.1% absolute from eight different solar cell manufacturers. Results from three new industrial CID mitigation tools are presented, reducing CID to 0.8-1.1% relative, compared to 4.2% relative on control cells. Similar advanced hydrogenation processes can also be applied to multi-crystalline silicon passivated emitter with rear local contact (PERC) cells, however to date, the processes take longer and are less effective. Modifications to the firing processes can also suppress CID in multi-crystalline cells during subsequent illumination. The most stable results are achieved with a multi-stage process consisting of a second firing process at a reduced firing temperature, followed by extended illuminated annealing.

Solid-state optical refrigeration to sub-100 Kelvin regime

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

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

DOE PAGES

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; ...

2016-02-05

We report that since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈91K from room temperature.

Solid-state optical refrigeration to sub-100 Kelvin regime

PubMed Central

Melgaard, Seth D.; Albrecht, Alexander R.; Hehlen, Markus P.; Sheik-Bahae, Mansoor

2016-01-01

Since the first demonstration of net cooling twenty years ago, optical refrigeration of solids has progressed to outperform all other solid-state cooling processes. It has become the first and only solid-state refrigerator capable of reaching cryogenic temperatures, and now the first solid-state cooling below 100 K. Such substantial progress required a multi-disciplinary approach of pump laser absorption enhancement, material characterization and purification, and thermal management. Here we present the culmination of two decades of progress, the record cooling to ≈ 91 K from room temperature. PMID:26847703

Evaluation strategies and uncertainty calculation of isotope amount ratios measured by MC ICP-MS on the example of Sr.

PubMed

Horsky, Monika; Irrgeher, Johanna; Prohaska, Thomas

2016-01-01

This paper critically reviews the state-of-the-art of isotope amount ratio measurements by solution-based multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) and presents guidelines for corresponding data reduction strategies and uncertainty assessments based on the example of n((87)Sr)/n((86)Sr) isotope ratios. This ratio shows variation attributable to natural radiogenic processes and mass-dependent fractionation. The applied calibration strategies can display these differences. In addition, a proper statement of uncertainty of measurement, including all relevant influence quantities, is a metrological prerequisite. A detailed instructive procedure for the calculation of combined uncertainties is presented for Sr isotope amount ratios using three different strategies of correction for instrumental isotopic fractionation (IIF): traditional internal correction, standard-sample bracketing, and a combination of both, using Zr as internal standard. Uncertainties are quantified by means of a Kragten spreadsheet approach, including the consideration of correlations between individual input parameters to the model equation. The resulting uncertainties are compared with uncertainties obtained from the partial derivatives approach and Monte Carlo propagation of distributions. We obtain relative expanded uncertainties (U rel; k = 2) of n((87)Sr)/n((86)Sr) of < 0.03 %, when normalization values are not propagated. A comprehensive propagation, including certified values and the internal normalization ratio in nature, increases relative expanded uncertainties by about factor two and the correction for IIF becomes the major contributor.

Foraminiferal Stable Isotope Geochemistry At The Micrometer Scale: Is It A Dream Or Reality?

NASA Astrophysics Data System (ADS)

Misra, S.; Shuttleworth, S.; Lloyd, N. S.; Sadekov, A.; Elderfield, H.

2012-12-01

Over last few decades trace metals and stable isotope compositions of foraminiferal shells became one of the major tools to study past oceans and associated climate change. Empirical calibrations of δ11B, δ18O, Mg/Ca, Cd/Ca, Ba/Ca shells compositions have linked them to various environmental parameters such as seawater pH, temperature, salinity and productivity. Despite their common use as proxies, little is known about mechanisms of trace metals incorporation into foraminiferal calcite. Trace metals partition coefficients for foraminiferal calcite is significantly different from inorganic calcite precipitates underlining strong biological control on metal transport to the calcification sites and their incorporation into the calcite. Microscale distribution of light elements isotopes (e.g. Li, B, Mg) could potentially provide unique inside into these biomineralization processes improving our understanding of foraminiferal geochemistry. In this work we explore potentials of using recent advances in analytical geochemistry by employing laser ablation and multi-collector ICP-MS to study microscale distribution of Mg isotopes across individual foraminiferal shells and δ11B, and δ7Li analyses of individual shell chambers. The analytical setup includes an Analyte.G2 193nm excimer laser ablation system with two volume ablation cell connected to a Thermo Scientific NEPTUNE Plus MC-ICP-MS with Jet Interface option. We will discuss method limitations and advantages for foraminiferal geochemistry as well as our data on Mg isotopes distribution within shells of planktonic foraminifera.

Long-distance relationship between large-scale tropical SSTs and ice core-derived oxygen isotopic records in the Third Pole Region

NASA Astrophysics Data System (ADS)

Thompson, L. G.; Yao, T.; Mosley-Thompson, E. S.; Lin, P.

2012-12-01

The tropical hydrological cycle is a key factor coupling isotopic records from ice core, speleothem and lake records with tropical SSTs and the vertical amplification of temperature in the Tropics. Stable isotopic ratios, particularly of oxygen, preserved in glacier ice provide high resolution records of climate changes over long time periods. In polar ice sheets the isotopic signal is driven primarily by temperature while in low-latitudes it depends on a variety of hydrologic and thermal influences in the broad geographic region that supplies moisture to the mountain glaciers. The strong correlation between ice core-derived isotopic records throughout the low- and mid-latitudes and tropical SSTs likely reflects the dominance of tropical evaporation in the flux of water vapor to the atmosphere and provides a possible explanation for the large-scale isotopic links among low- and mid-latitude paleoclimate records. Many low- to mid-latitude ice fields provide continuous, annually-resolved proxy records of climatic and environmental variability recorded by many preserved and measurable parameters including oxygen and hydrogen isotopic ratios and net mass balance (accumulation). These records present an opportunity to examine the nature of climate variability in these regions in greater detail and to extract new information about long-distance relationships in the climate system. Understanding these relationships is essential for proper interpretation of the isotopic records archived in glaciers, lakes, speleothems and other paleo-archives in the Third Pole (TP) Region. Here we compare high resolution records from Dasuopu Glacier in the Himalaya, a speleothem record from Wanxiang Cave in Gansu Province on the TP and the annually resolved ice core records from the Quelccaya Ice Cap in the tropical Andes of South America. The purpose is to explore the role of long-distance processes in determining the isotopic composition of paleo archives on the TP. Running correlations between the Quelccaya and Dasuopu records over the last 500 years reveal that through time isotopes and net balance are both positively and negatively correlated over multi-decades scales while correlation of the annual values over the entire period is quite low. The annual isotopic records are strongly correlated with tropical Pacific SSTs (R2 = 0.55) reflecting the strong linkage between tropical Pacific SSTs associated with ENSO and tropospheric temperatures in the low latitudes. The well-documented contemporaneous loss of ice cover on Quelccaya, Naimona'nyi, Kilimanjaro in eastern Africa and the ice fields near Puncak Jaya in Papua, Indonesia likely reflects the dominance of large-scale processes. Moreover, such widespread melting is consistent with model predictions for a vertical amplification of temperature in the tropics and with increasing isotopic enrichment with elevation across the Third Pole Region over the last 100 years.

The origin of Neoproterozoic Cap Carbonates: a view from Mg and Sr Isotopes

NASA Astrophysics Data System (ADS)

Liu, C.; Raub, T. D.; Evans, D. A.; Wang, Z.

2010-12-01

Neoproterozoic cap carbonates are suggested to document Earth’s transition from a ‘snowball earth’ to an ‘extreme greenhouse’ environment. Geochemistry of these rocks is essential for its paleo-environment reconstruction, and Mg and Sr isotopes can help to understand its origin and constrain geochemical evolution of the contemporary ocean. In this study, we studied Mg and Sr isotope composition of 18 cap dolostone samples from Nuccaleena formation carbonate and one from the the mixed siliciclastic transition at its base at Elatina Creek in Adelaide Geosyncline of South Australia. We established a step-leaching procedure using ammonium acetate, various concentrations of acetic acid, and HCl on four of these cap carbonate samples to untangle the isotopic signatures of its various constituent phases. 87Sr/86Sr values of the leachates in each sample decrease continuously as leaching process proceeds and sometimes rebound as silicates are dissolved. The lowest leachate 87Sr/86Sr values, down to 0.7084, are lower than the reported dolostone(~0.7096) but still higher than those of limestones overlying the dolostone in other basins(~0.7079), indicating an input of increasing level of weathering to the ocean over the course of cap-carbonate precipitation. In contrast, δ26MgDSM3 variation with progressing leaching steps exhibits a wave pattern (variation up to 0.4~0.5‰) during the leaching processes, due to different chemical affinity of Mg in various mineral phases. More importantly, Mg isotope composition of the portion that is associated with stratigraphically low, minimum Sr isotope composition is similar to those of contemporary corals (or inorganic aragonite precipitation), but up to ca. 0.6 per mil lower than stratigraphically-higher values, suggesting a warmer weather and/or more significant silicate weathering than contemporary Earth’s climate, and a transition from physical weathering to chemical weather during deglaciation.

Multi-Quasiparticle Gamma-Band Structure in Neutron-Deficient Ce and Nd Isotopes

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

Sheikh, Javid; Bhat, G. H.; Palit, R.

2009-01-01

The newly developed multi-quasiparticle triaxial projected shell-model approach is employed to study the high-spin band structures in neutron-deficient even-even Ce and Nd isotopes. It is observed that gamma bands are built on each intrinsic configuration of the triaxial mean-field deformation. Due to the fact that a triaxial configuration is a superposition of several K states, the projection from these states results in several low-lying bands originating from the same intrinsic configuration. This generalizes the well-known concept of the surface gamma oscillation in deformed nuclei based on the ground state to gamma bands built on multi-quasiparticle configurations. This new feature providesmore » an alternative explanation on the observation of two I=10 aligning states in ^{134}Ce and both exhibiting a neutron character.« less

Multi-Scale Effects of Nestling Diet on Breeding Performance in a Terrestrial Top Predator Inferred from Stable Isotope Analysis

PubMed Central

Resano-Mayor, Jaime; Hernández-Matías, Antonio; Real, Joan; Moleón, Marcos; Parés, Francesc; Inger, Richard; Bearhop, Stuart

2014-01-01

Inter-individual diet variation within populations is likely to have important ecological and evolutionary implications. The diet-fitness relationships at the individual level and the emerging population processes are, however, poorly understood for most avian predators inhabiting complex terrestrial ecosystems. In this study, we use an isotopic approach to assess the trophic ecology of nestlings in a long-lived raptor, the Bonelli’s eagle Aquila fasciata, and investigate whether nestling dietary breath and main prey consumption can affect the species’ reproductive performance at two spatial scales: territories within populations and populations over a large geographic area. At the territory level, those breeding pairs whose nestlings consumed similar diets to the overall population (i.e. moderate consumption of preferred prey, but complemented by alternative prey categories) or those disproportionally consuming preferred prey were more likely to fledge two chicks. An increase in the diet diversity, however, related negatively with productivity. The age and replacements of breeding pair members had also an influence on productivity, with more fledglings associated to adult pairs with few replacements, as expected in long-lived species. At the population level, mean productivity was higher in those population-years with lower dietary breadth and higher diet similarity among territories, which was related to an overall higher consumption of preferred prey. Thus, we revealed a correspondence in diet-fitness relationships at two spatial scales: territories and populations. We suggest that stable isotope analyses may be a powerful tool to monitor the diet of terrestrial avian predators on large spatio-temporal scales, which could serve to detect potential changes in the availability of those prey on which predators depend for breeding. We encourage ecologists and evolutionary and conservation biologists concerned with the multi-scale fitness consequences of inter-individual variation in resource use to employ similar stable isotope-based approaches, which can be successfully applied to complex ecosystems such as the Mediterranean. PMID:24743233

Modeling and Analysis of the Water Cycle: Seasonal and Event Variability at the Walnut River Research Watershed

NASA Astrophysics Data System (ADS)

Miller, M. A.; Miller, N. L.; Sale, M. J.; Springer, E. P.; Wesely, M. L.; Bashford, K. E.; Conrad, M. E.; Costigan, K. R.; Kemball-Cook, S.; King, A. W.; Klazura, G. E.; Lesht, B. M.; Machavaram, M. V.; Sultan, M.; Song, J.; Washington-Allen, R.

2001-12-01

A multi-laboratory Department of Energy (DOE) team (Argonne National Laboratory, Brookhaven National Laboratory, Los Alamos National Laboratory, Lawrence Berkeley National Laboratory, Oak Ridge National Laboratory) has begun an investigation of hydrometeorological processes at the Whitewater subbasin of the Walnut River Watershed in Kansas. The Whitewater sub-basin is viewed as a DOE long-term hydrologic research watershed and resides within the well-instrumented Atmospheric Radiation Measurement/Cloud Radiation Atmosphere Testbed (ARM/CART) and the proposed Arkansas-Red River regional hydrologic testbed. The focus of this study is the development and evaluation of coupled regional to watershed scale models that simulate atmospheric, land surface, and hydrologic processes as systems with linkages and feedback mechanisms. This pilot is the precursor to the proposed DOE Water Cycle Dynamics Prediction Program. An important new element is the introduction of water isotope budget equations into mesoscale and hydrologic modeling. Two overarching hypotheses are part of this pilot study: (1) Can the predictability of the regional water balance be improved using high-resolution model simulations that are constrained and validated using new water isotope and hydrospheric water measurements? (2) Can water isotopic tracers be used to segregate different pathways through the water cycle and predict a change in regional climate patterns? Initial results of the pilot will be presented along with a description and copies of the proposed DOE Water Cycle Dynamics Prediction Program.

Multi-saline sample distillation apparatus for hydrogen isotope analyses : design and accuracy

USGS Publications Warehouse

Hassan, Afifa Afifi

1981-01-01

A distillation apparatus for saline water samples was designed and tested. Six samples may be distilled simultaneously. The temperature was maintained at 400 C to ensure complete dehydration of the precipitating salts. Consequently, the error in the measured ratio of stable hydrogen isotopes resulting from incomplete dehydration of hydrated salts during distillation was eliminated. (USGS)

A Chondrule from the Mokoia (CV3) Chondrite with Anomalously Low 26Mg*: Evidence for a Multi-Stage History-

NASA Astrophysics Data System (ADS)

Claydon, J. L.; Elliott, T.; Coath, C. D.; Chen, H. W.; Taylor, C. A.; Russell, S. S.

2015-07-01

MC-ICP-MS measurements of Mg isotopes in chondrule MOK13B reveal that it may have formed from low-Al/Mg material that underwent chemical fractionation to increase Al/Mg after decay of 26-Al, or it may sample a region with anomalous Al or Mg isotopes.

Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

NASA Astrophysics Data System (ADS)

Coleman, M.; Rhorssen, M.; Mielke, R. E.

2008-12-01

Isotopic variations measured within a single crystal of hydrated magnesium sulfate are greater than 30 permil for delta 2-H, almost 10 permil for δ18O in water of hydration; and greater than 3 permil in sulfate oxygen. These results are interpreted to indicate the relative humidity of the system during evaporation (15 to 20 percent in this test case) and constrain the volume of water involved. The theoretical basis of this system is the isotopic fractionation between the species in solution and those precipitated as evaporite salts. Precipitation preferentially accumulates more of the heavy isotopes of sulfur and oxygen in mineral sulfate, relative to sulfate in solution. During the course of mineral growth this leads to successive depletion of the respective heavier isotopes in the residual brine reflected in a parallel trend in successive precipitates or even in successive zones within a single crystal. The change in isotopic composition at any one time during the process, relative to the initial value, can be described by an isotopic version of the Rayleigh Fractionation equation, depending only on the extent of the completion of the process and the relevant fractionation factor. Evaporation preferentially removes isotopically lighter hydrogen and oxygen leading to successive extents of enrichment in the respective heavier isotopes in the residual water. However, the relative effects on hydrogen and oxygen isotopes differs as function of relative humidity [1]. ALL OF THESE CHANGES ARE PRESERVED IN THE MINERAL ISOTOPE COMPOSITIONS. We precipitated barium sulfate from epsomite or gypsum samples, which was reduced at 1450°C in the presence of graphite and glassy carbon in a Finnigan TC/EA to produce CO for O isotopic analysis in a Finnigan 253 mass spectrometer, while a separate subsample was oxidized to SO2 in a Costech Elemental Analyzer. However, to make progress with this approach we needed to make a large number of measurements of hydration water and so we developed a new analytical method [2]. We use a modification of the standard TC/EA continuous-flow protocol to measure both hydrogen and oxygen of water of hydration from the same small sample. We have proved the concept of this new approach by analyzing zones within crystals and individual grains, growing epsomite (magnesium sulfate heptahydrate) in the laboratory and by analysis of natural gypsum evaporites. We are now exploring the effects of varying the controlling parameters. Eventual application to Martian sulfates will reveal amount of water involved in sulfate formation, its isotopic composition(s) and details of the paleo-atmospheric humidity. [1] Gat JR and Gonfiantini R, (Eds) (1981) IAEA Technical Report Series. [2] Rohrssen MK, Brunner B Mielke RE and Coleman M (2008) Analyt. Chem. (in press).

Multi-stage metasomatism revealed by trace element and Li isotope distributions in minerals of peridotite xenoliths from Allègre volcano (French Massif Central)

NASA Astrophysics Data System (ADS)

Gu, Xiaoyan; Deloule, Etienne; France, Lydéric; Ingrin, Jannick

2016-11-01

The modal, chemical, and isotopic compositions of mantle peridotite are largely modified by metasomatic processes, which may affect them repeatedly. Xenoliths are commonly used to characterize those metasomatic processes along with the structure, and chemical and isotopic compositions of mantle domains. Nevertheless, the original mantle signatures born by mantle xenoliths are potentially obscured by the interactions occurring between the host magma and the xenolith itself. Here we attempt to identify to which degree the original Li content and isotopic composition, as well as other trace element contents of mantle xenoliths, can be modified by interaction with the host magma. Peridotite xenoliths that have suffered extensive exchange with the entraining magma were sampled in the solidified lava lake of Allègre, Southern French Massif Central, in order to decipher the signature related to peridotite-melt interaction, and to further unravel the evolution of the sub-continental lithospheric mantle. In-situ trace element analyses of clinopyroxene (Cpx) were performed via LA-ICP-MS, and the Li content and isotopic composition of pyroxene and olivine (Ol) via SIMS. Negative HFSE anomalies (Ti/Eu ratios as low as 437) and markedly high LREE/HREE ratios ((La/Yb)N as high as 79) are characteristic of mantle metasomatism at depth. Lithium isotope systematics indicates that at least two different metasomatic events affected the peridotite. Exceptionally high Li contents in Cpx (up to 50 ppm) and slight Li enrichment of Ol rims are ascribed to diffusive Li influx with a positive δ7Li value (+ 3.2‰) from the host magma after entrainment. Conversely, Ol cores preserve extremely light Li isotopic compositions (δ7Li as low as - 25‰) with high Li contents (up to 4.4 ppm) compared to normal mantle, indicating a metasomatic event that occurred before xenolith entrainment. The negative δ7Li signature of this early metasomatism may be related to subduction-related fluids released during the Variscan orogeny. Trace element distributions in minerals reveal that the HFSE and REE composition of Cpx and the negative δ7Li signature in Ol cores were not acquired simultaneously. Therefore at least three successive metasomatic events affected the Allegre peridotites, as revealed through the use of detailed in-situ Li isotopic analyses to trace melt-rock interactions.

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.

Stellar Origins of C-13 and N-15-Enriched Presolar SiC Grains

NASA Technical Reports Server (NTRS)

Liu, Nan; Nittler, Larry R.; Alexander, Conel M. O’D.; Wang, Jianhua; Pignatari, Marco; Jose, Jordi; Nguyen, Ann

2016-01-01

Extreme excesses of 13 C ( C (12 C/ 13 C<10) and 15 N ( N (14 N/ 15 N< 20) in rare presolar SiC 20) in rare presolar SiClar SiC grains have been considered diagnostic of an origin in classical novae [1], though an origin in core-collapse supernovae (CCSNe) has also been proposed [2]. We report multi-element isotopic data for 19 13 C- and 15 N-enriched presolar SiC grains(12 C/13 C<16 and 14 N/ 15 N<150) from an acid resistant residue of the Murchison meteorite. These grains are enriched in 13 C and15 N, but with quite diverse Si isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures. Four grains with isotopic signatures.

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

PubMed

Yurimoto, H; Ito, M; Nagasawa, H

1998-12-04

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

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

PubMed

Yurimoto; Ito; Nagasawa

1998-12-04

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

Nuclear quantum effects and kinetic isotope effects in enzyme reactions.

PubMed

Vardi-Kilshtain, Alexandra; Nitoker, Neta; Major, Dan Thomas

2015-09-15

Enzymes are extraordinarily effective catalysts evolved to perform well-defined and highly specific chemical transformations. Studying the nature of rate enhancements and the mechanistic strategies in enzymes is very important, both from a basic scientific point of view, as well as in order to improve rational design of biomimetics. Kinetic isotope effect (KIE) is a very important tool in the study of chemical reactions and has been used extensively in the field of enzymology. Theoretically, the prediction of KIEs in condensed phase environments such as enzymes is challenging due to the need to include nuclear quantum effects (NQEs). Herein we describe recent progress in our group in the development of multi-scale simulation methods for the calculation of NQEs and accurate computation of KIEs. We also describe their application to several enzyme systems. In particular we describe the use of combined quantum mechanics/molecular mechanics (QM/MM) methods in classical and quantum simulations. The development of various novel path-integral methods is reviewed. These methods are tailor suited to enzyme systems, where only a few degrees of freedom involved in the chemistry need to be quantized. The application of the hybrid QM/MM quantum-classical simulation approach to three case studies is presented. The first case involves the proton transfer in alanine racemase. The second case presented involves orotidine 5'-monophosphate decarboxylase where multidimensional free energy simulations together with kinetic isotope effects are combined in the study of the reaction mechanism. Finally, we discuss the proton transfer in nitroalkane oxidase, where the enzyme employs tunneling as a catalytic fine-tuning tool. Copyright © 2015 Elsevier Inc. All rights reserved.

DIVISION OF ISOTOPES DEVELOPMENT RESEARCH AND DEVELOPMENT PROJECTS: 1968. Progress Reports on Sponsored Work.

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

None

1969-01-01

This is the second edition of the Division of Isotopes Development project summaries. It presents a short summary of objectives, results, and future plans for each research or development project sponsored by the Division within each of eight program areas.

Validation of the determination of the B isotopic composition in Roman glasses with laser ablation multi-collector inductively coupled plasma-mass spectrometry

NASA Astrophysics Data System (ADS)

Devulder, Veerle; Gerdes, Axel; Vanhaecke, Frank; Degryse, Patrick

2015-03-01

The applicability of laser ablation multi-collector inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) for the determination of the B isotopic composition in Roman glasses was investigated. The δ11B values thus obtained provide information on the natron flux used during the glass-making process. The glass samples used for this purpose were previously characterized using pneumatic nebulization (PN) MC-ICP-MS. Unfortunately, this method is time-consuming and labor-intensive and consumes some 100 mg of sample, which is a rather high amount for ancient materials. Therefore, the use of the less invasive and faster LA-MC-ICP-MS approach was explored. In this work, the results for 29 Roman glasses and 4 home-made glasses obtained using both techniques were compared to assess the suitability of LA-MC-ICP-MS in this context. The results are in excellent agreement within experimental uncertainty. No difference in overall mass discrimination was observed between the Roman glasses, NIST SRM 610 reference glass and B6 obsidian. The expanded uncertainty of the LA-MC-ICP-MS approach was estimated to be < 2‰, which is similar to that obtained upon sample digestion and PN-MC-ICP-MS measurement.

Chemical and isotopic fractionations by evaporation and their cosmochemical implications

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Nagahara, Hiroko

2001-07-01

A kinetic model for evaporation of a multi-component condensed phase with a fixed rate constant of the reaction is developed. A binary system with two isotopes for one of the components undergoing simple thermal histories (e.g., isothermal heating) is investigated in order to evaluate the extent of isotopic and chemical fractionations during evaporation. Diffusion in the condensed phase and the effect of back reaction from ambient gas are taken into consideration. Chemical and isotopic fractionation factors and the Péclet number for evaporation are the three main parameters that control the fractionation. Dust enrichment factor (η), the ratio of the initial dust quantity to that required for attainment of gas-dust equilibrium, is critical when back reactions become significant. Dust does not reach equilibrium with gas at η < 1. Notable chemical and isotopic fractionations usually take place under these conditions. There are two circumstances in which isotopic fractionation of a very volatile element does not accompany chemical fractionation during isothermal heating. One is free evaporation when diffusion in the condensed phase is very slow (η = 0), and the other is evaporation in the presence of ambient gas (η > 0). In the former case, a quasi-steady state in the diffusion boundary layer is maintained for isotopic fractionation but not for chemical fractionation. In the latter case, the back reaction brings the strong isotopic fractionation generated in the earlier stage of evaporation back to a negligibly small value in the later stage before complete evaporation. The model results are applied to cosmochemical fractionation of volatile elements during evaporation from a condensed phase that can be regarded as a binary solution phase. The wide range of potassium depletion without isotopic fractionation in various types of chondrules (Alexander et al., 2000) is explained by instantaneous heating followed by cooling in a closed system with various degrees of dust enrichment (η = 0.001-10) and cooling rates of less than ˜5°C/min. The extent of decoupling between isotopic and chemical fractionations of various elements in chondrules and matrix minerals may constrain the time scale and the conditions of heating and cooling processes in the early solar nebula.

Degradation of Perchloroethene by zero-valent iron evaluated by carbon isotope fractionation

NASA Astrophysics Data System (ADS)

Leitner, Simon; Watzinger, Andrea; Reichenauer, Thomas G.

2014-05-01

Perchloroethene (PCE) is a widely spread groundwater contaminant in formally used industrial sites. Zero valent iron (ZVI) is used for in situ chemical reduction (ISCR) of PCE contaminants in the groundwater. A key factor in the application of in situ remediation technologies is a proper monitoring of contaminant reduction. The measurement of the stable isotope ratio is a promising method that is already used for quantifying microbial degradation of chlorinated contaminants. The carbon isotope ratio of PCE, measured by - isotope ratio mass spectrometry coupled to a gas chromatograph via a combustion interface (GC-C-IRMS), increases during degradation of PCE and can be directly related to the degree of degradation. It can be used to directly quantify chemical degradation and thus serves as a useful monitoring tool for groundwater remediation. An experiment to determine the carbon isotopic fractionation factor was performed as a lab experiment using Nanofer Star (NANOIRON). Two different PCE concentrations (c1: 220mgL-1, c2: 110mgL-1) mixed with 0.5 g of ZVI were sealed under deoxygenated conditions in 250 ml glas bottles locked with mininert caps. The bottles were incubated on a shaker for 865 h. Samples were taken weekly to measure the change in the carbon isotopic ratio of PCE as well as its concentration. Results showed a strong increase in the carbon isotope ratio (δ-value) of PCE (start: -27 o end: -4 ), which indicates a significant dechlorination process of PCE. Beside PCE also one degradation product (Trichloroethylene - TCE) was measured. TCE was further dechlorinated as indicated by the δ-value change of TCE from -26 o to -4 oȦn unexpected intermediate value of -45 o for TCE was observed in the experiment. This fluctuation could be induced by the time depending concentration due to degradation and conversation processes. Furthermore, it seems that the progress of the δ-value is affected by the starting concentration of PCE (δ-value of c1 < c2) as there is a higher ratio of PCE to ZVI.

Geochemistry and the understanding of ground-water systems

USGS Publications Warehouse

Glynn, Pierre D.; Plummer, Niel

2005-01-01

Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems.

Stable isotope insights into the weathering processes of a phosphogypsum disposal area.

PubMed

Papaslioti, Evgenia-Maria; Pérez-López, Rafael; Parviainen, Annika; Macías, Francisco; Delgado-Huertas, Antonio; Garrido, Carlos J; Marchesi, Claudio; Nieto, José M

2018-04-28

Highly acidic phosphogypsum wastes with elevated potential for contaminant leaching are stack-piled near coastal areas worldwide, threatening the adjacent environment. Huge phosphogypsum stacks were disposed directly on the marshes of the Estuary of Huelva (SW Spain) without any impermeable barrier to prevent leaching and thus, contributing to the total contamination of the estuarine environment. According to the previous weathering model, the process water ponded on the surface of the stack, initially used to carry the waste, was thought to be the main washing agent through its infiltration and subsequently the main component of the leachates emerging as the edge outflows. Preliminary restorations have been applied to the site and similar ones are planned for the future considering process water as the only pollution agent. Further investigation to validate the pollution pathway was necessary, thus an evaluation of the relationship between leachates and weathering agents of the stack was carried out using stable isotopes (δ 18 O, δ 2 H, and δ 34 S) as geochemical tracers. Quantification of the contribution of all possible end-members to the phosphogypsum leachates was also conducted using ternary mixing via the stable isotopic tracers. The results ruled out ponded process water as main vector of edge outflow pollution and unveiled a continuous infiltration of estuarine waters to the stack implying that is subjected to an open weathering system. The isotopic tracers revealed a progressive contribution downstream from fluvial to marine signatures in the composition of the edge outflows, depending on the location of each disposal zone within the different estuarine morphodynamic domains. Thus, the current study suggests that the access of intertidal water inside the phosphogypsum stack, for instance through secondary tidal channels, is the main responsible for the weathering of the waste in depth, underlying the necessity for new, more effective restorations plans. Copyright © 2018 Elsevier Ltd. All rights reserved.

Constraints on Nucleosynthesis from Xenon Isotopes in Presolar Material

NASA Astrophysics Data System (ADS)

Gilmour, J. D.; Turner, G.

2007-03-01

By applying theoretical constraints to three-dimensional fits of xenon isotope data from presolar grains, we show that they strongly suggest a nucleosynthesis process that produces ``r-process'' isotopes without producing s-process isotopes (128Xe, 130Xe) and without producing the conventional r-process isotope 136Xe. It is one of three distinct nucleosynthetic sources that are necessary and sufficient to explain the gross variation in xenon isotopic data across all presolar material. The other source contributing r-process isotopes is responsible for the heavy isotope signature identified in nanodiamonds, which is also present in presolar SiC, and is associated with light isotope enrichment. The relative enrichments of heavy and light isotopes in this component in nanodiamonds and SiC grains are different, implying that the parent nucleosynthetic processes are not inextricably linked. Because minor variations in the isotopic compositions of xenon trapped in nanodiamonds show that two distinct sites contributed nanodiamonds to the early solar system within the average grain lifetime, it is suggested that Type IIa supernovae (SNe IIa) are not the source of the nanodiamonds. The s-process signature derived is consistent with that derived from mixing lines between grain subpopulations for isotopes on the s-process path. This implies that a pure end-member is present in the grains (although not approached in analyses). Our approach is more general and provides a less restrictive set of numerical constraints to be satisfied by proposed theoretical treatments of nucleosynthesis.

High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

Wall, Andrew J.; Capo, Rosemary C.; Stewart, Brian W.

2016-09-22

This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

High-Throughput Method for Strontium Isotope Analysis by Multi-Collector-Inductively Coupled Plasma-Mass Spectrometer

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

Hakala, Jacqueline Alexandra

2016-11-22

This technical report presents the details of the Sr column configuration and the high-throughput Sr separation protocol. Data showing the performance of the method as well as the best practices for optimizing Sr isotope analysis by MC-ICP-MS is presented. Lastly, this report offers tools for data handling and data reduction of Sr isotope results from the Thermo Scientific Neptune software to assist in data quality assurance, which help avoid issues of data glut associated with high sample throughput rapid analysis.

A Procedure to Determine the Coordinated Chromium and Calcium Isotopic Composition of Astromaterials Including the Chelyabinsk Meteorite

NASA Technical Reports Server (NTRS)

Tappa, M. J.; Mills, R. D.; Ware, B.; Simon, J. I.

2014-01-01

The isotopic compositions of elements are often used to characterize nucelosynthetic contributions in early Solar System objects. Coordinated multiple middle-mass elements with differing volatilities may provide information regarding the location of condensation of early Solar System solids. Here we detail new procedures that we have developed to make high-precision multi-isotope measurements of chromium and calcium using thermal ionization mass spectrometry, and characterize a suite of chondritic and terrestrial material including two fragments of the Chelyabinsk LL-chondrite.

Femtosecond Laser Ablation Multicollector ICPMS Analysis of Uranium Isotopes in NIST Glass

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

Duffin, Andrew M.; Springer, Kellen WE; Ward, Jesse D.

We have utilized femtosecond laser ablation coupled to multi-collector inductively couple plasma mass spectrometry to measure the uranium isotopic content of NIST 61x (x=0,2,4,6) glasses. The uranium content of these glasses is a linear two-component mixing between isotopically natural uranium and the isotopically depleted spike used in preparing the glasses. Laser ablation results match extremely well, generally within a few ppm, with solution analysis following sample dissolution and chemical separation. In addition to isotopic data, sample utilization efficiency measurements indicate that over 1% of ablated uranium atoms reach a mass spectrometer detector, making this technique extremely efficient. Laser sampling alsomore » allows for spatial analysis and our data indicate that rare uranium concentration inhomogeneities exist in NIST 616 glass.« less

Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO 2- reduction by Fe(II) and its production of N 2O

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

Johnston, David; Wankel, Scott David; Buchwald, Carolyn

Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO 2 -) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N 2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions.more » We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO 2 - reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N 2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO 2 - reduction by Fe(II) may represent an important abiotic source of environmental N 2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO 2 - reduction and N 2O formation, helping future studies constrain the relative roles of abiotic and biological N 2O production pathways.« less

Isotopic analysis of Cu in blood serum by multi-collector ICP-mass spectrometry: a new approach for the diagnosis and prognosis of liver cirrhosis?

PubMed

Costas-Rodríguez, Marta; Anoshkina, Yulia; Lauwens, Sara; Van Vlierberghe, Hans; Delanghe, Joris; Vanhaecke, Frank

2015-03-01

The isotopic composition of blood serum Cu has been investigated as a potential parameter for the diagnosis and prognosis of liver cirrhosis. Serum samples from supposedly healthy women (reference population) and from a group of female patients suffering from liver cirrhosis of different etiologies were analysed. The procedure for isolation of serum Cu and the measurement protocol for its isotopic analysis by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) were evaluated. Significant differences in the isotopic composition of Cu were observed between the reference population and the patients. A wide spread in δ(65)Cu was observed within the cirrhosis population and δ(65)Cu seems to be linked to the severity of the disease. Patients with end-stage liver disease showed a significantly lighter serum Cu isotopic composition. Many clinical parameters used for the diagnosis and monitoring of liver diseases, i.e. the levels of aspartate aminotransferase, De Ritis ratio, prothrombin and international normalized ratio, albumin, bilirubin, Na and C-reactive protein, correlate well with the δ(65)Cu values, as did the ceruloplasmin level and the ceruloplasmin/Cu concentration ratio. The isotopic composition of serum Cu appears to reveal the synthetic and hepatocellular function of the liver synergistically with inflammation and fluid retention in the cohort studied. A relevant relationship was also observed between δ(65)Cu and scores of mortality risk, such as the Model for End-stage Liver Disease (MELD) and MELD-Na. Thus, the isotopic composition of serum Cu shows potential as a new approach for the prognosis of liver disease, and although further investigation is required, for evaluation of the mortality risk in end-stage liver disease and prioritization of liver transplants.

sources and processes identification for Zn cycling in the Seine river, France

NASA Astrophysics Data System (ADS)

gelabert, A.; Jouvin, D.; Morin, G.; Louvat, P.; Guinoiseau, D.; Benedetti, M. F.

2011-12-01

Because the availability of global freshwater stocks is predicted to become a major problem in a near future, new directives on water policy have been established in Europe. As a result, an accurate determination of the ecological status of the Seine river watershed is required. However, important evaluation limitation still exist, partly because the metal cycling in this system is not fully understood with for instance half the Seine river Zn not having clearly identified sources. Recent developments in isotopic measurements for new stable isotopes (Zn, Cu) allow many progresses in understanding the dynamics of metals in natural systems. But this technique alone does not always provide a precise distinction between mixing of water sources and biochemical processes able to induce isotopic fractionation. Along with an isotopic approach, this study propose to use XAS (X-ray Absorption Spectroscopy) to determine precisely the speciation of Zn complexes, and thus to define the proportion of water mixing vs. processes for Zn transfer in the watershed. A geographical sampling transect has been performed downstream Paris. Significant isotopic signature variations have been observed, varying from δ66Zn = 0.04 ± 0.04 to 0.18 ± 0.04 in the particulate part, and from δ66Zn= -0.28 ± 0.04 to 0.08 ± 0.04 for the dissolved part. The XAS analysis performed on the same samples at the Zn K-edge confirmed this heterogeneity by showing different speciations with a major contribution of sulfides, iron oxides and organic ligands. Interestingly, the wastewater treatment plant in Achères constitutes an important location in the system by contributing to the enrichment of heavy Zn to the Seine River particulate material. This change in isotopic signature follows a change in Zn speciation with decrease in sulfides contribution after Achères. A second important location is the confluence between the Seine and a minor river (Epte river) with a significant decrease in the δ66Zn for the particulate part. However, no major changes in Zn speciation have been observed. The cause for this isotopic decrease remains unclear but could be either 1) the mobilization of unknown sources, especially in this area (for the sampling point after the convergence) where the river is connected to numerous small lakes, or 2) the presence of biogeochemical processes able to induce a Zn isotopic fractionation. For instance, microorganisms present in freshwaters are known to be able to fractionate Zn during sorption processes, and they do not necessarily induce a change in the first shells of the Zn complexes if the sorbed metal was previously complexed with organic ligands in the river (fulvic substances with carboxylic or phenolic functional groups for instance). Although additional studies on the Seine river need to be conducted in order to reach a more complete understanding of this watershed functioning, these important results demonstrate the value of combining both the XAS and isotopic approaches in order to understand the behaviour of metals in such complex environments.

Developing a Multi Sensor Scanning System for Hardwood Inspection and Processing

Treesearch

Richard W. Conners; D.Earl Kline; Philip A. Araman

1995-01-01

For the last few years the authors as part of the Center for Automated Processing of Hardwoods have been attempting to develop a multiple sensor hardwood defect detection system. This development activity has been ongoing for approximately 6 years, a very long time in the commercial development world. This paper will report the progress that has been made and will...

Rare Isotopes Physics in the Multimessenger Era

NASA Astrophysics Data System (ADS)

Schatz, Hendrik

2018-06-01

While these isotopes only exist for fractions of seconds, their properties shape the resulting cosmic distribution of elements and the astronomical observables including spectra, neutrinos, and gravitational waves. The long standing challenge in nuclear astrophysics of the production of the relevant isotopes in the laboratory is now overcome with a new generation of rare isotope accelerator facilities now coming online. One example is the FRIB facility under construction at Michigan State University for the US Department of Energy, Office of Science, Office of Nuclear Physics. These new capabilities in nuclear physics coincide with advances in astronomy directly related to the cosmic sites where these isotopes are created, in particular in time domain and gravitational wave astronomy. I will discuss the importance of rare isotope physics in interpreting multi-messenger observations and how advances in nuclear physics and astronomy when combined promise to lead us towards a comprehensive theory of the origin of the elements.

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

NASA Astrophysics Data System (ADS)

Kaown, Dugin; Koh, Eun-Hee; Mayer, Bernhard; Kim, Heejung; Park, Dong Kyu; Park, Byeong-Hak; Lee, Kang-Kun

2018-01-01

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO3-N (74-83 mg L-1). The δ15N-NO3 values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ15N-NO3 values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ15N-NO3 and δ18O-NO3 values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between -4.8 and -7.9‰ and O isotope enrichment factors varying between -3.8 and -4.9‰. Similar δD and δ18O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10-20 years) than in the north (20-30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.

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...

PROSPECT - A Precision Oscillation and Spectrum Experiment

NASA Astrophysics Data System (ADS)

Zhang, Xianyi; Prospect Collaboration

2017-01-01

PROSPECT, the PRecision Oscillation and SPECTrum Experiment, is a multi-phased short baseline reactor antineutrino experiment that aims to precisely measure the U-235 antineutrino spectrum and prob for oscillation effects involving a possible Δm2 1 eV2 scale sterile neutrino. In PROSPECT Phase-I, an optically segmented Li-6 loaded liquid scintillator detector will be deployed at at the baseline of 7-12m from the High Flux Isotope Reactor at the Oak Ridge National Laboratory. PROSPECT will measure the spectrum of U-235 to aid in resolving the unexplained inconsistency between predictive spectral models and recent experimental measurements using LEU cores, while the oscillation measurement will probe the best fit region suggested by global fitting studies within 1-year data taking. This talk will introduce the design of PROSPECT Phase-I, the discovery potential of the experiment, and the progress the collaboration has made toward realizing PROSPECT Phase-I. Department of Energy

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene.

PubMed

Van Breukelen, Boris M; Thouement, Héloïse A A; Stack, Philip E; Vanderford, Mindy; Philp, Paul; Kuder, Tomasz

2017-09-01

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ 37 Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ 2 H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

DOE PAGES

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.; ...

2017-10-25

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Geochemical and multi-isotopic ( 87Sr/ 86Sr, 143Nd/ 144Nd, 238U/ 235U) perspectives of sediment sources, depositional conditions, and diagenesis of the Marcellus Shale, Appalachian Basin, USA

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

Phan, Thai T.; Gardiner, James B.; Capo, Rosemary C.

Here, we investigate sediment sources, depositional conditions and diagenetic processes affecting the Middle Devonian Marcellus Shale in the Appalachian Basin, eastern USA, a major target of natural gas exploration. Multiple proxies, including trace metal contents, rare earth elements (REE), the Sm-Nd and Rb-Sr isotope systems, and U isotopes were applied to whole rock digestions and sequentially extracted fractions of the Marcellus shale and adjacent units from two locations in the Appalachian Basin. The narrow range of εNd values (from –7.8 to –6.4 at 390 Ma) is consistent with derivation of the clastic sedimentary component of the Marcellus Shale from amore » well-mixed source of fluvial and eolian material of the Grenville orogenic belt, and indicate minimal post-depositional alteration of the Sm-Nd system. While silicate minerals host >80% of the REE in the shale, data from sequentially extracted fractions reflect post-depositional modifications at the mineralogical scale, which is not observed in whole rock REE patterns.« less

Design and construction of a multi-layer CsI(Tl) telescope for high-energy reaction studies

NASA Astrophysics Data System (ADS)

Yan, D.; Sun, Z. Y.; Yue, K.; Wang, S. T.; Zhang, X. H.; Yu, Y. H.; Chen, J. L.; Tang, S. W.; Fang, F.; Zhou, Y.; Sun, Y.; Wang, Z. M.; Sun, Y. Z.

2017-01-01

A prototype of a new CsI(Tl) telescope, which will be used in the reaction studies of light isotopes with energy of several hundred AMeV, was constructed and tested at the Institute of Modern Physics, Chinese Academy of Sciences. The telescope has a multi-layer structure, and the range information was obtained to improve the particle identification performance. This prototype has seven layers of different thickness. An energy resolution of 5.0% (FWHM) was obtained for one of the layers in a beam test experiment. Positive improvement for the identification of 14O and 15O isotopes was achieved using the range information.

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.

Improved spectral comparisons of paleoclimate models and observations via proxy system modeling: Implications for multi-decadal variability

NASA Astrophysics Data System (ADS)

Dee, S. G.; Parsons, L. A.; Loope, G. R.; Overpeck, J. T.; Ault, T. R.; Emile-Geay, J.

2017-10-01

The spectral characteristics of paleoclimate observations spanning the last millennium suggest the presence of significant low-frequency (multi-decadal to centennial scale) variability in the climate system. Since this low-frequency climate variability is critical for climate predictions on societally-relevant scales, it is essential to establish whether General Circulation models (GCMs) are able to simulate it faithfully. Recent studies find large discrepancies between models and paleoclimate data at low frequencies, prompting concerns surrounding the ability of GCMs to predict long-term, high-magnitude variability under greenhouse forcing (Laepple and Huybers, 2014a, 2014b). However, efforts to ground climate model simulations directly in paleoclimate observations are impeded by fundamental differences between models and the proxy data: proxy systems often record a multivariate and/or nonlinear response to climate, precluding a direct comparison to GCM output. In this paper we bridge this gap via a forward proxy modeling approach, coupled to an isotope-enabled GCM. This allows us to disentangle the various contributions to signals embedded in ice cores, speleothem calcite, coral aragonite, tree-ring width, and tree-ring cellulose. The paper addresses the following questions: (1) do forward-modeled ;pseudoproxies; exhibit variability comparable to proxy data? (2) if not, which processes alter the shape of the spectrum of simulated climate variability, and are these processes broadly distinguishable from climate? We apply our method to representative case studies, and broaden these insights with an analysis of the PAGES2k database (PAGES2K Consortium, 2013). We find that current proxy system models (PSMs) can help resolve model-data discrepancies on interannual to decadal timescales, but cannot account for the mismatch in variance on multi-decadal to centennial timescales. We conclude that, specific to this set of PSMs and isotope-enabled model, the paleoclimate record may exhibit larger low-frequency variability than GCMs currently simulate, indicative of incomplete physics and/or forcings.

Determining metal assimilation efficiency in aquatic invertebrates using enriched stable metal isotope tracers

USGS Publications Warehouse

Croteau, M.-N.; Luoma, S.N.; Pellet, B.

2007-01-01

We employ a novel approach that combines pulse-chase feeding and multi-labelled stable isotopes to determine gut passage time (GPT), gut retention time (GRT), food ingestion rate (IR) and assimilation efficiency (AE) of three trace elements for a freshwater gastropod. Lettuce isotopically enriched in 53Cr, 65Cu and 106Cd was fed for 2 h to Lymnaea stagnalis. The release of tracers in feces and water was monitored for 48 h, during which unlabelled lettuce was provided ad libidum. The first defecation of 53Cr occurred after 5 h of depuration (GPT), whereas 90% of the ingested 53Cr was recovered in the feces after 22.5 h of depuration (GRT). 53Chromium was not significantly accumulated in the soft tissues upon exposure. In contrast, 65Cu and 106Cd assimilation was detectable for most experimental snails, i.e., 65/63Cu and 106/114Cd ratios in exposed snails were higher than those for controls. Food IR during the labelled feeding phase was 0.16 ?? 0.07 g g-1 d-1. IR was inferred from the amount of 53Cr egested in the feces during depuration and the concentration of 53Cr in the labelled lettuce. Assimilation efficiencies (??95% CI) determined using mass balance calculations were 84 ?? 4% for Cu and 85 ?? 3% for Cd. The ratio method yields similar AE estimates. Expanding the application of this novel stable isotope tracer technique to other metals in a wide variety of species will provide unique opportunities to evaluate the interplay between digestive processes and dietary influx of metals. Understanding the biological processes that modulate dietborne metal uptake is crucial to assess the toxicity of dietborne metals. ?? 2007 Elsevier B.V. All rights reserved.

Shallow-level magma-sediment interaction and explosive behaviour at Anak Krakatau (Invited)

NASA Astrophysics Data System (ADS)

Troll, V. R.; Jolis, E. M.; Dahren, B.; Deegan, F. M.; Blythe, L. S.; Harris, C.; Berg, S. E.; Hilton, D. R.; Freda, C.

2013-12-01

Crustal contamination of ascending arc magmas is generally thought to be a significant process which occurs at lower- to mid-crustal magma storage levels where magmas inherit their chemical and isotopic character by blending, assimilation and differentiation [1]. Anak Krakatau, like many other volcanoes, erupts shallow-level crustal xenoliths [2], indicating a potential role for upper crustal modification and hence late-stage changes to magma rheology and thus potential eruptive behaviour. Distinguishing deep vs. shallow crustal contamination processes at Krakatau, and elsewhere, is therefore crucial to understand and assess pre-eruptive magmatic conditions and their associated hazard potential. Here we report on a multi-disciplinary approach to unravel the crustal plumbing system of the persistently-active and dominantly explosive Anak Krakatau volcano [2, 3], employing rock-, mineral- and gas-isotope geochemistry and link these results with seismic tomography [4]. We show that pyroxene crystals formed at mid- and lower-crustal levels (9-11 km) and carry almost mantle-like isotope signatures (O, Sr, Nd, He), while feldspar crystals formed dominantly at shallow levels (< 5km) and display unequivocal isotopic evidence for late stage contamination (O, Sr, Nd). This obeservation places a significant element of magma-crust interaction into the uppermost, sediment-rich crust beneath the volcano. Magma storage in the uppermost crust can thus offer a possible explanation for the compositional modifications of primitive Krakatau magmas, and likely provides extra impetus to increased explosivity at Anak Krakatau. [1] Annen, et al., 2006. J. Petrol. 47, 505-539. [2] Gardner, et al., 2013. J. Petrol. 54, 149-182. [3] Dahren, et al., 2012. Contrib. Mineral. Petrol. 163, 631-651. [4] Jaxybulatov, et al., 2011. J. Volcanol. Geoth. Res. 206, 96-105.

Denitrification constitutes an import N sink in subtropical N-saturated forests - a nitrate dual isotope study

NASA Astrophysics Data System (ADS)

Yu, Lonfei; Zhu, Jing; Mulder, Jan; Dörsch, Peter

2016-04-01

Forests in China receive variable but increasing amounts of nitrogen from the atmosphere causing N saturation and nitrate runoff. Surprisingly high N-retention has been reported from subtropical forests, suggesting active mechanisms of N removal. Here we report a multi-site study of 15N and 18O abundances in soil nitrate (NO3-) across seven forested catchments spanning from temperate to subtropical China. In each catchment, samples were taken on one date during one or two summer along the hydrological continuum comprising hillslope positions and riparian zones. We had found previously in an intensive multi-year study at one of the sites, that the spatial pattern of summertime 15N and 18O in soil nitrate was remarkably stable across climatically distinct years, suggesting persistent N removal by denitrification at the foot of hill slopes and in groundwater discharge zones (Yu et al., submitted). In the present study, we extended the scope to five subtropical Chinese catchments and compared them with two temperate forests. Our data confirm the general pattern of efficient nitrification on hillslopes and strong denitrification in riparian zones in the subtropical catchments but not in the temperate ones. This is likely because high summer rainfalls at the monsoonal sites connect N mineralization and oxidation in upland positions with NO3- reduction in ground water discharge zones via NO3- runoff, rendering subtropical forests an efficient sink for reactive N with implications for regional N budgets. The impact of N deposition level, hydrology and edaphic factors on the predictive power of nitrate isotope signatures for N removal processes will be discussed. Yu L, Zhu J, Mulder J, Dörsch P: Spatiotemporal patterns in dual nitrate isotopes reveal efficient N transformation and denitrification along a hydrological continuum in N-saturated, subtropical forest. Submitted

Modelling the isotopic evolution of the Earth.

PubMed

Paul, Debajyoti; White, William M; Turcotte, Donald L

2002-11-15

We present a flexible multi-reservoir (primitive lower mantle, depleted upper mantle, upper continental crust, lower continental crust and atmosphere) forward-transport model of the Earth, incorporating the Sm-Nd, Rb-Sr, U-Th-Pb-He and K-Ar isotope-decay systematics. Mathematically, the model consists of a series of differential equations, describing the changing abundance of each nuclide in each reservoir, which are solved repeatedly over the history of the Earth. Fluxes between reservoirs are keyed to heat production and further constrained by estimates of present-day fluxes (e.g. subduction, plume flux) and current sizes of reservoirs. Elemental transport is tied to these fluxes through 'enrichment factors', which allow for fractionation between species. A principal goal of the model is to reproduce the Pb-isotope systematics of the depleted upper mantle, which has not been done in earlier models. At present, the depleted upper mantle has low (238)U/(204)Pb (mu) and (232)Th/(238)U (kappa) ratios, but Pb-isotope ratios reflect high time-integrated values of these ratios. These features are reproduced in the model and are a consequence of preferential subduction of U and of radiogenic Pb from the upper continental crust into the depleted upper mantle. At the same time, the model reproduces the observed Sr-, Nd-, Ar- and He-isotope ratios of the atmosphere, continental crust and mantle. We show that both steady-state and time-variant concentrations of incompatible-element concentrations and ratios in the continental crust and upper mantle are possible. Indeed, in some cases, incompatible-element concentrations and ratios increase with time in the depleted mantle. Hence, assumptions of a progressively depleting or steady-state upper mantle are not justified. A ubiquitous feature of this model, as well as other evolutionary models, is early rapid depletion of the upper mantle in highly incompatible elements; hence, a near-chondritic Th/U ratio in the upper mantle throughout the Archean is unlikely. The model also suggests that the optimal value of the bulk silicate Earth's K/U ratio is close to 10000; lower values suggested recently seem unlikely.

133 Ba+: a new ion qubit

NASA Astrophysics Data System (ADS)

Christensen, Justin; Hucul, David; Campbell, Wesley; Hudson, Eric

2017-04-01

133 Ba+ combines many of the advantages of commonly used trapped ion qubits. 133Ba+ has a nuclear spin 1/2, allowing for a robust hyperfine qubit with simple state preparation and readout. The existence of long-lived metastable D-states and a lack of low-lying F-states simplifies shelving, which will allow high fidelity state detection. The visible wavelength optical transitions enable the use of high-power lasers, low-loss fibers, high quantum efficiency detectors, and other optical technologies developed for visible wavelength light. Furthermore, background-free qubit readout, where the readout is insensitive to laser scatter, is possible in 133Ba+, and simplifies its use in small ion traps and the study of ions near surfaces. We report progress on realizing this qubit. We load barium ions into an ion trap using thermal ionization from a platinum ribbon. We experimentally demonstrate the isotopic purification of large numbers of barium ions using laser heating and cooling along with mass filtering to produce isotopically pure chains of any naturally-occurring barium isotope. This purification process has allowed us to laser cool rare, naturally-occurring barium isotopes 132Ba+and130Ba+, and we report the isotope shifts from 138Ba+ of the P1/2 to D3/2 transitions near 650 nm for the first time. In addition, we have developed an ion gun to produce high luminosity ion beams with adjustable mean kinetic energy by combining a surface ionization source and ion optics.

Lithium isotope as a proxy for water/rock interaction between hydrothermal fluids and oceanic crust at Milos, Greece

NASA Astrophysics Data System (ADS)

Lou, U.-Lat; You, Chen-Feng; Wu, Shein-Fu; Chung, Chuan-Hsiung

2014-05-01

Hydrothermal activity at Milos in the Aegean island (Greece) is mainly located at rather shallow depth (about 5 m). It is interesting to compare these chemical compositions and the evolution processes of the hydrothermal fluids at deep sea hydrothermal vents in Mid-ocean Ridge (MOR). Lithium (Li) is a highly mobile element and its isotopic composition varies at different geological settings. Therefore, Li and its isotope could be used as an indicator for many geochemical processes. Since 6Li preferential retained in the mineral phase where 7Li is leached into fluid phase during basalt alteration, the Li isotopic fractionation between the rocks and the fluids reflect sensitively the degree of water-rock interaction. In this study, Bio-Rad AG-50W X8 cation exchange resin was used for purifying the hydrothermal fluids to separate Li from other matrix elements. The Li isotopic composition (δ7Li) was determined by Multi-collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS) with precision better than 0.2‰ (2σ, n=20). The Li concentration in the hydrothermal fluids falls between 0.02 to 10.31 mM. The δ7Li values vary from +1.9 to +29.7‰, indicating significant seawater contamination have occurred. These hydrothermal fluids fit well with seawater and brine two end-member binary mixing model. During phase separation, lithium, boron, chlorine, iodine, bromine, sodium and potassium were enriched in the brine phase. On the other hand, aluminum, sulphur and iron were enriched in the vapor phase. There is no significant isotope fractionation between the two phases. The water/rock ratio (W/R) calculated is low (about 1.5 to 1.8) for the Milos fluids, restricted seawater recharge into the oceanic crust. Moreover, the oceanic crust in the region becomes less altered since the W/R is low. The δ7Li value of the hydrothermal fluids can be used as a sensitive tool for studying water-rock interaction.

Compositional variation through time and space in Quaternary magmas of the Chyulu Hills Volcanic Province, Kenya

NASA Astrophysics Data System (ADS)

Widom, E.; Kuentz, D. C.

2017-12-01

The Chyulu Hills Volcanic Province, located in southern Kenya >100 km east of the Kenya Rift Valley, has produced mafic, monogenetic eruptions throughout the Quaternary. The volcanic field is considered to be an off-rift manifestation of the East African Rift System, and is known for the significant compositional variability of its eruptive products, which range from nephelinites to basanites, alkali basalts, hawaiites, and orthopyroxene-normative subalkaline basalts [1]. Notably, erupted compositions vary systematically in time and space: Pleistocene volcanism, occurring in the northern Chyulu Hills, was characterized by highly silica-undersaturated magmas, whereas Holocene volcanism, restricted to the southern Chyulu Hills, is less silica-understaturated, consistent with a progressive decrease in depth and increase in degree of melting with time, from north to south [1]. Pronounced negative K anomalies, and enriched trace element and Sr-Nd-Pb isotope signatures have been attributed to a metasomatized, amphibole-bearing, sub-continental lithospheric mantle (SCLM) source [2]. Seismic evidence for a partially molten zone in the SCLM beneath this region [3] may be consistent with such an interpretation. We have analyzed Chyulu Hills samples for Os, Hf and high precision Pb isotopes to further evaluate the magma sources and petrogenetic processes leading to systematic compositional variation in time and space. Sr-Nd-Pb-Hf isotope systematics and strong negative correlations of 206Pb/204Pb and highly incompatible trace element ratios with SiO2 are consistent with the progression from a deeper, HIMU-type source to a shallower, EM-type source. Os isotope systematics, however, suggest a more complex relationship; although all samples are more radiogenic than primitive mantle, the least radiogenic values (similar to primitive OIB) are found in magmas with intermediate SiO2, and those with lower or higher SiO2 are more radiogenic. This may be explained by interaction between mantle plume-derived magmas and heterogeneous metasomatized SCLM, consistent with the radiogenic Os isotope compositions found in some highly metasomatized mantle xenoliths associated with the Tanzanian craton [4]. [1] Spath et al., 2000; [2] Spath et al., 2001; [3] Ritter & Kasper, 1997; [4] Nelson et al., 2012.

Nitrogen Isotopic Composition of Proteinaceous Coral Skeletal Amino Acids Records Change in Source Nitrate to the Euphotic Zone in the Western Tropical Pacific

NASA Astrophysics Data System (ADS)

Williams, B.; Thibodeau, B.; Chikaraishi, Y.; Ohkouchi, N.; Grottoli, A. G.

2014-12-01

Instrumental and proxy data and global climate model experiments indicate a multi-decadal shoaling of the western tropical Pacific (WTP) thermocline potentially related to a shift in ENSO frequency. In the WTP, the nutricline coincides with the thermocline, and a shoaling of the nutricline brings more nitrate-rich seawater higher in the water column and within the sunlit euphotic zone. In the nutrient-poor WTP, this incursion of nitrate-rich water at the bottom of the euphotic zone may stimulate productivity in the water column. However, there is a general paucity of measurements below the surface with which to investigate recent changes in seawater chemistry. Nitrogen isotope (δ15N) measurements of particulate organic matter (POM) can elucidate the source of nitrogen to the WTP and related trophic dynamics. This POM is the food source to the long-lived proteinaceous corals, and drives the nitrogen isotopic composition of their skeleton. Here, we report time series δ15N values from the banded skeletons of proteinaceous corals from offshore Palau in the WTP that provide proxy information about past changes in euphotic zone nitrogen dynamics. Bulk skeletal δ15N values declined between 1977 and 2010 suggesting a progressively increasing contribution of deep water with isotopically-light nitrate to the euphotic zone and/or a shortening of the planktonic food web. Since only some amino acids are enriched in δ15N with each trophic transfer in a food web, we measured the δ15N composition of seven individual amino acids in the same coral skeleton. The δ15N time series of the individual amino acids also declined over time, mirroring the bulk values. These new data indicate that the changes in the source nitrogen to the base of the euphotic zone drives a decline in coral skeletal δ15N values, consistent with the shoaling nutricline, with no coinciding alteration of the trophic structure in the WTP.

Multi-Isotope Secondary Ion Mass Spectrometry Combining Heavy Water 2H with 15N Labeling As Complementary Tracers for Metabolic Heterogeneity at the Single-Cell Level

NASA Astrophysics Data System (ADS)

Kopf, S.; McGlynn, S.; Cowley, E.; Green, A.; Newman, D. K.; Orphan, V. J.

2014-12-01

Metabolic rates of microbial communities constitute a key physiological parameter for understanding the in situ growth constraints for life in any environment. Isotope labeling techniques provide a powerful approach for measuring such biological activity, due to the use of isotopically enriched substrate tracers whose incorporation into biological materials can be detected with high sensitivity by isotope-ratio mass spectrometry. Nano-meter scale secondary ion mass spectrometry (NanoSIMS) combined with stable isotope labeling provides a unique tool for studying the spatiometabolic activity of microbial populations at the single cell level in order to assess both community structure and population diversity. However, assessing the distribution and range of microbial activity in complex environmental systems with slow-growing organisms, diverse carbon and nitrogen sources, or heterotrophic subpopulations poses a tremendous technical challenge because the introduction of isotopically labeled substrates frequently changes the nutrient availability and can inflate or bias measures of activity. Here, we present the use of hydrogen isotope labeling with deuterated water as an important new addition to the isotopic toolkit and apply it for the determination of single cell microbial activities by NanoSIMS imaging. This tool provides a labeling technique that minimally alters any aquatic chemical environment, can be administered with strong labels even in minimal addition (natural background is very low), is an equally universal substrate for all forms of life even in complex, carbon and nitrogen saturated systems, and can be combined with other isotopic tracers. The combination of heavy water labeling with the most commonly used NanoSIMS tracer, 15N, is technically challenging but opens up a powerful new set of multi-tracer experiments for the study of microbial activity in complex communities. We present the first truly simultaneous single cell triple isotope system measurements of 2H/1H, 13C/12C and 15N/14N and apply it to study of microbial metabolic heterogeneity and nitrogen metabolism in a continuous culture case study. Our data provide insight into both the diversity of microbial activity rates, as well as patterns of ammonium utilization at the single cell level.

A Multi-Proxy Paradigm in the Pursuit of Ocean Paleoredox

NASA Astrophysics Data System (ADS)

Anbar, A. D.; Duan, Y.; Kendall, B.; Reinhard, C.; Severmann, S.; Lyons, T. W.

2011-12-01

The geologic record provides abundant evidence for variations in ocean oxygenation throughout Earth history. Expansion of ocean anoxic zones is expected in the future as a consequence of global climate change, with attendant effects on global nutrient inventories, carbon cycling and fluxes of trace greenhouse gases to the atmosphere. Therefore, studying ancient ocean redox variations not only teaches us about the history of the Earth system, but also provides insights into how the system may respond to analogous human perturbations. However, the extent, duration, causes, and consequences of most past variations are poorly understood. This problem motivates the development of paleoredox proxies, including novel stable isotope systems such as Mo, Fe, U and Tl. Experience with these emerging isotope systems demonstrates great promise but also many challenges. The Mo isotope system is illustrative. To first order, the geochemical cycling and isotope systematics of this element are straightforward, making it a useful proxy. However, critical unresolved issues include: (a) uncertainties in the ocean inputs through time; (b) ambiguities about fractionation mechanisms; (c) inadequate understanding of how modern analogs map to ancient systems. Similar challenges confront all the novel isotope systems. The way forward requires integration of multiple isotopic proxies, as well as information gleaned from careful analyses of element concentrations. For example, an episode of Mo enrichment in the 2.5 Ga Mt. McRae Shale is generally interpreted as resulting from buildup of Mo in seawater due to oxidative weathering. This enrichment is therefore thought to indicate a "whiff" of O2 in the environment prior to the Great Oxidation Event that began at 2.4 Ga. Molybdenum isotopes are consistent with this interpretation. However, Mo enrichment due to enhanced input from low-T hydrothermal sources in an anoxic regime cannot be completely excluded given the current state of knowledge of Mo isotope systematics from such sources. By considering sedimentary Fe enrichments together with Fe isotopes, we find that the Mo enrichment correlates with the telltale signature of a shelf-to-basin Fe redox "shuttle". Uranium isotopes also exhibit variations indicative of redox transformations. This multi-proxy dataset therefore paints a robust picture of trace metal redox cycling consistent with the "whiff" interpretation.

Development of laser ablation multi-collector inductively coupled plasma mass spectrometry for boron isotopic measurement in marine biocarbonates: new improvements and application to a modern Porites coral.

PubMed

Thil, François; Blamart, Dominique; Assailly, Caroline; Lazareth, Claire E; Leblanc, Thierry; Butsher, John; Douville, Eric

2016-02-15

Laser Ablation coupled to Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICPMS) is a powerful tool for the high-precision measurement of the isotopic ratios of many elements in geological samples, with the isotope ratio ((11) B/(10) B) of boron being used as an indicator of the pH of oceanic waters. Most geological samples or standards are polished and ablation occurs on flat surfaces. However, the shape and the irregularities of marine biocarbonates (e.g., corals, foraminifera) can make precise isotopic measurements of boron difficult. Even after polishing, the porosity properties and the presence of holes or micro-fractures affect the signal and the isotopic ratio when ablating the material, especially in raster mode. The effect of porosity and of the crater itself on the (11) B signal and the isotopic ratio acquired by LA-MC-ICPMS in both raster and spot mode was studied. Characterization of the craters was then performed with an optical profilometer to determine their shapes and depths. Surface state effects were examined by analyzing the isotopic fractionation of boron in silicate (NIST-SRM 612 and 610 standards) and in carbonate (corals). Surface irregularities led to a considerable loss of signal when the crater depth exceeded 20 µm. The stability and precision were degraded when ablation occurred in a deep cavity. The effect of laser focusing and of blank correction was also highlighted and our observations indicate that the accuracy of the boron isotopic ratio does not depend on the shape of the surface. After validation of the analytical protocol for boron isotopes, a raster application on a Porites coral, which grew for 18 months in an aquarium after field sampling, was carried out. This original LA-MC-ICPMS study revealed a well-marked boron isotope ratio temporal variability, probably related to growth rate and density changes, irrespective of the pH of the surrounding seawater. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Li-Zn-Pb multi isotopic characterization of the Loire River Basin, France

NASA Astrophysics Data System (ADS)

Millot, R.; Desaulty, A.; Widory, D.; Bourrain, X.

2013-12-01

The Loire River in France is approximately 1010 km long and drains an area of 117 800 km2. Upstream, the Loire River flows following a south to north direction from the Massif Central down to the city of Orléans, 650 km from its source. The Loire River is one of the main European riverine inputs to the Atlantic Ocean. Over time, its basin has been exposed to numerous sources of anthropogenic metal pollutions, such as metal mining, industry, agriculture and domestic inputs. The Loire River basin is thus an excellent study site to develop new isotope systematics for tracking anthropogenic sources of metal pollutions (Zn and Pb) and also to investigate Li isotope tracing that can provide key information on the nature of weathering processes at the Loire River Basin scale. Preliminary data show that Li-Zn-Pb concentrations and isotopic compositions span a wide range in river waters of the Loire River main stream and the main tributaries. There is a clear contrast between the headwaters upstream and rivers located downstream in the lowlands. In addition, one of the major tributaries within the Massif Central (the Allier River) is clearly influenced by inputs resulting from mineralizations and thermomineral waters. The results showed that, on their own, each of these isotope systematics reveals important information about the geogenic or anthropogenic origin Li-Zn-Pb. Considered together, they are however providing a more integrated understanding of the overall budgets of these elements at the scale of the Loire River Basin.

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

NASA Astrophysics Data System (ADS)

Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

2010-08-01

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.

Variation of lithium isotope geochemistry during basalt weathering and secondary mineral transformations in Hawaii

NASA Astrophysics Data System (ADS)

Ryu, Jong-Sik; Vigier, Nathalie; Lee, Sin-Woo; Lee, Kwang-Sik; Chadwick, Oliver A.

2014-11-01

Lithium isotopes are a potential tracer of silicate weathering but the relationship between lithium isotope compositions and weathering state still need to be established with precision. Here, we report Li concentrations and Li isotope compositions of soils developed along a 4 million year humid-environment chronosequence in the Hawaiian Islands. Li concentrations are variable with depth and age, ranging from 0.24 to 21.3 ppm, and significant Li depletions (up to 92%) relative to parent basalts are systematically enhanced towards the surface. Our calculations show that the relative contribution from atmospheric deposits to the Li soil budget remains small, with a maximum contribution from dust Li of 20% at the oldest site. This is explained by the capacity of the weathering products to retain, within the profiles, the Li coming from basalt alteration, and allows us to explore more specifically the role of alteration processes on soil Li isotope signatures. The δ7Li values display a large range between -2.5‰ and +13.9‰. The youngest soils (0.3 ka) display the same δ7Li value as fresh basalt, regardless of depth, despite ∼30% Li loss by leaching, indicating that there is little Li isotope fractionation during the incipient stage of weathering. δ7Li values for the older soils (⩾20 ka) vary non-linearly as a function of time and can be explained by progressive mineral transformations starting with the synthesis of metastable short-range order (nano-crystalline) minerals and followed by their transformation into relatively inert secondary minerals. Results highlight significant Li isotope fractionation during secondary mineral formation and in particular during Li uptake by kaolinite. Finally, we suggest that the non-monotonous evolution of the regolith δ7Li value over the last 4 Ma is consistent with climatic variations, where congruent release of Li isotopes occurs during warmer periods.

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our results show that (1) diffusive isotopic fractionations depend on the direction of diffusion in composition space, (2) diffusive isotopic fractionations scale with effective binary diffusion coefficient, as previously noted by Watkins et al. (2011), (3) self-diffusion is not decoupled from chemical diffusion, (4) self diffusion can be faster than or slower than chemical diffusion and (5) off-diagonal terms in the chemical diffusion matrix have isotopic mass-dependence. The results imply that relatively large isotopic fractionations can be generated by multicomponent diffusion even in the absence of large concentration gradients of the diffusing element. The new formulations for isotope diffusion can be tested with further experimentation and provide an improved framework for interpreting mass-dependent isotopic variations in natural liquids.

Uranium Measurement Improvements at the Savannah River Technology Center

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

Shick, C. Jr.

Uranium isotope ratio and isotope dilution methods by mass spectrometry are used to achieve sensitivity, precision and accuracy for various applications. This report presents recent progress made at SRTC in the analysis of minor isotopes of uranium. Comparison of routine measurements of NBL certified uranium (U005a) using the SRTC Three Stage Mass Spectrometer (3SMS) and the SRTC Single Stage Mass Spectrometer (SSMS). As expected, the three stage mass spectrometer yielded superior sensitivity, precision, and accuracy for this application.

New constraints on the sources and behavior of neodymium and hafnium in seawater from Pacific Ocean ferromanganese crusts

USGS Publications Warehouse

van de Flierdt, T.; Frank, M.; Lee, D.-C.; Halliday, A.N.; Reynolds, B.C.; Hein, J.R.

2004-01-01

The behavior of dissolved Hf in the marine environment is not well understood due to the lack of direct seawater measurements of Hf isotopes and the limited number of Hf isotope time-series obtained from ferromanganese crusts. In order to place better constraints on input sources and develop further applications, a combined Nd-Hf isotope time-series study of five Pacific ferromanganese crusts was carried out. The samples cover the past 38 Myr and their locations range from sites at the margin of the ocean to remote areas, sites from previously unstudied North and South Pacific areas, and water depths corresponding to deep and bottom waters. For most of the samples a broad coupling of Nd and Hf isotopes is observed. In the Equatorial Pacific ENd and EHf both decrease with water depth. Similarly, ENd and EHf both increase from the South to the North Pacific. These data indicate that the Hf isotopic composition is, in general terms, a suitable tracer for ocean circulation, since inflow and progressive admixture of bottom water is clearly identifiable. The time-series data indicate that inputs and outputs have been balanced throughout much of the late Cenozoic. A simple box model can constrain the relative importance of potential input sources to the North Pacific. Assuming steady state, the model implies significant contributions of radiogenic Nd and Hf from young circum-Pacific arcs and a subordinate role of dust inputs from the Asian continent for the dissolved Nd and Hf budget of the North Pacific. Some changes in ocean circulation that are clearly recognizable in Nd isotopes do not appear to be reflected by Hf isotopic compositions. At two locations within the Pacific Ocean a decoupling of Nd and Hf isotopes is found, indicating limited potential for Hf isotopes as a stand-alone oceanographic tracer and providing evidence of additional local processes that govern the Hf isotopic composition of deep water masses. In the case of the Southwest Pacific there is evidence that decoupling may have been the result of changes in weathering style related to the buildup of Antarctic glaciation. Copyright ?? 2004 Elsevier Ltd.

Experimental Assessment of Carbon Isotopes of Light Hydrocarbons under Different Redox Conditions

NASA Astrophysics Data System (ADS)

Fu, Q.; Chen, X.

2017-12-01

Hydrocarbons can be derived from a variety of carbon sources, by different processes, and under a wide range of physicochemical conditions. Other than bacterial activities facilitating biogenic hydrocarbon formation at low temperatures, decomposition of complex organic matter in sedimentary rocks at elevated temperatures produce thermogenic hydrocarbons, whereas abiogenic hydrocarbons are mainly generated through Fischer-Tropsch type synthesis with mineral catalysts. The carbon isotope has been used extensively to distinguish hydrocarbons of different origins and their formation conditions. For each type of hydrocarbons, however, environmental conditions may change reaction pathways and corresponding isotope fractionations. To better understand the variation of carbon isotopes caused by environmental variables, mineral constraints in particular, a series of laboratory experiments are conducted. In experiments where thermogenic hydrocarbons are formed, oil shale is the source material with different gypsum contents (0, 0.3, 0.5, and 1 wt.%). The abundance of generated light straight chain hydrocarbons decreases with increasing gypsum content, but their carbon isotopes become heavier. For example, the δ13C value of methane increases from -55.1‰ to -41.4‰ with gypsum varying between 0 and 1 wt.%. In similar experiments with the presence of MnO2, carbon isotope values of light alkanes are also higher, but with limited magnitudes (e.g., 3 to 4‰ for methane). In another experiment with dissolved H2 gas of 100 mmol/kg, light alkanes become depleted in 13C than experiments without H2. For example, there is a depletion of 2.7‰ for methane. The variation of carbon isotope values of light alkanes suggests the redox condition, constrained by mineral assemblage, fluid composition, and physical environment, play an important role in isotope fractionation. The pathway of hydrocarbon generation may be different under oxidized or reducing conditions. A set of experiments, in which abiogenic hydrocarbons are formed, is currently in progress. Combined together, they would facilitate our understanding of carbon isotope fractionation under geological conditions, and effective use of carbon isotopes as a diagnostic tool for hydrocarbons that are poorly understood in terms of origin and evolution.

Zinc isotope ratio imaging of rat brain thin sections from stable isotope tracer studies by LA-MC-ICP-MS.

PubMed

Urgast, Dagmar S; Hill, Sarah; Kwun, In-Sook; Beattie, John H; Goenaga-Infante, Heidi; Feldmann, Jörg

2012-10-01

Zinc stable isotope tracers (⁶⁷Zn and ⁷⁰Zn) were injected into rats at two different time points to investigate the feasibility of using tracers to study zinc kinetics at the microscale within distinct tissue features. Laser ablation coupled to multi-collector ICP-MS was used to analyse average isotope ratios in liver thin sections and to generate bio-images showing zinc isotope ratio distribution in brain thin sections. Average isotope ratios of all samples from treated animals were found to be statistically different (P < 0.05) from samples from untreated control animals. Furthermore, differing isotope ratios in physiological features of the brain, namely hippocampus, amygdala, cortex and hypothalamus, were identified. This indicates that these regions differ in their zinc metabolism kinetics. While cortex and hypothalamus contain more tracer two days after injection than 14 days after injection, the opposite is true for hippocampus and amygdala. This study showed that stable isotope tracer experiments can be combined with laser ablation MC-ICP-MS to measure trace element kinetics in tissues at a microscale level.

An in-depth evaluation of accuracy and precision in Hg isotopic analysis via pneumatic nebulization and cold vapor generation multi-collector ICP-mass spectrometry.

PubMed

Rua-Ibarz, Ana; Bolea-Fernandez, Eduardo; Vanhaecke, Frank

2016-01-01

Mercury (Hg) isotopic analysis via multi-collector inductively coupled plasma (ICP)-mass spectrometry (MC-ICP-MS) can provide relevant biogeochemical information by revealing sources, pathways, and sinks of this highly toxic metal. In this work, the capabilities and limitations of two different sample introduction systems, based on pneumatic nebulization (PN) and cold vapor generation (CVG), respectively, were evaluated in the context of Hg isotopic analysis via MC-ICP-MS. The effect of (i) instrument settings and acquisition parameters, (ii) concentration of analyte element (Hg), and internal standard (Tl)-used for mass discrimination correction purposes-and (iii) different mass bias correction approaches on the accuracy and precision of Hg isotope ratio results was evaluated. The extent and stability of mass bias were assessed in a long-term study (18 months, n = 250), demonstrating a precision ≤0.006% relative standard deviation (RSD). CVG-MC-ICP-MS showed an approximately 20-fold enhancement in Hg signal intensity compared with PN-MC-ICP-MS. For CVG-MC-ICP-MS, the mass bias induced by instrumental mass discrimination was accurately corrected for by using either external correction in a sample-standard bracketing approach (SSB) or double correction, consisting of the use of Tl as internal standard in a revised version of the Russell law (Baxter approach), followed by SSB. Concomitant matrix elements did not affect CVG-ICP-MS results. Neither with PN, nor with CVG, any evidence for mass-independent discrimination effects in the instrument was observed within the experimental precision obtained. CVG-MC-ICP-MS was finally used for Hg isotopic analysis of reference materials (RMs) of relevant environmental origin. The isotopic composition of Hg in RMs of marine biological origin testified of mass-independent fractionation that affected the odd-numbered Hg isotopes. While older RMs were used for validation purposes, novel Hg isotopic data are provided for the latest generations of some biological RMs.

Identifying calcium sources at an acid deposition-impacted spruce forest: a strontium isotope, alkaline earth element multi-tracer approach

Treesearch

Thomas D. Bullen; Scott W. Bailey

2005-01-01

Depletion of calcium from forest soils has important implications for forest productivity and health. Ca is available to fine feeder roots from a number of soil organic and mineral sources. but identifying the primary source or changes of sources in response to environmental change is problematic. We used strontium isotope and alkaline earth element concentration...

Cu, Fe, and Zn Isotope Variations Within a High-Temperature Mid-Ocean Ridge Sulfide Structure

NASA Astrophysics Data System (ADS)

Ewing, S. M.; Nelson, B. K.; Kelley, D. S.; Nielsen, D. C.

2006-12-01

Hydrothermal processes at mid-ocean ridges play an important role in controlling the transition metal budget of seawater and the crust through which it circulates. Preliminary work has shown stable metal isotope variations accompany these processes. We report Cu, Zn, and Fe isotope analyses of transects through a high temperature sulfide structure ("Fin") collected during the 1998 Edifice Rex Sulfide Recovery Project. We analyzed two horizontal transects through the sulfide edifice, from inner conduit to outer surface. Transects A and F are 9 and 6 cm in length, respectively. Each displays radially zoned mineralogy progressing from a chalcopyrite (ccp) zone through zones of zinc sulfide, pyrite-anhydrite (pyr-anh) matrix, zinc sulfide-anhydrite (zns-anh) matrix, to an outer well-cemented silica (Si) zone. Additional ccp and pyr-anh zones appear in transect A resulting from a smaller breakout conduit. In transect A, Cu displays the most isotopic variation, with little variation in Fe and Zn isotopes. From the inner ccp zone outward, the Cu isotope profile shows a 0.4‰ (±0.05‰ 2σ) increase in the first pyr-anh zone over the coarse-grained ccp zone. The δ65Cu drops by 0.6‰ in the secondary ccp zone and recovers to values of the innermost wall in the following zone where it is constant until the outermost portion of the Si rich zone, which shows a 1.3‰ increase over inner zone values. The Zn isotope profile has a total variation of 0.27‰ (±0.05‰ 2σ), with a 0.2‰ increase in the first pyr- anh zone followed by a .27‰ decrease in the adjacent zone, and recovering to its heaviest values in the second pyr-anh zone. The Zn profile lacks any significant increase of the δ^{64}Zn in the outermost zones. The Fe isotope profile shows very little variation across the chimney wall, but does have a sharp 0.7‰ (±0.1‰ 2σ) increase in the δ56Fe in the well-cemented Si rich zone. In transect F, the Cu isotope profile again shows the most variation, but displays a more pronounced jump of 1.3‰ at the zinc sulfide boundary and no obvious increase of the δ65Cu in the Si rich zone. Similarly with Zn, there is a 0.35‰ increase of the δ^{64}Zn, but no outer wall increase. Fe, on the other hand, has variation of the same order as transect A, and shows a 0.6‰ increase of the δ56Fe in both the zns-anh and Si rich zones. These profiles are likely the result of a combination of diffusion and advection processes, fluid mineral equilibria, and mineral-mineral equilibria. High δ values of the outer zones likely reflect oxidation reactions with seawater. Processes responsible for isotopic variations within interior zones of the structure are ambiguous. Kinetic effects and biological activity may play a role, as Zn, which is not redox sensitive and only minimally coordination sensitive, has profiles that are qualitatively similar to Cu and Fe, but less analytically pronounced. Our findings are within the range of other published results, and further illustrate such measurable metal isotope variation exists not only on the vent field scale among chimneys, but systematically within chimney walls.

Nuclear Resonance Fluorescence of U-235

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

Warren, Glen A.; Caggiano, Joseph A.; Hensley, Walter K.

Nuclear resonance fluorescence is a physical process that provides an isotopic-specific signature that could be used for the identification and characterization of materials. The technique involves the detection of prompt discrete-energy photons emitted from a sample which is exposed to photons in the MeV energy range. Potential applications of the technique range from detection of high explosives to characterization of special nuclear materials. One isotope of significant interest is 235U. Pacific Northwest National Laboratory and Passport Systems have collaborated to conduct measurements to search for a nuclear resonance fluorescence response of 235U below 3 MeV using a 200 g samplemore » of highly enriched uranium. Nine 235U resonances between 1650 and 2010 keV were identified in the preliminary analysis. Analysis of the measurement data to determine the integrated cross sections of the resonances is in progress.« less

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones.

PubMed

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-12-16

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ 66 Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ 66 Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO 4 2- complexes preferentially incorporate heavy δ 66 Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge.

Ion implantation system and process for ultrasensitive determination of target isotopes

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

Farmer, III, Orville T.; Liezers, Martin

2016-09-13

A system and process are disclosed for ultrasensitive determination of target isotopes of analytical interest in a sample. Target isotopes may be implanted in an implant area on a high-purity substrate to pre-concentrate the target isotopes free of contaminants. A known quantity of a tracer isotope may also be implanted. Target isotopes and tracer isotopes may be determined in a mass spectrometer. The present invention provides ultrasensitive determination of target isotopes in the sample.

Apparatus and process for separating hydrogen isotopes

DOEpatents

Heung, Leung K; Sessions, Henry T; Xiao, Xin

2013-06-25

The apparatus and process for separating hydrogen isotopes is provided using dual columns, each column having an opposite hydrogen isotopic effect such that when a hydrogen isotope mixture feedstock is cycled between the two respective columns, two different hydrogen isotopes are separated from the feedstock.

Iron Isotope Variations in Reduced Groundwater and in Drinking Water Supplies: A Case Study of Hanoi, Vietnam

NASA Astrophysics Data System (ADS)

Teutsch, N.; Berg, M.; von Gunten, U.; Halliday, A.

2004-12-01

In reduced groundwater iron is involved in biotic and abiotic transformation processes, both of which could lead to iron isotope fractionation. The reduced groundwater aquifers in the area of the Vietnamese capital of Hanoi are the main drinking water sources for the city. These groundwaters contain arsenic, which imposes a serious health threat to millions of people. Dissolved arsenic is related to the reducing conditions prevalent in the groundwater, and iron and arsenic contents are correlated in the sediments. We are employing iron isotope composition as a tool to better understand the processes leading to the transformation of iron in the groundwater and its role in various biogeochemical processes in reduced environments. Drinking water is supplied to the city of Hanoi from several water treatment plants (WTP) which pump the raw groundwater from a lower aquifer, while the rural surroundings pump untreated groundwater from an upper aquifer by private tubewells. Surface water from the Red River delta is the main source of recharge to these two aquifers. Due to high content of particulate natural organic matter (NOM) in the sediment leading to extensive microbial activity, the groundwaters are anoxic and rich in dissolved iron(II). The iron(II) removal in the WTPs is carried by a multi-step treatment including aeration, settling, filtration, and chlorination. We have collected natural groundwater samples for isotopic analysis from two aquifers at several locations, a groundwater depth profile and its corresponding sediment phases from the upper aquifer and the underlying aquitard, raw and treated water from several WTPs, as well as the corresponding iron(III) precipitates. The iron concentrations of groundwaters analysed in this study range from 3 to 28 mg/L and δ 57Fe (57/54 deviation from IRMM 014) values vary between -1.2 and +1.5 ‰ . The sediment depth profile has a δ 57Fe around +0.3 ‰ , which implies that the high values obtained in the groundwater nearby (+0.9 - +1.2 ‰ ) cannot be explained by a simple reductive dissolution process, which would be expected to favour the lighter Fe isotopes. Removal of iron in the WTP is followed by a strong decrease of δ 57Fe, probably due to formation of heavier Fe(III) phases. High δ 57Fe values are found in both aquifers and correspond to high concentrations of iron in the groundwater. We hypothesize that the iron isotopic variations observed so far are an indication for iron sources and transformation processes that could not be detected by only measuring dissolved iron concentrations. Current investigations will further explore this hypothesis.

Hydrochemical and isotopic characterization of groundwater in the Ghis-Nekor plain (northern Morocco)

NASA Astrophysics Data System (ADS)

Chafouq, D.; El Mandour, A.; Elgettafi, M.; Himi, M.; Chouikri, I.; Casas, A.

2018-03-01

The coastal aquifer of Ghis-Nekor (Morocco) was studied to identify the major processes causing salinization of groundwater. In fact, a geochemical approach multi tracer (general chemistry and isotopes - δ2H, δ18O-H2O, δ34S, δ18O-SO4) was utilized, with the hydrodynamics to explain the processes responsible for the salinization of groundwater, and for identttifying areas most vulnerable to seawater intrusion. The recharge of the aquifer is mainly by the Al-Khattabi dam, the Nekor River and the Ghis River, on the eastern border of the plain. The water that feeds the aquifer shows a relatively high level of salinity and for this reason, the majority of sampled wells indicate high values of electric conductivity and total salinity which arrives at 7.5 g L-1. The plot of the geochemical results analyzes of groundwater in the Piper diagram shows two distinct chemical facies; sodium chloride-facies and chlorinated calcium and magnesium sulfated facies. The concentrations of 18O range between -4.15‰ and -5.73‰, while the values of 2H range between -28.4‰ and -41.7‰. The Nekor river water is depleted in heavy isotopes, and the isotopic compositions are in the order on -6‰ for 18O and -40.5‰ for deuterium. Most of the wells have a slope <8 indicating a slight evaporation before infiltration. The data show low and variable d-excess values (range from -0.02‰ to 11.6‰), reflect recharge during different climatic conditions. The isotopic concentrations of 18O-SO4 vary between 4.35‰ and 8.60‰, while the 34S isotope values range from -4.3‰ to 9.9‰. For Ghis River, these values are between -4.4‰ and 4.95‰, respectively, for sulfur and oxygen. The interpretation of the chemical and isotopic results suggesting the intrusion of seawater to increase salinity of groundwater in the region is low. However, only the NE area shows probable contamination of seawater. In contrast, wells are saline independent of seawater intrusion, the origin of the high salinity can be related to: 1- the accumulation of rivers fluid intake and water dam rich dissolved salts and sulphates, 2- the anthropogenic pollution (domestic sewage, agricultural inputs, septic uses).

Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair

PubMed Central

Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

2016-01-01

The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of −19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved. PMID:27616586

Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair

NASA Astrophysics Data System (ADS)

Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

2016-09-01

The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of -19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved.

Carbon isotope equilibration during sulphate-limited anaerobic oxidation of methane

NASA Astrophysics Data System (ADS)

Yoshinaga, Marcos Y.; Holler, Thomas; Goldhammer, Tobias; Wegener, Gunter; Pohlman, John W.; Brunner, Benjamin; Kuypers, Marcel M. M.; Hinrichs, Kai-Uwe; Elvert, Marcus

2014-03-01

Collectively, marine sediments comprise the largest reservoir of methane on Earth. The flux of methane from the sea bed to the overlying water column is mitigated by the sulphate-dependent anaerobic oxidation of methane by marine microbes within a discrete sedimentary horizon termed the sulphate-methane transition zone. According to conventional isotope systematics, the biological consumption of methane leaves a residue of methane enriched in 13C (refs , , ). However, in many instances the methane within sulphate-methane transition zones is depleted in 13C, consistent with the production of methane, and interpreted as evidence for the intertwined anaerobic oxidation and production of methane. Here, we report results from experiments in which we incubated cultures of microbial methane consumers with methane and low levels of sulphate, and monitored the stable isotope composition of the methane and dissolved inorganic carbon pools over time. Residual methane became progressively enriched in 13C at sulphate concentrations above 0.5 mM, and progressively depleted in 13C below this threshold. We attribute the shift to 13C depletion during the anaerobic oxidation of methane at low sulphate concentrations to the microbially mediated carbon isotope equilibration between methane and carbon dioxide. We suggest that this isotopic effect could help to explain the 13C-depletion of methane in subseafloor sulphate-methane transition zones.

Homogeneous diet of contemporary Japanese inferred from stable isotope ratios of hair.

PubMed

Kusaka, Soichiro; Ishimaru, Eriko; Hyodo, Fujio; Gakuhari, Takashi; Yoneda, Minoru; Yumoto, Takakazu; Tayasu, Ichiro

2016-09-12

The globalization of food production and distribution has homogenized human dietary patterns irrespective of geography, but it is uncertain how far this homogenization has progressed. This study investigated the carbon and nitrogen isotope ratios in the scalp hair of 1305 contemporary Japanese and found values of -19.4 ± 0.6‰ and 9.4 ± 0.6‰ (mean ± SD), respectively. Within Japan, the inter-regional differences for both isotope ratios was less than 1‰, which indicates low dietary heterogeneity among prefectural divisions. The carbon and nitrogen isotope ratios of the hair showed a significant correlation with the results of questionnaires on self-reported dietary habits. The carbon isotope ratios from Japan were lower than those in samples from the USA but higher than those in samples from Europe. These differences stem from the varying dietary proportions of food products originally derived from C3 and C4 plants. The dietary variation of Japan is as small as those of Europe and USA and smaller than those of some Asian countries. These results indicate that dietary homogeneity has progressed in Japan, which may indicate the influence from the spread of the Western-style diet and food globalization, although dietary heterogeneity among countries is still preserved.

Experimental Evidence for Fast Lithium Diffusion and Isotope Fractionation in Water-bearing Rhyolitic Melts at Magmatic Conditions

NASA Astrophysics Data System (ADS)

Cichy, S. B.; Till, C. B.; Roggensack, K.; Hervig, R. L.; Clarke, A. B.

2015-12-01

The aim of this work is to extend the existing database of experimentally-determined lithium diffusion coefficients to more natural cases of water-bearing melts at the pressure-temperature range of the upper crust. In particular, we are investigating Li intra-melt and melt-vapor diffusion and Li isotope fractionation, which have the potential to record short-lived magmatic processes (seconds to hours) in the shallow crust, especially during decompression-induced magma degassing. Hydrated intra-melt Li diffusion-couple experiments on Los Posos rhyolite glass [1] were performed in a piston cylinder at 300 MPa and 1050 °C. The polished interfaces between the diffusion couples were marked by addition of Pt powder for post-run detection. Secondary ion mass spectrometry analyses indicate that lithium diffuses extremely fast in the presence of water. Re-equilibration of a hydrated ~2.5 mm long diffusion-couple experiment was observed during the heating period from room temperature to the final temperature of 1050 °C at a rate of ~32 °C/min. Fractionation of ~40‰ δ7Li was also detected in this zero-time experiment. The 0.5h and 3h runs show progressively higher degrees of re-equilibration, while the isotope fractionation becomes imperceptible. Li contamination was observed in some experiments when flakes filed off Pt tubing were used to mark the diffusion couple boundary, while the use of high purity Pt powder produced better results and allowed easier detection of the diffusion-couple boundary. The preliminary lithium isotope fractionation results (δ7Li vs. distance) support findings from [2] that 6Li diffuses substantially faster than 7Li. Further experimental sets are in progress, including lower run temperatures (e.g. 900 °C), faster heating procedure (~100 °C/min), shorter run durations and the extension to mafic systems. [1] Stanton (1990) Ph.D. thesis, Arizona State Univ., [2] Richter et al. (2003) GCA 67, 3905-3923.

Stable isotope composition of cocoa beans of different geographical origin.

PubMed

Perini, Matteo; Bontempo, Luana; Ziller, Luca; Barbero, Alice; Caligiani, Augusta; Camin, Federica

2016-09-01

The isotopic profile (δ(13) C, δ(15) N, δ(18) O, δ(2) H, δ(34) S) was used to characterise a wide selection of cocoa beans from different renowned production areas (Africa, Asia, Central and South America). The factors most influencing the isotopic signatures of cocoa beans were climate and altitude for δ(13) C and the isotopic composition of precipitation water for δ(18) O and δ(2) H, whereas δ(15) N and δ(34) S were primarily affected by geology and fertilisation practises. Multi-isotopic analysis was shown to be sufficiently effective in determining the geographical origin of cocoa beans, and combining it with Canonical Discriminant Analysis led to more than 80% of samples being correctly reclassified. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Aliphatic and aromatic plant biopolymer dynamics in soil particles isolated from sequential density fractionation

NASA Astrophysics Data System (ADS)

Caldwell, B.; Filley, T.; Sollins, P.; Lajtha, K.; Swanston, C.; Kleber, M.; Kramer, M.

2007-12-01

A recent multi-layer-based soil organic matter-mineral interaction mechanistic model to describe the nature of soil organic matter-mineral surface mechanism for soil organic matter stabilization predicts that proteinaceous and aliphatic materials establish the core of strong binding-interactions upon which other organic matter is layered. A key methodology providing data underpinning this hypothesis is sequential density fractionation where soil is partitioned into particles of increasing density with the assumption that a partial control on organic matter distribution through density series is the thickness of its layering. Four soils of varying mineralogy and texture were investigated for their biopolymer, isotopic, and mineralogical properties. Light fractions (<1.8 g/cm3), although dominanted by organic detritus, did not always contain the highest concentration of lignin and substituted fatty acids from cutin and suberin while heavier fractions, 1.8-2.6 g/cm3, exhibited a progressive decrease in concentration in plant derived biopolymers with density. Extractable lignin phenols exhibited a progressive oxidation state with density. The concentration of biopolymers roughly mirrored the C:N ratio of soil particles which dropped consistently with increasing particle density. Although, in all soils, both lignin phenols and SFA concentration generally decreased with increasing density the ratio SFA/lignin varied with density and depending upon the soil. All soils, except the oxisol, exhibited an increase in SFA with respect to lignin suggesting a selective stabilization of those material with respect to lignin. In the oxisol, which showed little variation in its hematite dominated mineralogy across density, SFA/lignin remained constant, potentially indicating a greater capacity to stabilize lignin in that system. Interestingly, the lignin oxidation state increased with density in the oxisol. Given the variation in soil character, the consistency in these trends it suggests a general phenomenon of progressive decay in plant derived material with thinness of mineral coating but an overall relative increase in aliphatic character-all consistent with the multi-layer model.

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.

ICT: isotope correction toolbox.

PubMed

Jungreuthmayer, Christian; Neubauer, Stefan; Mairinger, Teresa; Zanghellini, Jürgen; Hann, Stephan

2016-01-01

Isotope tracer experiments are an invaluable technique to analyze and study the metabolism of biological systems. However, isotope labeling experiments are often affected by naturally abundant isotopes especially in cases where mass spectrometric methods make use of derivatization. The correction of these additive interferences--in particular for complex isotopic systems--is numerically challenging and still an emerging field of research. When positional information is generated via collision-induced dissociation, even more complex calculations for isotopic interference correction are necessary. So far, no freely available tools can handle tandem mass spectrometry data. We present isotope correction toolbox, a program that corrects tandem mass isotopomer data from tandem mass spectrometry experiments. Isotope correction toolbox is written in the multi-platform programming language Perl and, therefore, can be used on all commonly available computer platforms. Source code and documentation can be freely obtained under the Artistic License or the GNU General Public License from: https://github.com/jungreuc/isotope_correction_toolbox/ {christian.jungreuthmayer@boku.ac.at,juergen.zanghellini@boku.ac.at} Supplementary data are available at Bioinformatics online. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Mass fractionation processes of transition metal isotopes

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Nitrogen-isotopes and multi-parameter sewage water test for identification of nitrate sources: Groundwater body Marchfeld East of Vienna

NASA Astrophysics Data System (ADS)

Kralik, Martin

2017-04-01

The application of nitrogen and oxygen isotopes in nitrate allows, under favourable circumstances, to identify potential sources such as precipitation, chemical fertilisers and manure or sewage water. Without any additional tracer, the source distinction of nitrate from manure or sewage water is still difficult. Even the application of boron isotopes can in some cases not avoid ambiguous interpretation. Therefore, the Environment Agency Austria developed a new multi parametrical indicator test to allow the identification and quantification of pollution by domestic sewage water. The test analyses 8 substances well known to occur in sewage water: Acesulfame and sucralose (two artificial, calorie-free sweeteners), benzotriazole and tolyltriazole (two industrial chemicals/corrosion inhibitors), metoprolol, sotalol, carbamazepine and the metabolite 10,11-Dihydro-10,11-dihydroxycarbamazepine (pharmaceuticals) [1]. These substances are polar and degradation in the aquatic system by microbiological processes is not documented. These 8 Substances do not occur naturally which make them ideal tracers. The test can detect wastewater in the analysed water sample down to 0.1 %. This ideal coupling of these analytic tests helps to identify the nitrogen sources in the groundwater body Marchfeld East of Vienna to a high confidence level. In addition, the results allow a reasonable quantification of nitrogen sources from different types of fertilizers as well as sewage water contributions close to villages and in wells recharged by bank filtration. Recent investigations of groundwater in selected wells in Marchfeld [2] indicated a clear nitrogen contribution by wastewater leakages (sewers or septic tanks) to the total nitrogen budget. However, this contribution is shrinking and the main source comes still from agricultural activities. [1] Humer, F.; Weiss, S.; Reinnicke, S.; Clara, M.; Grath, J.; Windhofer, G. (2013): Multi parametrical indicator test for urban wastewater influence. EGU General Assembly 2013, held 7-12 April, 2013 in Vienna, Austria, id. EGU2013-5332, EGU2013-5332. [2] Kralik, M.; Humer, F. & Grath, J. (2008): Pilotprojekt Grundwasseralter: Herkunftsanalyse von Nitrat mittels Stickstoff-, Sauerstoff-, Schwefel und Kohlenstoffisotopen. 57 S.2, Environment Agency Austria/Ministry of Agriculture, Forestry, Environment and Water Management, Vienna.

RTI Scheduling Processes for Middle Schools. Information Brief

ERIC Educational Resources Information Center

Prewett, Sara; Mellard, Daryl; Lieske-Lupo, Jessica

2011-01-01

Response to intervention integrates assessment and intervention within a multi-level prevention system to maximize student achievement and to reduce behavior problems. With RTI, schools identify students at risk for poor learning outcomes, monitor student progress, provide evidence-based interventions and adjust the intensity and nature of those…

A Bayesian Framework of Uncertainties Integration in 3D Geological Model

NASA Astrophysics Data System (ADS)

Liang, D.; Liu, X.

2017-12-01

3D geological model can describe complicated geological phenomena in an intuitive way while its application may be limited by uncertain factors. Great progress has been made over the years, lots of studies decompose the uncertainties of geological model to analyze separately, while ignored the comprehensive impacts of multi-source uncertainties. Great progress has been made over the years, while lots of studies ignored the comprehensive impacts of multi-source uncertainties when analyzed them item by item from each source. To evaluate the synthetical uncertainty, we choose probability distribution to quantify uncertainty, and propose a bayesian framework of uncertainties integration. With this framework, we integrated data errors, spatial randomness, and cognitive information into posterior distribution to evaluate synthetical uncertainty of geological model. Uncertainties propagate and cumulate in modeling process, the gradual integration of multi-source uncertainty is a kind of simulation of the uncertainty propagation. Bayesian inference accomplishes uncertainty updating in modeling process. Maximum entropy principle makes a good effect on estimating prior probability distribution, which ensures the prior probability distribution subjecting to constraints supplied by the given information with minimum prejudice. In the end, we obtained a posterior distribution to evaluate synthetical uncertainty of geological model. This posterior distribution represents the synthetical impact of all the uncertain factors on the spatial structure of geological model. The framework provides a solution to evaluate synthetical impact on geological model of multi-source uncertainties and a thought to study uncertainty propagation mechanism in geological modeling.

Progress on Platforms, Sensors and Applications with Unmanned Aerial Vehicles in soil science and geomorphology

NASA Astrophysics Data System (ADS)

Anders, Niels; Suomalainen, Juha; Seeger, Manuel; Keesstra, Saskia; Bartholomeus, Harm; Paron, Paolo

2014-05-01

The recent increase of performance and endurance of electronically controlled flying platforms, such as multi-copters and fixed-wing airplanes, and decreasing size and weight of different sensors and batteries leads to increasing popularity of Unmanned Aerial Systems (UAS) for scientific purposes. Modern workflows that implement UAS include guided flight plan generation, 3D GPS navigation for fully automated piloting, and automated processing with new techniques such as "Structure from Motion" photogrammetry. UAS are often equipped with normal RGB cameras, multi- and hyperspectral sensors, radar, or other sensors, and provide a cheap and flexible solution for creating multi-temporal data sets. UAS revolutionized multi-temporal research allowing new applications related to change analysis and process monitoring. The EGU General Assembly 2014 is hosting a session on platforms, sensors and applications with UAS in soil science and geomorphology. This presentation briefly summarizes the outcome of this session, addressing the current state and future challenges of small-platform data acquisition in soil science and geomorphology.

MuLoG, or How to Apply Gaussian Denoisers to Multi-Channel SAR Speckle Reduction?

PubMed

Deledalle, Charles-Alban; Denis, Loic; Tabti, Sonia; Tupin, Florence

2017-09-01

Speckle reduction is a longstanding topic in synthetic aperture radar (SAR) imaging. Since most current and planned SAR imaging satellites operate in polarimetric, interferometric, or tomographic modes, SAR images are multi-channel and speckle reduction techniques must jointly process all channels to recover polarimetric and interferometric information. The distinctive nature of SAR signal (complex-valued, corrupted by multiplicative fluctuations) calls for the development of specialized methods for speckle reduction. Image denoising is a very active topic in image processing with a wide variety of approaches and many denoising algorithms available, almost always designed for additive Gaussian noise suppression. This paper proposes a general scheme, called MuLoG (MUlti-channel LOgarithm with Gaussian denoising), to include such Gaussian denoisers within a multi-channel SAR speckle reduction technique. A new family of speckle reduction algorithms can thus be obtained, benefiting from the ongoing progress in Gaussian denoising, and offering several speckle reduction results often displaying method-specific artifacts that can be dismissed by comparison between results.

High-precision Ru isotopic measurements by multi-collector ICP-MS.

PubMed

Becker, Harry; Dalpe, Claude; Walker, Richard J

2002-06-01

Ruthenium isotopic data for a pure Aldrich ruthenium nitrate solution obtained using a Nu Plasma multi collector inductively coupled plasma-mass spectrometer (MC-ICP-MS) shows excellent agreement (better than 1 epsilon unit = 1 part in 10(4)) with data obtained by other techniques for the mass range between 96 and 101 amu. External precisions are at the 0.5-1.7 epsilon level (2sigma). Higher sensitivity for MC ICP-MS compared to negative thermal ionization mass spectrometry (N-TIMS) is offset by the uncertainties introduced by relatively large mass discrimination and instabilities in the plasma source-ion extraction region that affect the long-term reproducibility. Large mass bias correction in ICP mass spectrometry demands particular attention to be paid to the choice of normalizing isotopes. Because of its position in the mass spectrum and the large mass bias correction, obtaining precise and accurate abundance data for 104Ru by MC-ICP-MS remains difficult. Internal and external mass bias correction schemes in this mass range may show similar shortcomings if the isotope of interest does not lie within the mass range covered by the masses used for normalization. Analyses of meteorite samples show that if isobaric interferences from Mo are sufficiently large (Ru/Mo < 10(4)), uncertainties on the Mo interference correction propagate through the mass bias correction and yield inaccurate results for Ru isotopic compositions. Second-order linear corrections may be used to correct for these inaccuracies, but such results are generally less precise than N-TIMS data.

Isotope effect of mercury diffusion in air

PubMed Central

Koster van Groos, Paul G.; Esser, Bradley K.; Williams, Ross W.; Hunt, James R.

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature. PMID:24364380

Isotope effect of mercury diffusion in air.

PubMed

Koster van Groos, Paul G; Esser, Bradley K; Williams, Ross W; Hunt, James R

2014-01-01

Identifying and reducing impacts from mercury sources in the environment remains a considerable challenge and requires process based models to quantify mercury stocks and flows. The stable isotope composition of mercury in environmental samples can help address this challenge by serving as a tracer of specific sources and processes. Mercury isotope variations are small and result only from isotope fractionation during transport, equilibrium, and transformation processes. Because these processes occur in both industrial and environmental settings, knowledge of their associated isotope effects is required to interpret mercury isotope data. To improve the mechanistic modeling of mercury isotope effects during gas phase diffusion, an experimental program tested the applicability of kinetic gas theory. Gas-phase elemental mercury diffusion through small bore needles from finite sources demonstrated mass dependent diffusivities leading to isotope fractionation described by a Rayleigh distillation model. The measured relative atomic diffusivities among mercury isotopes in air are large and in agreement with kinetic gas theory. Mercury diffusion in air offers a reasonable explanation of recent field results reported in the literature.

Century long assessment of herbaceous plants' physiological responses to climate change in Switzerland

NASA Astrophysics Data System (ADS)

Moreno-Gutierrez, Cristina; Kahmen, Ansgar

2017-04-01

The isotopic analysis of archived plant material offers the exceptional opportunity to reconstruct the physiological activity of plants over long time periods and thus, to assess plant responses to environmental changes during the last centuries. In addition, the stable isotope analysis of herbarium samples offers the opportunity to reconstruct the physiological processes of a large range of different plant species and from different environments. Interestingly, only few studies have to date assessed these archives. We will present a novel analysis of leaf nitrogen, oxygen and carbon isotope ratios of more than a thousand herbarium specimens collected since 1800 until present from the unique herbaria hold at the University of Basel. The objective of our study was to assess century-long physiological responses of herbaceous plant species from different plant functional groups and along an altitudinal gradient in Switzerland. The goal of our study was to determine with our investigations the long-term responses of plants to climate change. Such investigations are important as they allow to assess long-term processes of acclimation and adaptation in plants to global enviromental change. In our study we found that herbaceous plants have increased their intrinsic water use efficiency in response to increasing atmospheric CO2 concentration but this increment was higher in plants from higher altitudes, due to the higher efficiency of CO2 assimilation of alpine plants compared to plants from lowlands. There were also differences among functional groups, with grasses and forbs showing the highest increments. In addition, herbaceous plants showed a decreasing trend with time in their N isotopic composition, which may indicate progressive N limitation due to higher biological activity with increasing atmospheric CO2 concentration.

Methane concentration and isotopic composition (δ13C-CH4) in the Nerja Cave system (South Spain)

NASA Astrophysics Data System (ADS)

Vadillo, Iñaki; Etiope, Giuseppe; Benavente, José; Ojeda, Lucia; Liñán, Cristina; Carrasco, Francisco

2016-04-01

Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (δ13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. δ13C increases correspondingly from -47 ‰ to -41 ‰ (VPDB). CH4 is systematically 13C-enriched (δ13C > -45) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of sub-atmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.

Parent Body Influences on Amino Acids in the Tagish Lake Meteorite

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Callahan, M. P.; Dworkin, J. P.; Elsila, J. E.; Herd, C. D. K.

2010-01-01

The Tagish Lake meteorite is a primitive C2 carbonaceous chondrite with a mineralogy, oxygen isotope, and bulk chemical. However, in contrast to many CI and CM carbonaceous chondrites, the Tagish Lake meteorite was reported to have only trace levels of indigenous amino acids, with evidence for terrestrial L-amino acid contamination from the Tagish Lake meltwater. The lack of indigenous amino acids in Tagish Lake suggested that they were either destroyed during parent body alteration processes and/or the Tagish Lake meteorite originated on a chemically distinct parent body from CI and CM meteorites where formation of amino acids was less favorable. We recently measured the amino acid composition of three different lithologies (11h, 5b, and 11i) of pristine Tagish Lake meteorite fragments that represent a range of progressive aqueous alteration in order 11h < 5b < 11i as inferred from the mineralogy, petrology, bulk isotopes, and insoluble organic matter structure. The distribution and enantiomeric abundances of the one- to six-carbon aliphatic amino acids found in hot-water extracts of the Tagish Lake fragments were determined by ultra performance liquid chromatography fluorescence detection and time of flight mass spectrometry coupled with OPA/NAC derivatization. Stable carbon isotope analyses of the most abundant amino acids in 11h were measured with gas chromatography coupled with quadrupole mass spectrometry and isotope ratio mass spectrometry.

Target analyte quantification by isotope dilution LC-MS/MS directly referring to internal standard concentrations--validation for serum cortisol measurement.

PubMed

Maier, Barbara; Vogeser, Michael

2013-04-01

Isotope dilution LC-MS/MS methods used in the clinical laboratory typically involve multi-point external calibration in each analytical series. Our aim was to test the hypothesis that determination of target analyte concentrations directly derived from the relation of the target analyte peak area to the peak area of a corresponding stable isotope labelled internal standard compound [direct isotope dilution analysis (DIDA)] may be not inferior to conventional external calibration with respect to accuracy and reproducibility. Quality control samples and human serum pools were analysed in a comparative validation protocol for cortisol as an exemplary analyte by LC-MS/MS. Accuracy and reproducibility were compared between quantification either involving a six-point external calibration function, or a result calculation merely based on peak area ratios of unlabelled and labelled analyte. Both quantification approaches resulted in similar accuracy and reproducibility. For specified analytes, reliable analyte quantification directly derived from the ratio of peak areas of labelled and unlabelled analyte without the need for a time consuming multi-point calibration series is possible. This DIDA approach is of considerable practical importance for the application of LC-MS/MS in the clinical laboratory where short turnaround times often have high priority.

Bromine isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry with a conventional sample introduction system.

PubMed

de Gois, Jefferson S; Vallelonga, Paul; Spolaor, Andrea; Devulder, Veerle; Borges, Daniel L G; Vanhaecke, Frank

2016-01-01

A simple and accurate methodology for Br isotope ratio measurements in seawater by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) with pneumatic nebulization for sample introduction was developed. The Br(+) signals could be measured interference-free at high mass resolution. Memory effects for Br were counteracted using 5 mmol L(-1) of NH4OH in sample, standard, and wash solutions. The major cation load of seawater was removed via cation exchange chromatography using Dowex 50WX8 resin. Subsequent Br preconcentration was accomplished via evaporation of the sample solution at 90 °C, which did not induce Br losses or isotope fractionation. Mass discrimination was corrected for by external correction using a Cl-matched standard measured in a sample-standard bracketing approach, although Sr, Ge, and Se were also tested as potential internal standards for internal correction for mass discrimination. The δ(81)Br (versus standard mean ocean bromide (SMOB)) values thus obtained for the NaBr isotopic reference material NIST SRM 977 and for IRMM BCR-403 seawater certified reference material are in agreement with literature values. For NIST SRM 977, the (81)Br/(79)Br ratio (0.97291) was determined with a precision ≤0.08‰ relative standard deviation (RSD).

Some aspects of analytical chemistry as applied to water quality assurance techniques for reclaimed water: The potential use of X-ray fluorescence spectrometry for automated on-line fast real-time simultaneous multi-component analysis of inorganic pollutants in reclaimed water

NASA Technical Reports Server (NTRS)

Ling, A. C.; Macpherson, L. H.; Rey, M.

1981-01-01

The potential use of isotopically excited energy dispersive X-ray fluorescence (XRF) spectrometry for automated on line fast real time (5 to 15 minutes) simultaneous multicomponent (up to 20) trace (1 to 10 parts per billion) analysis of inorganic pollutants in reclaimed water was examined. Three anionic elements (chromium 6, arsenic and selenium) were studied. The inherent lack of sensitivity of XRF spectrometry for these elements mandates use of a preconcentration technique and various methods were examined, including: several direct and indirect evaporation methods; ion exchange membranes; selective and nonselective precipitation; and complexation processes. It is shown tha XRF spectrometry itself is well suited for automated on line quality assurance, and can provide a nondestructive (and thus sample storage and repeat analysis capabilities) and particularly convenient analytical method. Further, the use of an isotopically excited energy dispersive unit (50 mCi Cd-109 source) coupled with a suitable preconcentration process can provide sufficient sensitivity to achieve the current mandated minimum levels of detection without the need for high power X-ray generating tubes.

Sulfur Isotope Fractionation in Marine Pore waters from the Offshore Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Yu, T. L.; Chen, N. C.; Wang, B. S.; Lin, L. H.; Yang, T. F.; Chen, Y. G.; Shen, C. C.

2017-12-01

In this study, we selected two marine sediment cores, 474cm C11 and 252cm EN1, with different sulfate reduction rate due to anaerobic oxidation of methane (AOM) in offshore southwestern Taiwan, to clarify the regional sulfur biogeochemical process. Sulfur isotopic composition in pore waters was determined on a multi-collector inductively coupled mass spectrometer, Thermo NEPTUNE, with 2-sigma reproducibility of ±0.18‰. Our results show that correlation between δ34S values of 21.7-40.6‰ and 21.5-54.3‰, and sulfate contents of 7.1-26.6 and 1.2-27.6mM follows a closed system Rayleigh fractionation model above the sulfate-methane transition zone (SMTZ) at depths of 172.5 cm for core C11 and 212.5 cm for core EN1 below sea floor. At the SMTZ, δ34S reaches the summit of 40.6 ‰, followed by a decreasing trend to 16-20‰ at depth of 172.5-470.0 cm for core C11. Our results suggest that sulfur in pore fluids offshore southwestern Taiwan is controlled by multiple processes including microbial sulfate reduction, barite dissolution and clay dehydration.

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‰.

Correlation of morphological and molecular parameters for colon cancer

NASA Astrophysics Data System (ADS)

Yuan, Shuai; Roney, Celeste A.; Li, Qian; Jiang, James; Cable, Alex; Summers, Ronald M.; Chen, Yu

2010-02-01

Colorectal cancer (CRC) is the second leading cause of cancer death in the United States. There is great interest in studying the relationship among microstructures and molecular processes of colorectal cancer during its progression at early stages. In this study, we use our multi-modality optical system that could obtain co-registered optical coherence tomography (OCT) and fluorescence molecular imaging (FMI) images simultaneously to study CRC. The overexpressed carbohydrate α-L-fucose on the surfaces of polyps facilitates the bond of adenomatous polyps with UEA-1 and is used as biomarker. Tissue scattering coefficient derived from OCT axial scan is used as quantitative value of structural information. Both structural images from OCT and molecular images show spatial heterogeneity of tumors. Correlations between those values are analyzed and demonstrate that scattering coefficients are positively correlated with FMI signals in conjugated. In UEA-1 conjugated samples (8 polyps and 8 control regions), the correlation coefficient is ranged from 0.45 to 0.99. These findings indicate that the microstructure of polyps is changed gradually during cancer progression and the change is well correlated with certain molecular process. Our study demonstrated that multi-parametric imaging is able to simultaneously detect morphology and molecular information and it can enable spatially and temporally correlated studies of structure-function relationships during tumor progression.

Mechanisms controlling the silicon isotopic compositions of river waters

NASA Astrophysics Data System (ADS)

Georg, R. B.; Reynolds, B. C.; Frank, M.; Halliday, A. N.

2006-09-01

It has been proposed that silicon (Si) isotopes are fractionated during weathering and biological activity leading to heavy dissolved riverine compositions. In this study, the first seasonal variations of stable isotope compositions of dissolved riverine Si are reported and compared with concomitant changes in water chemistry. Four different rivers in Switzerland were sampled between March 2004 and July 2005. The unique high-resolution multi-collector ICP-MS Nu1700, has been used to provide simultaneous interference-free measurements of 28Si, 29Si and 30Si abundances with an average limiting precision of ± 0.04‰ on δ 30Si. This precision facilitates the clarification of small temporal variations in isotope composition. The average of all the data for the 40 samples is δ 30Si = + 0.84 ± 0.19‰ (± 1σ SD). Despite significant differences in catchment lithologies, biomass, climate, total dissolved solids and weathering fluxes the averaged isotopic composition of dissolved Si in each river is strikingly similar with means of + 0.70 ± 0.12‰ for the Birs,+ 0.95 ± 0.22‰ for the Saane,+ 0.93 ± 0.12‰ for the Ticino and + 0.79 ± 0.19‰ for the Verzasca. However, the δ 30Si undergoes seasonal variations of up to 0.6‰. Comparisons between δ 30Si and physico-chemical parameters, such as the concentration of dissolved Si and other cations, the discharge of the rivers, and the resulting weathering fluxes, permits an understanding of the processes that control the Si budget and the fate of dissolved Si within these rivers. The main mechanism controlling the Si isotope composition of the mountainous Verzasca River appears to be a two component mixing between the seepage of soil/ground waters, with heavier Si produced by clay formation and superficial runoff associated with lighter Si during high discharge events. A biologically-mediated fractionation can be excluded in this particular river system. The other rivers display increasing complexity with increases in the proportion of forested and cultivated landscapes as well as carbonate rocks in the catchment. In these instances it is impossible to resolve the extent of the isotopic fractionation and contributed flux of Si contributed by biological processes as opposed to abiotic weathering. The presence of seasonal variations in Si isotope composition in mountainous rivers provides evidence that extreme changes in climate affect the overall composition of dissolved Si delivered to the oceans. The oceanic Si isotope composition is very sensitive to even small changes in the riverine Si isotope composition and this parameter appears to be more critical than plausible changes in the Si flux. Therefore, concurrent changes in weathering style may need to be considered when using the Si isotopic compositions of diatoms, sponges and radiolaria as paleoproductivity proxies.

Mathematical Model of Nonstationary Separation Processes Proceeding in the Cascade of Gas Centrifuges in the Process of Separation of Multicomponent Isotope Mixtures

NASA Astrophysics Data System (ADS)

Orlov, A. A.; Ushakov, A. A.; Sovach, V. P.

2017-03-01

We have developed and realized on software a mathematical model of the nonstationary separation processes proceeding in the cascades of gas centrifuges in the process of separation of multicomponent isotope mixtures. With the use of this model the parameters of the separation process of germanium isotopes have been calculated. It has been shown that the model adequately describes the nonstationary processes in the cascade and is suitable for calculating their parameters in the process of separation of multicomponent isotope mixtures.

Nucleosynthetic Heterogeneity Controls Vanadium Isotope Variations in Bulk Chondrites

NASA Technical Reports Server (NTRS)

Nielsen, S. G.; Righter, K.; Wu, F.; Owens, J. D.; Prytulak, J.; Burton, K.; Parkinson, I.; Davis, D.

2018-01-01

The vanadium (V) isotope composition of early solar system materials have been hypothesized to be sensitive to high energy irradiation that originated from the young Sun. Vanadium has two isotopes with masses 50 and 51 that have (51)V/(50)V ratio of approximately 410. High energy irradiation produces (50)V from various target isotopes of Ti, Cr and Fe, which would result in light V isotope compositions (expressed as delta (51)V in per mille = 1000 x (((51)V/(50)V(sub sample)/(51)V/(50)V(sub AlfaAesar)) - 1)) relative to a presumably chondritic starting composition. Recently published V isotope data for calcium aluminium inclusions (CAIs) has revealed some very negative values relative to chondrites (by almost -4 per mille) that were indeed interpreted to reflect irradiation processes despite the fact that the studied CAIs all exhibited significant initial abundances of (10)Be, while only a few CAIs displayed light V isotope compositions. It is difficult to relate V isotope variations directly to a singular process because V only possesses two isotopes. Therefore, V isotope variations can principally be produced both mass dependent and independent processes. Mass dependent kinetic stable isotope fractionation is common in CAIs for refractory elements due to partial condensation/evaporation processes. The element strontium (Sr) has an almost identical condensation temperature to V and studies of stable Sr isotope compositions in CAIs reveal both heavy and light values relative to chondrites of several permil. These variations are similar in magnitude to those reported for V isotopes in CAIs, which suggests it is possible that some of the V isotope variation in CAIs could be due to kinetic stable isotope fractionation during condensation/evaporation processes.

Illuminating hydrological processes at the soil-vegetation-atmosphere interface with water stable isotopes

NASA Astrophysics Data System (ADS)

Sprenger, Matthias; Leistert, Hannes; Gimbel, Katharina; Weiler, Markus

2016-09-01

Water stable isotopes (18O and 2H) are widely used as ideal tracers to track water through the soil and to separate evaporation from transpiration. Due to the technical developments in the last two decades, soil water stable isotope data have become easier to collect. Thus, the application of isotope methods in soils is growing rapidly. Studies that make use of soil water stable isotopes often have a multidisciplinary character since an interplay of processes that take place in the vadose zone has to be considered. In this review, we provide an overview of the hydrological processes that alter the soil water stable isotopic composition and present studies utilizing pore water stable isotopes. The processes that are discussed include the water input as precipitation or throughfall, the output as evaporation, transpiration, or recharge, and specific flow and transport processes. Based on the review and supported by additional data and modeling results, we pose a different view on the recently proposed two water world hypothesis. As an alternative to two distinct pools of soil water, where one pool is enriched in heavy isotopes and used by the vegetation and the other pool does not undergo isotopic fractionation and becomes recharge, the water gets successively mixed with newly introduced rainwater during the percolation process. This way, water initially isotopically enriched in the topsoil loses the fractionation signal with increasing infiltration depth, leading to unfractionated isotopic signals in the groundwater.

Development of a sensitive setup for laser spectroscopy studies of very exotic calcium isotopes

NASA Astrophysics Data System (ADS)

Garcia Ruiz, R. F.; Gorges, C.; Bissell, M.; Blaum, K.; Gins, W.; Heylen, H.; Koenig, K.; Kaufmann, S.; Kowalska, M.; Krämer, J.; Lievens, P.; Malbrunot-Ettenauer, S.; Neugart, R.; Neyens, G.; Nörtershäuser, W.; Yordanov, D. T.; Yang, X. F.

2017-04-01

An experimental setup for sensitive high-resolution measurements of hyperfine structure spectra of exotic calcium isotopes has been developed and commissioned at the COLLAPS beam line at ISOLDE, CERN. The technique is based on the radioactive detection of decaying isotopes after optical pumping and state selective neutralization (ROC) (Vermeeren et al 1992 Phys. Rev. Lett. 68 1679). The improvements and developments necessary to extend the applicability of the experimental technique to calcium isotopes produced at rates as low as few ions s-1 are discussed. Numerical calculations of laser-ion interaction and ion-beam simulations were explored to obtain the optimum performance of the experimental setup. Among the implemented features are a multi-step optical pumping region for sensitive measurements of isotopes with hyperfine splitting, a high-voltage platform for adequate control of low-energy ion beams and simultaneous β-detection of neutralized and remaining ions. The commissioning of the experimental setup, and the first online results on neutron-rich calcium isotopes are presented.

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.

Isotopic fractionation of nitrogen and carbon in Paleoarchean cherts from Pilbara craton, Western Australia: Origin of 15N-depleted nitrogen

NASA Astrophysics Data System (ADS)

Pinti, Daniele L.; Hashizume, Ko; Sugihara, Akiyo; Massault, Marc; Philippot, Pascal

2009-07-01

Nitrogen and carbon isotopic compositions, together with mineralogy and trace element geochemistry, were studied in a few kerogen-rich Paleoarchean cherts, a barite and a dolomitic stromatolite belonging to the eastern (Dixon Island Formation) and western (Dresser and Strelley Pool Chert Formations; North Pole Dome and Marble Bar) terranes of Pilbara Craton, Western Australia. The aim of the study was to search for 15N-depleted isotopic signatures, often found in kerogens of this period, and explain the origin of these anomalies. Trace elements suggest silica precipitation by hydrothermal fluids as the main process of chert formation with a contamination from volcanoclastic detritus. This is supported by the occurrence of hydrothermal-derived minerals in the studied samples indicating precipitation temperatures up to 350 °C. Only a dolomitic stromatolite from Strelley Pool shows a superchondritic Y/Ho ratio of 72 and a positive Eu/Eu * anomaly of 1.8, characteristic of chemical precipitates from the Archean seawater. The bulk δ 13C vs. δ 15N values measured in the cherts show a roughly positive co-variation, except for one sample from the North Pole (PI-85-00). The progressive enrichment in 15N and 13C from a pristine source having δ 13C ⩽ -36‰ and δ 15N ⩽ -4‰ is correlated with a progressive depletion in N content and to variations in Ba/La and Co/As ratios. These trends have been interpreted as a progressive hydrothermal alteration of the cherts by metamorphic fluids. Isotopic exchange at 350 °C between NH 4+(rock) and N 2(fluid) may explain the isotopic and elemental composition of N in the studied cherts. However, we need to assume isotopic exchange at 350 °C between carbonate C and graphite to explain the large 13C enrichment recorded. Only sample PI-85-00 shows a large N loss (90%) with a positive δ 15N value (+11‰), while C (up to 120 ppm and δ 13C -38‰) seems to be unaffected. This pattern has been interpreted as the result of devolatilization and alteration (oxidation) of graphite by low-temperature fluids. The 15N- 13C-depleted pristine source has δ 15N values from -7‰ to -4‰ and 40Ar/ 36Ar ratios from 30,000 to 60,000, compatible with an inorganic mantle N source, although the elemental abundance ratios N/C and 40Ar/C are not exactly the same with the mantle source. The component alternatively could be explained by elemental fractionation from metabolic activity of chemolithoautotrophs and methanogens at the proximity to the hydrothermal vents. However, ambiguities between mantle vs organic sources of N subsist and need further experimental work to be fully elucidated.

Development of a Germanium Small-Animal SPECT System

NASA Astrophysics Data System (ADS)

Johnson, Lindsay C.; Ovchinnikov, Oleg; Shokouhi, Sepideh; Peterson, Todd E.

2015-10-01

Advances in fabrication techniques, electronics, and mechanical cooling systems have given rise to germanium detectors suitable for biomedical imaging. We are developing a small-animal SPECT system that uses a double-sided Ge strip detector. The detector's excellent energy resolution may help to reduce scatter and simplify processing of multi-isotope imaging, while its ability to measure depth of interaction has the potential to mitigate parallax error in pinhole imaging. The detector's energy resolution is <; 1% FWHM at 140 keV and its spatial resolution is approximately 1.5 mm FWHM. The prototype system described has a single-pinhole collimator with a 1-mm diameter and a 70-degree opening angle with a focal length variable between 4.5 and 9 cm. Phantom images from the gantry-mounted system are presented, including the NEMA NU-2008 phantom and a hot-rod phantom. Additionally, the benefit of energy resolution is demonstrated by imaging a dual-isotope phantom with 99mTc and 123I without cross-talk correction.

Towards an optimal adaptation of exposure to NOAA assessment methodology in Multi-Source Industrial Scenarios (MSIS): the challenges and the decision-making process

NASA Astrophysics Data System (ADS)

López de Ipiña, JM; Vaquero, C.; Gutierrez-Cañas, C.

2017-06-01

It is expected a progressive increase of the industrial processes that manufacture of intermediate (iNEPs) and end products incorporating ENMs (eNEPs) to bring about improved properties. Therefore, the assessment of occupational exposure to airborne NOAA will migrate, from the simple and well-controlled exposure scenarios in research laboratories and ENMs production plants using innovative production technologies, to much more complex exposure scenarios located around processes of manufacture of eNEPs that, in many cases, will be modified conventional production processes. Here will be discussed some of the typical challenging situations in the process of risk assessment of inhalation exposure to NOAA in Multi-Source Industrial Scenarios (MSIS), from the basis of the lessons learned when confronted to those scenarios in the frame of some European and Spanish research projects.

Spreaders and Sponges define metastasis in lung cancer: A Markov chain Monte Carlo Mathematical Model

PubMed Central

Newton, Paul K.; Mason, Jeremy; Bethel, Kelly; Bazhenova, Lyudmila; Nieva, Jorge; Norton, Larry; Kuhn, Peter

2013-01-01

The classic view of metastatic cancer progression is that it is a unidirectional process initiated at the primary tumor site, progressing to variably distant metastatic sites in a fairly predictable, though not perfectly understood, fashion. A Markov chain Monte Carlo mathematical approach can determine a pathway diagram that classifies metastatic tumors as ‘spreaders’ or ‘sponges’ and orders the timescales of progression from site to site. In light of recent experimental evidence highlighting the potential significance of self-seeding of primary tumors, we use a Markov chain Monte Carlo (MCMC) approach, based on large autopsy data sets, to quantify the stochastic, systemic, and often multi-directional aspects of cancer progression. We quantify three types of multi-directional mechanisms of progression: (i) self-seeding of the primary tumor; (ii) re-seeding of the primary tumor from a metastatic site (primary re-seeding); and (iii) re-seeding of metastatic tumors (metastasis re-seeding). The model shows that the combined characteristics of the primary and the first metastatic site to which it spreads largely determine the future pathways and timescales of systemic disease. For lung cancer, the main ‘spreaders’ of systemic disease are the adrenal gland and kidney, whereas the main ‘sponges’ are regional lymph nodes, liver, and bone. Lung is a significant self-seeder, although it is a ‘sponge’ site with respect to progression characteristics. PMID:23447576

Following isotopes in pulse-chase enriched aspen seedlings

NASA Astrophysics Data System (ADS)

Norris, C. E.; Wasylishen, R. E.; Landhäusser, S.; Quideau, S. A.

2011-12-01

One method to quantitatively trace biogeochemical fluxes through ecosystems, such as organic matter decomposition, is to use plant material enriched with stable isotopes. However, as plant macromolecules are known to vary in their rate of formation and decomposition, both the enrichment levels and the location of enrichment within the plant material should be characterized prior to decomposition and tracing studies. Aspen (Populus tremuloides Michx.) is a common tree species with a diverse organic matter chemical structure found in the western Canadian boreal forest. This study used a multi pulse and multi chase enrichment of stable isotopes (15N and 13C) on aspen seedlings to determine the seedling enrichment, isotope movement among plant tissues and translocation of isotopes within plant macromolecules e.g., carbohydrates and lignin. As expected, all tissues experienced increased enrichment with multiple pulses. An initial enrichment with 13C was observed in the leaves followed by translocation to the stems and roots while the 15N moved upward from the roots to leaves. The macromolecular chemistry of the organic carbon was further characterized using 13C solid state nuclear magnetic resonance spectroscopy. After the initial two hour chase period enrichment of the O-alkyl type (carbohydrate) carbon within the leaves was identified, followed by redistribution to more complex carbon compounds after the one week chase period. Root and stem tissues did not show the same pattern. Rather, changes in 13C enrichment were observed in shifting ethyl and methyl alkyl (lipid) carbon peak intensities for the stem samples while roots did not preferentially allocate 13C to a specific macromolecule. These results confirm that stable isotope enrichment of plants was non-uniform across macromolecules and tissue types. Enrichment of aspen seedlings was therefore dependant on the pulse-chase sequence used.

Intrapopulation variability shaping isotope discrimination and turnover: experimental evidence in arctic foxes.

PubMed

Lecomte, Nicolas; Ahlstrøm, Oystein; Ehrich, Dorothée; Fuglei, Eva; Ims, Rolf A; Yoccoz, Nigel G

2011-01-01

Tissue-specific stable isotope signatures can provide insights into the trophic ecology of consumers and their roles in food webs. Two parameters are central for making valid inferences based on stable isotopes, isotopic discrimination (difference in isotopic ratio between consumer and its diet) and turnover time (renewal process of molecules in a given tissue usually measured when half of the tissue composition has changed). We investigated simultaneously the effects of age, sex, and diet types on the variation of discrimination and half-life in nitrogen and carbon stable isotopes (δ¹⁵N and δ¹³C, respectively) in five tissues (blood cells, plasma, muscle, liver, nail, and hair) of a top predator, the arctic fox Vulpes lagopus. We fed 40 farmed foxes (equal numbers of adults and yearlings of both sexes) with diet capturing the range of resources used by their wild counterparts. We found that, for a single species, six tissues, and three diet types, the range of discrimination values can be almost as large as what is known at the scale of the whole mammalian or avian class. Discrimination varied depending on sex, age, tissue, and diet types, ranging from 0.3‰ to 5.3‰ (mean  = 2.6‰) for δ¹⁵N and from 0.2‰ to 2.9‰ (mean  = 0.9‰) for δ¹³C. We also found an impact of population structure on δ¹⁵N half-life in blood cells. Varying across individuals, δ¹⁵N half-life in plasma (6 to 10 days) was also shorter than for δ¹³C (14 to 22 days), though δ¹⁵N and δ¹³C half-lives are usually considered as equal. Overall, our multi-factorial experiment revealed that at least six levels of isotopic variations could co-occur in the same population. Our experimental analysis provides a framework for quantifying multiple sources of variation in isotopic discrimination and half-life that needs to be taken into account when designing and analysing ecological field studies.

Reverse weathering in marine sediments and the geochemical cycle of potassium in seawater: Insights from the K isotopic composition (41K/39K) of deep-sea pore-fluids

USGS Publications Warehouse

Santiago Ramos, Danielle P.; Morgan, Leah; Lloyd, Nicholas S.; Higgins, John A.

2018-01-01

In situ Al-silicate formation, also known as “reverse weathering,” is an important sink of many of the major and minor cations in seawater (e.g. Mg, K, and Li). However, the importance of this sink in global geochemical cycles and isotopic budgets of these elements remains poorly constrained. Here, we report on the potassium isotopic composition (41">41K/39">39K) of deep-sea sediment pore-fluids from four (Integrated) Ocean Drilling Program sites (1052, U1378, U1395 and U1403) to characterize potassium isotopic fractionation associated with the formation of authigenic Al-silicate minerals in marine sediments and its role in elevating the 41">41K/39">39K of seawater relative to bulk silicate Earth. Isotopic ratios are obtained by high-resolution multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in cold plasma conditions with a long-term external reproducibility of ca. 0.17‰. We find that, although all sites are characterized by pore-fluid K concentrations that decline with increasing depth, their K isotopic profiles vary systematically from site-to-site; at sites characterized by rapid sedimentation rates, pore-fluid profiles of 41">41K/39">39K are relatively invariant whereas at sites characterized by slow sedimentation rates, 41">41K/39">39K declines with depth by up to 1.8‰. Results from 1-D diffusion-advection-reaction models suggest that these differences may result from a complex interplay between sedimentation rate and fractionation of K isotopes during diffusion, Al-silicate authigenesis, and ion exchange. Model simulations suggest fractionation factors between 0.9980 and 1.0000 for reverse weathering reactions in deep-sea sediments. Although deep-sea sites do not constitute major sinks of K in seawater, some of the processes responsible for K isotopic fractionation at these sites (diffusion and Al-silicate authigenesis) likely play a role in determining the 41">41K/39">39K of seawater.

Nuclear reactions in shock wave front during supernova events

NASA Technical Reports Server (NTRS)

Lavrukhina, A. K.

1985-01-01

The new unique isotopic anomalous coponent of Xe(XeX) was found in the carbonaceous chondrites. It is enriched in light shielded isotopes (124Xe and 126Xe) and in heavy nonshielded isotopes (134Xe and 136Xe. All characteristics of Xe-X can be explained by a model of nucleosynthesis of the Xe isotopes in shock wave front passed through the He envelope during supernova events. The light isotopes are created by p process and the heavy isotopes are created by n process (slow r process). They were captured with high temperature carbon grains condensing by supernova shock waves.

Chemical and oxygen isotopic properties of ordinary chondrites (H5, L6) from Oman: Signs of isotopic equilibrium during thermal metamorphism

NASA Astrophysics Data System (ADS)

Ali, Arshad; Nasir, Sobhi J.; Jabeen, Iffat; Al Rawas, Ahmed; Banerjee, Neil R.; Osinski, Gordon R.

2017-10-01

Mean bulk chemical data of recently found H5 and L6 ordinary chondrites from the deserts of Oman generally reflect isochemical features which are consistent with the progressive thermal metamorphism of a common, unequilibrated starting material. Relative differences in abundances range from 0.5-10% in REE (Eu = 14%), 6-13% in siderophile elements (Co = 48%), and >10% in lithophile elements (exceptions are Ba, Sr, Zr, Hf, U = >30%) between H5 and L6 groups. These differences may have accounted for variable temperature conditions during metamorphism on their parent bodies. The CI/Mg-normalized mean abundances of refractory lithophile elements (Al, Ca, Sm, Yb, Lu, V) show no resolvable differences between H5 and L6 suggesting that both groups have experienced the same fractionation. The REE diagram shows subtle enrichment in LREE with a flat HREE pattern. Furthermore, overall mean REE abundances are 0.6 × CI with enriched La abundance ( 0.9 × CI) in both groups. Precise oxygen isotope compositions demonstrate the attainment of isotopic equilibrium by progressive thermal metamorphism following a mass-dependent isotope fractionation trend. Both groups show a slope-1/2 line on a three-isotope plot with subtle negative deviation in Δ17O associated with δ18O enrichment relative to δ17O. These deviations are interpreted as the result of liberation of water from phyllosilicates and evaporation of a fraction of the water during thermal metamorphism. The resultant isotope fractionations caused by the water loss are analogous to those occurring between silicate melt and gas phase during CAI and chondrule formation in chondrites and are controlled by cooling rates and exchange efficiency.

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

PubMed

Peck, William H; Tubman, Stephanie C

2010-02-24

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

[Research progress on food sources and food web structure of wetlands based on stable isotopes].

PubMed

Chen, Zhan Yan; Wu, Hai Tao; Wang, Yun Biao; Lyu, Xian Guo

2017-07-18

The trophic dynamics of wetland organisms is the basis of assessing wetland structure and function. Stable isotopes of carbon and nitrogen have been widely applied to identify trophic relationships in food source, food composition and food web transport in wetland ecosystem studies. This paper provided an overall review about the current methodology of isotope mixing model and trophic level in wetland ecosystems, and discussed the standards of trophic fractionation and baseline. Moreover, we characterized the typical food sources and isotopic compositions of wetland ecosystems, summarized the food sources in different trophic levels of herbivores, omnivores and carnivores based on stable isotopic analyses. We also discussed the limitations of stable isotopes in tra-cing food sources and in constructing food webs. Based on the current results, development trends and upcoming requirements, future studies should focus on sample treatment, conservation and trophic enrichment measurement in the wetland food web, as well as on combing a variety of methodologies including traditional stomach stuffing, molecular markers, and multiple isotopes.

Iron and nickel isotope compositions of presolar silicon carbide grains from supernovae

NASA Astrophysics Data System (ADS)

Kodolányi, János; Stephan, Thomas; Trappitsch, Reto; Hoppe, Peter; Pignatari, Marco; Davis, Andrew M.; Pellin, Michael J.

2018-01-01

We report the carbon, silicon, iron, and nickel isotope compositions of twenty-five presolar SiC grains of mostly supernova (SN) origin. The iron and nickel isotope compositions were measured with the new Chicago Instrument for Laser Ionization, CHILI, which allows the analysis of all iron and nickel isotopes without the isobaric interferences that plagued previous measurements with the NanoSIMS. Despite terrestrial iron and nickel contamination, significant isotopic anomalies in 54Fe/56Fe, 57Fe/56Fe, 60Ni/58Ni, 61Ni/58Ni, 62Ni/58Ni, and 64Ni/58Ni were detected in nine SN grains (of type X). Combined multi-isotope data of three grains with the largest nickel isotope anomalies (>100‰ or <-100‰ in at least one isotope ratio, when expressed as deviation from the solar value) are compared with the predictions of two SN models, one with and one without hydrogen ingestion in the He shell prior to SN explosion. One grain's carbon-silicon-iron-nickel isotope composition is consistent with the prediction of the model without hydrogen ingestion, whereas the other two grains' isotope anomalies could not be reproduced using either SN models. The discrepancies between the measured isotope compositions and model predictions may indicate element fractionation in the SN ejecta prior to or during grain condensation, and reiterate the need for three-dimensional SN models.

Rare Isotopes in Cosmic Explosions and Accelerators on Earth

ScienceCinema

Schatz, Hendrick

2017-12-28

Rare isotopes are nature’s stepping stones to produce the heavy elements, and they are produced in large quantities in stellar explosions. Despite their fleeting existence, they shape the composition of the universe and the observable features of stellar explosions. The challenge for nuclear science is to produce and study the very same rare isotopes so as to understand the origin of the elements and a range of astronomical observations. I will review the progress that has been made to date in astronomy and nuclear physics, and the prospects of finally addressing many of the outstanding issues with the future Facility for Rare Isotope Beams (FRIB), which DOE will build at Michigan State University.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2014-08-01

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

The nitrogen isotopic ratio of HC3N towards the L1544 prestellar core

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Faure, A.; Vastel, C.; Magalhaes, V.; Lefloch, B.; Bachiller, R.

2018-06-01

The origin of the heavily fractionated reservoir of nitrogen in comets remains an issue in the theory of their formation and hence of the solar system. Whether the fractionated reservoir traced by comets is inherited from the interstellar cloud or is the product of processes taking place in the protostar, or in the protoplanetary disk, remains unclear. So far, observations of nitrogen isotopic ratios in protostars or prestellar cores have not securely identified such a fractionated reservoir owing to the intrinsic difficulty of direct isotopic ratios measurements. In this article, we report the detection of 5 rotational lines of HC3N, including the weaker components of the hyperfine multiplets, and two rotational lines of its 15N isotopologue, towards the L1544 prestellar core. Based on a MCMC/non-LTE multi-line analysis at the hyperfine level, we derive the column densities of HC3N (8.0 ± 0.4 × 1013cm-2) and HC_3^{15}N (2.0 ± 0.4 × 1011cm-2) and derive an isotopic ratio of 400±20(1σ). This value suggests that HC3N is slightly depleted in 15N in L1544 with respect to the elemental 14N/15N ratio of ≈330 in the present-day local interstellar medium. Our study also stresses the need for radiative calculations at the hyperfine level. Finally, the comparison of the derived ratio with those obtained in CN and HCN in the same core seems to favor CN+C2H2 as the dominant formation route to HC3N. However, uncertainties in the isotopic ratios preclude definitive conclusions.

Data Reduction of Laser Ablation Split-Stream (LASS) Analyses Using Newly Developed Features Within Iolite: With Applications to Lu-Hf + U-Pb in Detrital Zircon and Sm-Nd +U-Pb in Igneous Monazite

NASA Astrophysics Data System (ADS)

Fisher, Christopher M.; Paton, Chad; Pearson, D. Graham; Sarkar, Chiranjeeb; Luo, Yan; Tersmette, Daniel B.; Chacko, Thomas

2017-12-01

A robust platform to view and integrate multiple data sets collected simultaneously is required to realize the utility and potential of the Laser Ablation Split-Stream (LASS) method. This capability, until now, has been unavailable and practitioners have had to laboriously process each data set separately, making it challenging to take full advantage of the benefits of LASS. We describe a new program for handling multiple mass spectrometric data sets collected simultaneously, designed specifically for the LASS technique, by which a laser aerosol is been split into two or more separate "streams" to be measured on separate mass spectrometers. New features within Iolite (https://iolite-software.com) enable the capability of loading, synchronizing, viewing, and reducing two or more data sets acquired simultaneously, as multiple DRSs (data reduction schemes) can be run concurrently. While this version of Iolite accommodates any combination of simultaneously collected mass spectrometer data, we demonstrate the utility using case studies where U-Pb and Lu-Hf isotope composition of zircon, and U-Pb and Sm-Nd isotope composition of monazite were analyzed simultaneously, in crystals showing complex isotopic zonation. These studies demonstrate the importance of being able to view and integrate simultaneously acquired data sets, especially for samples with complicated zoning and decoupled isotope systematics, in order to extract accurate and geologically meaningful isotopic and compositional data. This contribution provides instructions and examples for handling simultaneously collected laser ablation data. An instructional video is also provided. The updated Iolite software will help to fully develop the applications of both LASS and multi-instrument mass spectrometric measurement capabilities.

A multi-isotopic approach to investigate the influence of land use on nitrate removal in a highly saline lake-aquifer system.

PubMed

Valiente, N; Carrey, R; Otero, N; Soler, A; Sanz, D; Muñoz-Martín, A; Jirsa, F; Wanek, W; Gómez-Alday, J J

2018-08-01

Endorheic or closed drainage basins in arid and semi-arid regions are vulnerable to pollution. Nonetheless, in the freshwater-saltwater interface of endorheic saline lakes, oxidation-reduction (redox) reactions can attenuate pollutants such as nitrate (NO 3 - ). This study traces the ways of nitrogen (N) removal in the Pétrola lake-aquifer system (central Spain), an endorheic basin contaminated with NO 3 - (up to 99.2mg/L in groundwater). This basin was declared vulnerable to NO 3 - pollution in 1998 due to the high anthropogenic pressures (mainly agriculture and wastewaters). Hydrochemical, multi-isotopic (δ 18 O NO3 , δ 15 N NO3 , δ 13 C DIC , δ 18 O H2O , and δ 2 H H2O ) and geophysical techniques (electrical resistivity tomography) were applied to identify the main redox processes at the freshwater-saltwater interface. The results showed that the geometry of this interface is influenced by land use, causing spatial variability of nitrogen biogeochemical processes over the basin. In the underlying aquifer, NO 3 - showed an average concentration of 38.5mg/L (n=73) and was mainly derived from agricultural inputs. Natural attenuation of NO 3 - was observed in dryland farming areas (up to 72%) and in irrigation areas (up to 66%). In the Pétrola Lake, mineralization and organic matter degradation in lake sediment play an important role in NO 3 - reduction. Our findings are a major step forward in understanding freshwater-saltwater interfaces as reactive zones for NO 3 - attenuation. We further emphasize the importance of including a land use perspective when studying water quality-environmental relationships in hydrogeological systems dominated by density-driven circulation. Copyright © 2018 Elsevier B.V. All rights reserved.

The Origin of 87Sr/86Sr in Cold Springs and Travertines of the Franciscan Complex near Cazadero, California

NASA Astrophysics Data System (ADS)

Marks, N.; Schiffman, P.; Yin, Q.; Zierenberg, R.

2005-12-01

Ultrabasic springs within the Franciscan Complex of the California Coast Range have been intensely investigated by geochemists and geobiologists. Springs located in Sonoma County in an area historically known as The Cedars are of particular interest to scientists exploring Martian analogues (Johnson et al. 2004) or investigating serpentinization processes (Barnes and O'Neil, 1969; Barnes et al. 1972). Laser ablation and solution phase multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) were used to obtain 87Sr/86Sr isotope ratios in fluid, travertine and serpentinite samples collected at the Cedars. 87Sr/86Sr isotopic ratios in the serpentinizing springs range from 0.70926 to 0.70955; the Mg2+-HCO3- type stream water has an isotopic ratio of 0.70848. The 87Sr/86Sr ratio in the travertines ranges from 0.70931 to 0.70966. The mean 87Sr/86Sr ratio of the travertine (0.7094) is far more radiogenic than typical mantle values of 0.703 to 0.705, indicating that the peridotite is an unlikely source of the radiogenic Sr. Similarly, the measured ratio is much higher than the expected Sr isotope ratio of seawater that might be trapped in Jurassic Franciscan Sediments or oceanic crust. Strontium leached from Franciscan sediments themselves should reflect a Sierran or Klamath source with expected values in the range of 0.705 to 0.706. Indeed the measured isotope ratios even exceed modern seawater values. The observed radiogenic values suggest the presence of older, potassium (and rubidium)-rich rocks within the fluid flow path. Alternatively, the presence of clay minerals that readily substitute Sr for Ca may well account for the radiogenic strontium signal. It is possible that the serpentinization observed at The Cedars initiated along a ridge flank and the Sr isotopic chemistry reflects the site of initiation. The radiogenic strontium in these springs may result from fluid interaction with seafloor sediments deposited along the flank of a slow spreading ridge. If this is the case, it may be possible to use 87Sr/86Sr to determine the location of serpentinization initiation (Gruau et al, 1998). Such a revelation might provide insight into the geochemical processes associated with mid-ocean ridge flank serpentinization at sites like Lost City (Kelley et al., 2005). The implications of this correlation could provide information about the preservation of geochemical systems through obduction of ophiolitic sequences and provide insights into ridge flank hydrothermal and serpentinizing processes.

A drift correction optimization technique for the reduction of the inter-measurement dispersion of isotope ratios measured using a multi-collector plasma mass spectrometer

NASA Astrophysics Data System (ADS)

Doherty, W.; Lightfoot, P. C.; Ames, D. E.

2014-08-01

The effects of polynomial interpolation and internal standardization drift corrections on the inter-measurement dispersion (statistical) of isotope ratios measured with a multi-collector plasma mass spectrometer were investigated using the (analyte, internal standard) isotope systems of (Ni, Cu), (Cu, Ni), (Zn, Cu), (Zn, Ga), (Sm, Eu), (Hf, Re) and (Pb, Tl). The performance of five different correction factors was compared using a (statistical) range based merit function ωm which measures the accuracy and inter-measurement range of the instrument calibration. The frequency distribution of optimal correction factors over two hundred data sets uniformly favored three particular correction factors while the remaining two correction factors accounted for a small but still significant contribution to the reduction of the inter-measurement dispersion. Application of the merit function is demonstrated using the detection of Cu and Ni isotopic fractionation in laboratory and geologic-scale chemical reactor systems. Solvent extraction (diphenylthiocarbazone (Cu, Pb) and dimethylglyoxime (Ni) was used to either isotopically fractionate the metal during extraction using the method of competition or to isolate the Cu and Ni from the sample (sulfides and associated silicates). In the best case, differences in isotopic composition of ± 3 in the fifth significant figure could be routinely and reliably detected for Cu65/63 and Ni61/62. One of the internal standardization drift correction factors uses a least squares estimator to obtain a linear functional relationship between the measured analyte and internal standard isotope ratios. Graphical analysis demonstrates that the points on these graphs are defined by highly non-linear parametric curves and not two linearly correlated quantities which is the usual interpretation of these graphs. The success of this particular internal standardization correction factor was found in some cases to be due to a fortuitous, scale dependent, parametric curve effect.

Separation of Isotopes by Electromigration in Fused Salts; SEPARATION DES ISOTOPES PAR ELECTROMIGRATION EN SELS FONDUS (in French)

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

Menes, F.

1961-12-01

A process is given for the separation of isotopes by reflux electromigration of fused salts. The process is carried out in a countercurrent manner on a fused mixture of a salt containing the isotopic cations with a salt having the same anion and a cation with a mobility as near as possible to that of the isotopic cations. An electrolytic cell for carrying out the process is described. Examples are presented of the process in which lithium-6 and lithium-7 are separated in a LiBr-KBr mixture, and calcium isotopes are separated in CaBr/sub 2/-KBr and CaBr/sub 2/- LiBr systems. (N.W.R.)

Identifying nitrogen sources to thermal tide pools in Kapoho, Hawai'i, U.S.A, using a multi-stable isotope approach.

PubMed

Wiegner, Tracy N; Mokiao-Lee, Ambyr U; Johnson, Erik E

2016-02-15

Nitrogen (N) enrichment often results in coastal eutrophication, even in remote areas like Hawai'i. Therefore, determining N sources to coastal waters is important for their management. This study identified N sources to tide pools in Kapoho, Hawai'i, and determined their relative importance using three stable isotopes (δ(15)N, δ(18)O, δ(11)B). Surface waters and macroalgal tissues were collected along 100-m onshore-offshore transects in areas of high groundwater input for three months at low tide. Water samples from possible N sources were also collected. Mixing model output, along with macroalgal δ(15)N values, indicated that agriculture soil (34%) was the largest anthropogenic N source followed by sewage (27%). These findings suggest that more effective fertilizer application techniques and upgrading sewage treatment systems can minimize N leaching into groundwater. Overall, our multi-stable isotope approach for identifying N sources was successful and may be useful in other coastal waters. Copyright © 2015 Elsevier Ltd. All rights reserved.

Seaching for a Silver Lining: Using Pb Isotopes to Constrain the Source of Argentiferous Galena at La Isabela

NASA Astrophysics Data System (ADS)

Thibodeau, A. M.; Killick, D. J.; Ruiz, J.; Chesley, J. T.; Baker, M.

2005-12-01

This study investigates the smelting and refining of argentiferous galena at La Isabela, Dominican Republic (1493-1498), the town founded by Columbus on his second voyage to the Americas. Archaeologists recovered approximately 100 kilograms of galena and 200 kilograms of metallurgical slag near the remains of a crude furnace unearthed at the site (Deagan and Cruxent 2002). The purpose of this study was to determine if these remains are evidence that members of Columbus's fleet prospected for silver during his second expedition. Samples of ore and slag were examined as metallographic polished sections, and petrographic thin sections by optical and scanning electron microscopes. The composition of the ore and slag allows us to infer these ores were processed in a two-stage procedure to produce silver metal and a lead silicate slag. Electron microprobe analysis of galena indicates highly variable but low Ag content (50 ppm), which may account for the fact some of the ore was left unprocessed. Lead isotope analysis by multi-collector ICP-MS indicates that the galena likely came from a single source and was not mined within the Caribbean. Instead, the isotopic signature of these ores is consistent with an Old World source, possibly in the Linares-La Carolina Pb-Zn vein field of southwestern Spain.

Transport, biodegradation and isotopic fractionation of chlorinated ethenes: modeling and parameter estimation methods

NASA Astrophysics Data System (ADS)

Béranger, Sandra C.; Sleep, Brent E.; Lollar, Barbara Sherwood; Monteagudo, Fernando Perez

2005-01-01

An analytical, one-dimensional, multi-species, reactive transport model for simulating the concentrations and isotopic signatures of tetrachloroethylene (PCE) and its daughter products was developed. The simulation model was coupled to a genetic algorithm (GA) combined with a gradient-based (GB) method to estimate the first order decay coefficients and enrichment factors. In testing with synthetic data, the hybrid GA-GB method reduced the computational requirements for parameter estimation by a factor as great as 300. The isotopic signature profiles were observed to be more sensitive than the concentration profiles to estimates of both the first order decay constants and enrichment factors. Including isotopic data for parameter estimation significantly increased the GA convergence rate and slightly improved the accuracy of estimation of first order decay constants.

Archival processes of the water stable isotope signal in East Antarctic ice cores

NASA Astrophysics Data System (ADS)

Casado, Mathieu; Landais, Amaelle; Picard, Ghislain; Münch, Thomas; Laepple, Thomas; Stenni, Barbara; Dreossi, Giuliano; Ekaykin, Alexey; Arnaud, Laurent; Genthon, Christophe; Touzeau, Alexandra; Masson-Delmotte, Valerie; Jouzel, Jean

2018-05-01

The oldest ice core records are obtained from the East Antarctic Plateau. Water isotopes are key proxies to reconstructing past climatic conditions over the ice sheet and at the evaporation source. The accuracy of climate reconstructions depends on knowledge of all processes affecting water vapour, precipitation and snow isotopic compositions. Fractionation processes are well understood and can be integrated in trajectory-based Rayleigh distillation and isotope-enabled climate models. However, a quantitative understanding of processes potentially altering snow isotopic composition after deposition is still missing. In low-accumulation sites, such as those found in East Antarctica, these poorly constrained processes are likely to play a significant role and limit the interpretability of an ice core's isotopic composition. By combining observations of isotopic composition in vapour, precipitation, surface snow and buried snow from Dome C, a deep ice core site on the East Antarctic Plateau, we found indications of a seasonal impact of metamorphism on the surface snow isotopic signal when compared to the initial precipitation. Particularly in summer, exchanges of water molecules between vapour and snow are driven by the diurnal sublimation-condensation cycles. Overall, we observe in between precipitation events modification of the surface snow isotopic composition. Using high-resolution water isotopic composition profiles from snow pits at five Antarctic sites with different accumulation rates, we identified common patterns which cannot be attributed to the seasonal variability of precipitation. These differences in the precipitation, surface snow and buried snow isotopic composition provide evidence of post-deposition processes affecting ice core records in low-accumulation areas.

Mathematical modeling of filling of gas centrifuge cascade for nickel isotope separation by various feed flow rate

NASA Astrophysics Data System (ADS)

Ushakov, Anton; Orlov, Alexey; Sovach, Victor P.

2018-03-01

This article presents the results of research filling of gas centrifuge cascade for separation of the multicomponent isotope mixture with process gas by various feed flow rate. It has been used mathematical model of the nonstationary hydraulic and separation processes occurring in the gas centrifuge cascade. The research object is definition of the regularity transient of nickel isotopes into cascade during filling of the cascade. It is shown that isotope concentrations into cascade stages after its filling depend on variable parameters and are not equal to its concentration on initial isotope mixture (or feed flow of cascade). This assumption is used earlier any researchers for modeling such nonstationary process as set of steady-state concentration of isotopes into cascade. Article shows physical laws of isotope distribution into cascade stage after its filling. It's shown that varying each parameters of cascade (feed flow rate, feed stage number or cascade stage number) it is possible to change isotope concentration on output cascade flows (light or heavy fraction) for reduction of duration of further process to set of steady-state concentration of isotopes into cascade.

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine).

PubMed

Vystavna, Yuliya; Diadin, Dmytro; Huneau, Frédéric

2018-05-01

Stable isotopes of hydrogen ( 2 H) and oxygen ( 18 O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November-March and an enrichment in April-October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.

Scaling GDL for Multi-cores to Process Planck HFI Beams Monte Carlo on HPC

NASA Astrophysics Data System (ADS)

Coulais, A.; Schellens, M.; Duvert, G.; Park, J.; Arabas, S.; Erard, S.; Roudier, G.; Hivon, E.; Mottet, S.; Laurent, B.; Pinter, M.; Kasradze, N.; Ayad, M.

2014-05-01

After reviewing the majors progress done in GDL -now in 0.9.4- on performance and plotting capabilities since ADASS XXI paper (Coulais et al. 2012), we detail how a large code for Planck HFI beams Monte Carlo was successfully transposed from IDL to GDL on HPC.

Optoelectronic Materials Center

DTIC Science & Technology

1991-06-11

surface - emitting GaAs/AIGaAs vertical - cavity laser (TJ- VCSEL ) incorporating wavelength-resonant...multi-quantum well, vertical cavity surface - emitted laser . This structure consists entirely of undoped epilayers, thus simplifying the problems of... cavity surface - emitting lasers ( VCSELs ) for doubling and for parallel optical data processing. Progress - GaAIAs/GaAs and InGaAs/GaAs RPG- VCSEL

Hydrochemical assessment of freshening saline groundwater using multiple end-members mixing modeling: A study of Red River delta aquifer, Vietnam

NASA Astrophysics Data System (ADS)

Kim, Ji-Hyun; Kim, Kyoung-Ho; Thao, Nguyen Thi; Batsaikhan, Bayartungalag; Yun, Seong-Taek

2017-06-01

In this study, we evaluated the water quality status (especially, salinity problems) and hydrogeochemical processes of an alluvial aquifer in a floodplain of the Red River delta, Vietnam, based on the hydrochemical and isotopic data of groundwater samples (n = 23) from the Kien Xuong district of the Thai Binh province. Following the historical inundation by paleo-seawater during coastal progradation, the aquifer has been undergone progressive freshening and land reclamation to enable settlements and farming. The hydrochemical data of water samples showed a broad hydrochemical change, from Na-Cl through Na-HCO3 to Ca-HCO3 types, suggesting that groundwater was overall evolved through the freshening process accompanying cation exchange. The principal component analysis (PCA) of the hydrochemical data indicates the occurrence of three major hydrogeochemical processes occurring in an aquifer, namely: 1) progressive freshening of remaining paleo-seawater, 2) water-rock interaction (i.e., dissolution of silicates), and 3) redox process including sulfate reduction, as indicated by heavy sulfur and oxygen isotope compositions of sulfate. To quantitatively assess the hydrogeochemical processes, the end-member mixing analysis (EMMA) and the forward mixing modeling using PHREEQC code were conducted. The EMMA results show that the hydrochemical model with the two-dimensional mixing space composed of PC 1 and PC 2 best explains the mixing in the study area; therefore, we consider that the groundwater chemistry mainly evolved by mixing among three end-members (i.e., paleo-seawater, infiltrating rain, and the K-rich groundwater). The distinct depletion of sulfate in groundwater, likely due to bacterial sulfate reduction, can also be explained by EMMA. The evaluation of mass balances using geochemical modeling supports the explanation that the freshening process accompanying direct cation exchange occurs through mixing among three end-members involving the K-rich groundwater. This study shows that the multiple end-members mixing model is useful to more successfully assess complex hydrogeochemical processes occurring in a salinized aquifer under freshening, as compared to the conventional interpretation using the theoretical mixing line based on only two end-members (i.e., seawater and rainwater).

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

The current view on the phosphorus (P) cycle in forest ecosystems relies mostly on measurements and correlations of pools, and to a lower extent on measurement of fluxes. We have no direct insight into the processes phosphate goes through at the ecosystem level, and into the relative importance of organic and mineral pools in sustaining P nutrition of trees. The analysis of oxygen isotopes associated to P (18Op) is expected to bring this type of information. The German Priority Program SPP 1685 aims to test the overall hypothesis that the P-depletion of soils drives forest ecosystems from P acquiring systems (efficient mobilization of P from the mineral phase) to P recycling systems (highly efficient cycling of P). Our contribution to this project will consist in studying the relative importance of biological and geochemical processes in controlling the P cycle in temperate beech forest ecosystems in Germany along a gradient of decreasing soil P availability. We will follow the fate of phosphate from litter fall to the uptake of P by plants via P release by decomposition of organic matter or after release from P-containing minerals, by using a multi-isotope approach (O in water and phosphate plus 33P). To address our research question we will rely on measurements in experimental forest sites and on laboratory incubations of the organic layer or the mineral soil. We present here the first results issued from the 2014 sampling on three study sites, where we characterized the P pools in surface soil horizons by a sequential extraction (modified after Tiessen and Moir, 2007) and we analysed the 18Op of the resin extractable- and microbial-P fractions. Contrary to what was previously found (e.g. Tamburini et al. 2012) the isotopic composition of these fractions in most of the samples does not reflect the equilibrium value (as the result of the dominance of the pyrophosphatase activity on the other enzymatic processes, Blake et al. 2005). Depending on the P availability in the soil, deviations from the equilibrium are more or less pronounced. We hypothesized that the 18Op is the result of other processes such the mineralization of organic P by phosphatases. These first results of 18Op on forest soils are suggesting that isotopic equilibrium driven by biological cycling (pyrophosphatase) is not always overprinting other processes. In addition, together with information on P speciation/concentration, 18Op seems to provide direct insights on P cycling at the ecosystem level. Blake R.E., Neil J.R.O., Surkov A.V. (2005) Biogeochemical cycling of phosphorus: insights from oxygen isotope effects of phosphoenzymes. American Journal of Science 305: 596-620 Moir J.O., Tiessen H. Characterization of available P by sequential extraction. Soil Sampling and Methods of Analysis, Second Edition. Ed. by M.R. Carter and E.G. Gregorich CRC Press 2007 Tamburini F., Pfahler V, Bünemann E.K., Guelland K., Bernasconi S.M., Frossard E. (2012) Oxygen Isotopes Unravel the Role of Microorganisms in Phosphate Cycling in Soils. Environmental Science & Technology 46: 5956-5962

Chemical evolution of Himalayan leucogranites based on an O, U-Pb and Hf study of zircon

NASA Astrophysics Data System (ADS)

Hopkinson, Thomas N.; Warren, Clare J.; Harris, Nigel B. W.; Hammond, Samantha J.; Parrish, Randall R.

2015-04-01

Crustal melting is a characteristic process at convergent plate margins, where crustal rocks are heated and deformed. Miocene leucogranite sheets and plutons are found intruded into the high-grade metasedimentary core (the Greater Himalayan Sequence, GHS) across the Himalayan orogen. Previously-published Himalayan whole-rock data suggest that these leucogranites formed from a purely meta-sedimentary source, isotopically similar to those into which they now intrude. Bulk rock analyses carry inherent uncertainties, however: they may hide contributions from different contributing sources, and post-crystallization processes such as fluid interaction may significantly alter the original chemistry. In contrast, zircon is more able to retain precise information of the contributing sources of the melt from which it crystallises whilst its resistant nature is impervious to post-magmatic processes. This multi-isotope study of Oligocene-Miocene leucogranite zircons from the Bhutan Himalaya, seeks to differentiate between various geochemical processes that contribute to granite formation. Hf and O isotopes are used to detect discrete changes in melt source while U-Pb isotopes provide the timing of zircon crystallisation. Our data show that zircon rims of Himalayan age yield Hf-O signatures that lie within the previously reported whole-rock GHS field, confirming the absence of a discernible mantle contribution to the leucogranite source. Importantly, we document a decrease in the minimum ɛHf values during Himalayan orogenesis through time, correlating to a change in Hf model age from 1.4 Ga to 2.4 Ga. Nd model ages for the older Lesser Himalayan metasediments (LHS) that underthrust the GHS are significantly older than those for the GHS (2.4-2.9 Ga compared with 1.4-2.2 Ga), and as such even minor contributions of LHS material incorporated into a melt would significantly increase the resulting Hf model age. Hence our leucogranite data suggest either a change of source within the GHS over time, or an increasing contribution from older Lesser Himalayan (LHS) material in the melt. This is the first time that an evolutionary trend in the chemistry of Himalayan crustal melts has been recognized. Thus these new data show that, at least in the Himalaya, accessory phase geochemistry can provide more detailed insight into tectonic processes than bulk rock geochemistry.

First observation of a mass independent isotopic fractionation in a condensation reaction

NASA Technical Reports Server (NTRS)

Thiemens, M. H.; Nelson, R.; Dong, Q. W.; Nuth, Joseph A., III

1994-01-01

Thiemens and Heidenreich (1983) first demonstrated that a chemically produced mass independent isotopic fractionation process could produce an isotopic composition which is identical to that observed in Allende inclusions. This raised the possibility that the meteoritic components could be produced by chemical, rather than nuclear processes. In order to develop a mechanistic model of the early solar system, it is important that relevant reactions be studied, particularly, those which may occur in the earliest condensation reactions. The isotopic results for isotopic fractionations associated with condensation processes are reported. A large mass independent isotopic fractionation is observed in one of the experiments.

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

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

Matsuyama, M.; Kondo, M.; Noda, N.

2015-03-15

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel ismore » limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)« less

Variability of Fe isotope compositions of hydrothermal sulfides and oxidation products at mid-ocean ridges

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Wang, Hao; Li, Zhenggang; Yu, Xing; Bi, Dongwei; He, Yongsheng

2018-04-01

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value - 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

Sulfate and sulfide sulfur isotopes (δ34S and δ33S) measured by solution and laser ablation MC-ICP-MS: An enhanced approach using external correction

USGS Publications Warehouse

Pribil, Michael; Ridley, William I.; Emsbo, Poul

2015-01-01

Isotope ratio measurements using a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS) commonly use standard-sample bracketing with a single isotope standard for mass bias correction for elements with narrow-range isotope systems measured by MC-ICP-MS, e.g. Cu, Fe, Zn, and Hg. However, sulfur (S) isotopic composition (δ34S) in nature can range from at least − 40 to + 40‰, potentially exceeding the ability of standard-sample bracketing using a single sulfur isotope standard to accurately correct for mass bias. Isotopic fractionation via solution and laser ablation introduction was determined during sulfate sulfur (Ssulfate) isotope measurements. An external isotope calibration curve was constructed using in-house and National Institute of Standards and Technology (NIST) Ssulfate isotope reference materials (RM) in an attempt to correct for the difference. The ability of external isotope correction for Ssulfate isotope measurements was evaluated by analyzing NIST and United States Geological Survey (USGS) Ssulfate isotope reference materials as unknowns. Differences in δ34Ssulfate between standard-sample bracketing and standard-sample bracketing with external isotope correction for sulfate samples ranged from 0.72‰ to 2.35‰ over a δ34S range of 1.40‰ to 21.17‰. No isotopic differences were observed when analyzing Ssulfide reference materials over a δ34Ssulfide range of − 32.1‰ to 17.3‰ and a δ33S range of − 16.5‰ to 8.9‰ via laser ablation (LA)-MC-ICP-MS. Here, we identify a possible plasma induced fractionation for Ssulfate and describe a new method using external isotope calibration corrections using solution and LA-MC-ICP-MS.

Weaning practices among pastoralists: New evidence of infant feeding patterns from Bronze Age Eurasia.

PubMed

Ventresca Miller, Alicia; Hanks, Bryan K; Judd, Margaret; Epimakhov, Andrey; Razhev, Dmitry

2017-03-01

This paper investigates infant feeding practices through stable carbon (δ 13 C) and nitrogen (δ 15 N) isotopic analyses of human bone collagen from Kamennyi Ambar 5, a Middle Bronze Age cemetery located in central Eurasia. The results presented are unique for the time period and region, as few cemeteries have been excavated to reveal a demographic cross-section of the population. Studies of weaning among pastoral societies are infrequent and this research adds to our knowledge of the timing, potential supplementary foods, and cessation of breastfeeding practices. Samples were collected from 41 subadults (<15 years) and 27 adults (15+ years). Isotopic reference sets from adult humans as well as faunal remains were utilized as these form the primary and complementary foods fed to infants. Slight shifts in δ 13 C and δ 15 N values revealed that weaning was a multi-stage process (breastfeeding, weaning, and complete cessation of nursing) that began at 6 months of age, occurred over several years of early childhood, and was completed by 4 years of age. Our results indicate that weaning was a multi-stage process that was unique among late prehistoric pastoralist groups in Eurasia that were dependent on milk products as a supplementary food. Our discussion centers on supporting this hypothesis with modern information on central and east Eurasian herding societies including the age at which complementary foods are introduced, the types of complementary foods, and the timing of the cessation of breastfeeding. Integral to this work is the nature of pastoral economies and their dependence on animal products, the impact of complementary foods on nutrition and health, and how milk processing may have affected nutrition content and digestibility of foods. This research on Eurasian pastoralists provides insights into the complexities of weaning among prehistoric pastoral societies as well as the potential for different complementary foods to be incorporated into infant diets in the past. © 2016 Wiley Periodicals, Inc.

Isotopically (δ13C and δ18O) heavy volcanic plumes from Central Andean volcanoes: a field study

NASA Astrophysics Data System (ADS)

Schipper, C. Ian; Moussallam, Yves; Curtis, Aaron; Peters, Nial; Barnie, Talfan; Bani, Philipson; Jost, H. J.; Hamilton, Doug; Aiuppa, Alessandro; Tamburello, Giancarlo; Giudice, Gaetano

2017-08-01

Stable isotopes of carbon and oxygen in volcanic gases are key tracers of volatile transfer between Earth's interior and atmosphere. Although important, these data are available for few volcanoes because they have traditionally been difficult to obtain and are usually measured on gas samples collected from fumaroles. We present new field measurements of bulk plume composition and stable isotopes (δ13CCO2 and δ18OH2O+CO2) carried out at three northern Chilean volcanoes using MultiGAS and isotope ratio infrared spectroscopy. Carbon and oxygen in magmatic gas plumes of Lastarria and Isluga volcanoes have δ13C in CO2 of +0.76‰ to +0.77‰ (VPDB), similar to slab carbonate; and δ18O in the H2O + CO2 system ranging from +12.2‰ to +20.7‰ (VSMOW), suggesting significant contributions from altered slab pore water and carbonate. The hydrothermal plume at Tacora has lower δ13CCO2 of -3.2‰ and δ18OH2O+CO2 of +7.0‰, reflecting various scrubbing, kinetic fractionation, and contamination processes. We show the isotopic characterization of volcanic gases in the field to be a practical complement to traditional sampling methods, with the potential to remove sampling bias that is a risk when only a few samples from accessible fumaroles are used to characterize a given volcano's volatile output. Our results indicate that there is a previously unrecognized, relatively heavy isotopic signature to bulk volcanic gas plumes in the Central Andes, which can be attributed to a strong influence from components of the subducting slab, but may also reflect some local crustal contamination. The techniques we describe open new avenues for quantifying the roles that subduction zones and arc volcanoes play in the global carbon cycle.

Sulfur isotopic and proteomic profiles of sulfate reducers grown under differential steady-states

NASA Astrophysics Data System (ADS)

Leavitt, W.; Venceslau, S.; Waldbauer, J.; Smith, D. A.; Boidi, F. J.; Bradley, A. S.

2016-12-01

Microbial sulfate reducers (MSR) drive the Earth's biogeochemical sulfur cycle. At the heart of this energy metabolism is a cascade of redox transformations coupling organic carbon and/or hydrogen oxidation to the dissimilatory reduction of sulfate to sulfide. The product sulfide is depleted in the heavier isotopes of sulfur, relative to the reactant sulfate, consistent with a normal kinetic isotope effect. However, the magnitude of the net fractionation during MSR can range over a range of 70 permil, consistent with a multi-step set of reactions. This range in MSR fractionation has been shown to mainly depend on: i) the cell-specific sulfate reduction rate (csSRR), and ii) the ambient sulfate concentration. However, the fractionation under identical conditions differs among strains (Bradley et al. 2016. Geobio), and so must also be mediated by strain-specific processes, such as the nature and quantity of individual proteins involved in sulfate reduction, electron transport, and growth. In recent work we have examined the influence of electron donor, electron acceptor, and co-limitation under controlled steady-state culture conditions in order better inform models of MSR isotope fractionation, and the physiological and isotopic response to differential environmental forcings (e.g. Leavitt et al. (2013) PNAS). Recent models of the fractionation response to MSR rate (c.f. Bradley 2016; Wing & Halevy, 2016) make specific predictions for the responses of the cellular metabolome and proteome. Here we compare the steady-state S-isotopic fractionation and proteome of `fast' versus `slow' grown D. vulgaris, using replicate chemostats under electron donor limitation. We observe clear and statistically robust changes in some key central MSR and C-metabolism enzymes, though a host of the critical energy-transfer enzymes show no statistically discernable change. We discuss these results in light of recent theoretical advances and their relevance to modern and ancient geochemical records.

High-precision 41K/39K measurements by MC-ICP-MS indicate terrestrial variability of δ41K

USGS Publications Warehouse

Morgan, Leah; Santiago Ramos, Danielle P.; Davidheiser-Kroll, Brett; Faithfull, John; Lloyd, Nicholas S.; Ellam, Rob M.; Higgins, John A.

2018-01-01

Potassium is a major component in continental crust, the fourth-most abundant cation in seawater, and a key element in biological processes. Until recently, difficulties with existing analytical techniques hindered our ability to identify natural isotopic variability of potassium isotopes in terrestrial materials. However, measurement precision has greatly improved and a range of K isotopic compositions has now been demonstrated in natural samples. In this study, we present a new technique for high-precision measurement of K isotopic ratios using high-resolution, cold plasma multi-collector mass spectrometry. We apply this technique to demonstrate natural variability in the ratio of 41K to 39K in a diverse group of geological and biological samples, including silicate and evaporite minerals, seawater, and plant and animal tissues. The total range in 41K/39K ratios is ca. 2.6‰, with a long-term external reproducibility of 0.17‰ (2, N=108). Seawater and seawater-derived evaporite minerals are systematically enriched in 41K compared to silicate minerals by ca. 0.6‰, a result consistent with recent findings1, 2. Although our average bulk-silicate Earth value (-0.54‰) is indistinguishable from previously published values, we find systematic δ41K variability in some high-temperature sample suites, particularly those with evidence for the presence of fluids. The δ41K values of biological samples span a range of ca. 1.2‰ between terrestrial mammals, plants, and marine organisms. Implications of terrestrial K isotope variability for the atomic weight of K and K-based geochronology are discussed. Our results indicate that high-precision measurements of stable K isotopes, made using commercially available mass spectrometers, can provide unique insights into the chemistry of potassium in geological and biological systems. 

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.

Spatially resolved analysis of plutonium isotopic signatures in environmental particle samples by laser ablation-MC-ICP-MS.

PubMed

Konegger-Kappel, Stefanie; Prohaska, Thomas

2016-01-01

Laser ablation-multi-collector-inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) was optimized and investigated with respect to its performance for determining spatially resolved Pu isotopic signatures within radioactive fuel particle clusters. Fuel particles had been emitted from the Chernobyl nuclear power plant (ChNPP) where the 1986 accident occurred and were deposited in the surrounding soil, where weathering processes caused their transformation into radioactive clusters, so-called micro-samples. The size of the investigated micro-samples, which showed surface alpha activities below 40 mBq, ranged from about 200 to 1000 μm. Direct single static point ablations allowed to identify variations of Pu isotopic signatures not only between distinct fuel particle clusters but also within individual clusters. The resolution was limited to 100 to 120 μm as a result of the applied laser ablation spot sizes and the resolving power of the nuclear track radiography methodology that was applied for particle pre-selection. The determined (242)Pu/(239)Pu and (240)Pu/(239)Pu isotope ratios showed a variation from low to high Pu isotope ratios, ranging from 0.007(2) to 0.047(8) for (242)Pu/(239)Pu and from 0.183(13) to 0.577(40) for (240)Pu/(239)Pu. In contrast to other studies, the applied methodology allowed for the first time to display the Pu isotopic distribution in the Chernobyl fallout, which reflects the differences in the spent fuel composition over the reactor core. The measured Pu isotopic signatures are in good agreement with the expected Pu isotopic composition distribution that is typical for a RBMK-1000 reactor, indicating that the analyzed samples are originating from the ill-fated Chernobyl reactor. The average Pu isotope ratios [(240)Pu/(239)Pu = 0.388(86), (242)Pu/(239)Pu = 0.028(11)] that were calculated from all investigated samples (n = 48) correspond well to previously published results of Pu analyses in contaminated samples from the vicinity of the Chernobyl NPP [e.g. (240)Pu/(239)Pu = 0.394(2) and (242)Pu/(239)Pu = 0.027(1); Nunnemann et al. (J Alloys Compd 271-273:45-48, 1998)].

Understanding r-process Nucleosynthesis through Nuclear Data

NASA Astrophysics Data System (ADS)

Surman, Rebecca

2018-06-01

The electromagnetic counterpart of the GW170817 neutron star merger provided the first direct evidence of the astrophysical formation of nuclei via rapid neutron capture (r-process) nucleosynthesis. Full understanding of this event from first principles and its role in galactic chemical evolution requires progress in a number of areas. One key area is nuclear physics. A neutron star merger r-process involves thousands of exotic nuclear species, the majority of which have never been studied in the laboratory. Here we will discuss r-process nuclear data needs and how nuclear physics uncertainties influence our interpretation of observed abundance patterns and kilonova signals. We will explore the promise of experimental campaigns at rare isotope beam facilities to reduce these uncertainties, and describe recent efforts to directly connect nuclear data to astrophysical environments via the ‘reverse-engineering’ of unknown nuclear properties from the r-process abundance pattern.

Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg–Fe isotopic analyses

USGS Publications Warehouse

Sio, Corliss Kin I.; Dauphas, Nicolas; Teng, Fang-Zhen; Chaussidon, Marc; Helz, Rosalind T.; Roskosz, Mathieu

2013-01-01

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (∼300 μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ26Mg from +0.1‰ to −0.2‰ and δ56Fe from −1.2‰ to −0.2‰ from core to rim), which can only be explained by Mg–Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D2/D1 = (m1/m2)β with βMg ∼0.16 and βFe ∼0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ56Fe measurements within precisions of ∼0.2‰ (1 SD) at spatial resolutions of ∼50 μm. δ56Fe and δ26Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ56Fe steeply trends toward lighter compositions and δ26Mg trends toward heavier compositions with higher Fo#. A plot of δ56Fe vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry.

High Throughput Strontium Isotope Method for Monitoring Fluid Flow Related to Geological CO2 Storage

NASA Astrophysics Data System (ADS)

Capo, R. C.; Wall, A. J.; Stewart, B. W.; Phan, T. T.; Jain, J. C.; Hakala, J. A.; Guthrie, G. D.

2012-12-01

Natural isotope tracers, such as strontium (Sr), can be a unique and powerful component of a monitoring strategy at a CO2 storage site, facilitating both the quantification of reaction progress for fluid-rock interactions and the tracking of brine migration caused by CO2 injection. Several challenges must be overcome, however, to enable the routine use of isotopic tracers, including the ability to rapidly analyze numerous aqueous samples with potentially complex chemical compositions. In a field situation, it might be necessary to analyze tens of samples over a short period of time to identify subsurface reactions and respond to unexpected fluid movement in the host formation. These conditions require streamlined Sr separation chemistry for samples ranging from pristine groundwaters to those containing high total dissolved solids, followed by rapid measurement of isotope ratios with high analytical precision. We have optimized Sr separation chemistry and MC-ICP-MS methods to provide rapid and precise measurements of isotope ratios in geologic, hydrologic, and environmental samples. These improvements will allow an operator to independently prepare samples for Sr isotope analysis off-site using fast, low cost chemical separation procedures and commercially available components. Existing vacuum-assisted Sr separation procedures were modified by using inexpensive disposable parts to eliminate cross contamination. Experimental results indicate that the modified columns provide excellent separation of Sr from chemically complex samples and that Sr can be effectively isolated from problematic matrix elements (e.g., Ca, Ba, K) associated with oilfield brines and formation waters. The separation procedure is designed for high sample throughput in which batches of 24 samples can be processed in approximately 2 hours, and are ready for Sr isotope measurements by MC-ICP-MS immediately after collection from the columns. Precise Sr isotope results can be achieved by MC-ICP-MS with a throughput of 4 to 5 samples per hour. Our mean measured value of NIST Sr isotope standard SRM 987 is 0.710265 ± 0.000014 (2σ, n = 94). A range of brines and CO2-rich fluids analyzed by this method yielded results within the analytical uncertainty of 87Sr/86Sr ratios previously determined by standard column separation and thermal ionization mass spectrometry. This method provides a fast and effective way to use Sr isotopes for monitoring purposes related to geological CO2 storage.

Defining a conceptual model for the coastal aquifers of Mediterranean islands, an example from Corsica (France)

NASA Astrophysics Data System (ADS)

Santoni, Sebastien; Garel, Emilie; Huneau, Frederic

2016-04-01

A hydrochemical and isotope study was conducted to identify the flow paths, the recharge areas and the geochemical processes governing the evolution of groundwater in a Mediterranean carbonate coastal aquifer. The study is expected to improve the hydrogeological conceptual model based on environmental tracer investigations tools to characterise and quantify the aquifer system of Bonifacio. The groundwater resource represents the unique drinking water resource of the southern Corsica and the region faces a high pressures over the groundwater resource during the touristic period (2,000,000 tourists per year). A well-documented description of the geology and structure of this basin was the starting point for a detailed hydrogeochemical and isotopic study at the aquifer scale. A hydrochemical (physico-chemical parameters, major ions) and isotope (δ2H, δ18O, 3H) survey of rainwater and groundwater has been carried out monthly during almost two years. A local meteoric water line has been defined and marine, terrestrial and anthropogenic influences on the recharge water hydrochemistry have been described. Preferential recharge during autumn/winter of rainfall is observed and a depletion in the isotopic signature for some groundwater samples suggests a recharge in higher altitude from the surrounding granites. A modification of the input signal during infiltration through the unsaturated zone appears and the groundwater hydrochemistry displays differential variations in time and space, with the presence of inertial water bodies in the lower aquifer mainly. In this context, CFCs (CFC-11, CFC-12, CFC-113) and SF6 were used to evaluate groundwater residence time. CFCs have been relevant despite the presence of a deep unsaturated zone and the computed rate of groundwater renewal is pluriannual to multi-decadal. Natural SF6 was found in granites and has been used as a direct tracer of groundwater origin, highlighting its role in the aquifer lateral recharge. Strontium isotopes (87Sr/86Sr) were used to improve knowledge of groundwater mineralization and mixing processes. The use 87Sr/86Sr vs δ18O was relevant and helped confirming and quantifying the granitic contribution to the aquifer recharge. To improve the quantification of the water balance terms, submarine groundwater discharges have been studied using aerial infrared images in conjunction with Radon and Radium isotopes (222Rn, 223,224Ra).

Preparation and purification of organic samples for selenium isotope studies.

PubMed

Banning, Helena; Stelling, Monika; König, Stephan; Schoenberg, Ronny; Neumann, Thomas

2018-01-01

Selenium (Se) is an important micronutrient but also a strong toxin with a narrow tolerance range for many organisms. As such, a globally heterogeneous Se distribution in soils is responsible for various disease patterns (i.e. Se excess and deficiency) and environmental problems, whereby plants play a key role for the Se entrance into the biosphere. Selenium isotope variations were proved to be a powerful tracer for redox processes and are therefore promising for the exploration of the species dependent Se metabolism in plants and the Se cycling within the Critical Zone. Plant cultivation setups enable systematic controlled investigations, but samples derived from them-plant tissue and phytoagar-are particularly challenging and require specific preparation and purification steps to ensure precise and valid Se isotope analytics performed with HG-MC-ICP-MS. In this study, different methods for the entire process from solid tissue preparation to Se isotope measurements were tested, optimized and validated. A particular microwave digestion procedure for plant tissue and a vacuum filtration method for phytoagar led to full Se recoveries, whereby unfavorable organic residues were reduced to a minimum. Three purification methods predominantly described in the literature were systematically tested with pure Se solution, high concentrated multi-element standard solution as well as plant and phytoagar as target matrices. All these methods efficiently remove critical matrix elements, but differ in Se recovery and organic residues. Validation tests doping Se-free plant material and phytoagar with a reference material of known Se isotope composition revealed the high impact of organic residues on the accuracy of MC-ICP-MS measurements. Only the purification method with no detectable organic residues, hydride generation and trapping, results in valid mass bias correction for plant samples with an average deviation to true δ82/76Se values of 0.2 ‰ and a reproducibility (2 SD) of ± 0.2 ‰. For phytoagar this test yields a higher deviation of 1.1 ‰ from the true value and a 2 SD of ± 0.1 ‰. The application of the developed methods to cultivated plants shows sufficient accuracy and precision and is a promising approach to resolve plant internal Se isotope fractionations, for which respective δ82/76Se values of +2.3 to +3.5 ‰ for selenate and +1.2 to +1.9 ‰ for selenite were obtained.

Preparation and purification of organic samples for selenium isotope studies

PubMed Central

Stelling, Monika; König, Stephan; Schoenberg, Ronny; Neumann, Thomas

2018-01-01

Selenium (Se) is an important micronutrient but also a strong toxin with a narrow tolerance range for many organisms. As such, a globally heterogeneous Se distribution in soils is responsible for various disease patterns (i.e. Se excess and deficiency) and environmental problems, whereby plants play a key role for the Se entrance into the biosphere. Selenium isotope variations were proved to be a powerful tracer for redox processes and are therefore promising for the exploration of the species dependent Se metabolism in plants and the Se cycling within the Critical Zone. Plant cultivation setups enable systematic controlled investigations, but samples derived from them–plant tissue and phytoagar–are particularly challenging and require specific preparation and purification steps to ensure precise and valid Se isotope analytics performed with HG-MC-ICP-MS. In this study, different methods for the entire process from solid tissue preparation to Se isotope measurements were tested, optimized and validated. A particular microwave digestion procedure for plant tissue and a vacuum filtration method for phytoagar led to full Se recoveries, whereby unfavorable organic residues were reduced to a minimum. Three purification methods predominantly described in the literature were systematically tested with pure Se solution, high concentrated multi-element standard solution as well as plant and phytoagar as target matrices. All these methods efficiently remove critical matrix elements, but differ in Se recovery and organic residues. Validation tests doping Se-free plant material and phytoagar with a reference material of known Se isotope composition revealed the high impact of organic residues on the accuracy of MC-ICP-MS measurements. Only the purification method with no detectable organic residues, hydride generation and trapping, results in valid mass bias correction for plant samples with an average deviation to true δ82/76Se values of 0.2 ‰ and a reproducibility (2 SD) of ± 0.2 ‰. For phytoagar this test yields a higher deviation of 1.1 ‰ from the true value and a 2 SD of ± 0.1 ‰. The application of the developed methods to cultivated plants shows sufficient accuracy and precision and is a promising approach to resolve plant internal Se isotope fractionations, for which respective δ82/76Se values of +2.3 to +3.5 ‰ for selenate and +1.2 to +1.9 ‰ for selenite were obtained. PMID:29509798

Watershed Scale Stable Isotope Distribution and Implications on Soil Organic Carbon Loss Monitoring under Hydrologic Uncertainty

NASA Astrophysics Data System (ADS)

Ahmed, I.; Karim, A.; Boutton, T. W.; Strom, K.; Fox, J.

2013-12-01

The thematic focus of this 3-year period multidisciplinary USDA-CBG collaborative applied research is integrated monitoring of soil organic carbon (SOC) loss from multi-use lands using state-of-the-art stable isotope science under uncertain hydrologic influences. In this study, SOC loss and water runoff are being monitored on a 150 square kilometer watershed in Houston, Texas, using natural rainfall events, and total organic carbon/nitrogen concentration (TOC/TN) and stable isotope ratio (δ13C, δ15N) measurements with different land-use types. The work presents the interdisciplinary research results to uncover statistically valid and scientifically sound ways to monitor SOC loss by (i) application of Bayesian Markov Chain Monte Carlo statistical models to assess the relationship between rainfall-runoff and SOC release during soil erosion in space and time, (ii) capturing the episodic nature of rainfall events and its role in the spatial distribution of SOC loss from water erosion, (iii) stable isotope composition guided fingerprinting (source and quantity) of SOC by considering various types of erosion processes common in a heterogeneous watershed, to be able to tell what percentage of SOC is lost from various land-use types (Fox and Papanicolaou, 2008), (iv) creating an integrated watershed scale statistical soil loss monitoring model driven by spatial and temporal correlation of flow and stable isotope composition (Ahmed et. al., 2013a,b), and (v) creation of an integrated decision support system (DSS) for sustainable management of SOC under hydrologic uncertainty to assist the end users. References: Ahmed, I., Karim, A., Boutton, T.W., and Strom, K.B. (2013a). 'Monitoring Soil Organic Carbon Loss from Erosion Using Stable Isotopes.' Proc., Soil Carbon Sequestration, International Conference, May 26-29, Reykjavik, Iceland. Ahmed, I, Bouttom, T.W., Strom, K. B., Karim, A., and Irvin-Smith, N. (2013b). 'Soil carbon distribution and loss monitoring in the urbanized Buffalo Bayou watershed, Houston, Texas.' Proc., 4th Annual All Investigators Meeting of the North American Carbon Program, February 4-7, Albuquerque, NM. Fox, J.F. and Papanicolaou, A.N. (2008). An un-mixing model to study watershed erosion processes. Advances in Water Resources, 31, 96-108. ______________________________ * Corresponding author';s e-mail: ifahmed@pvamu.edu

Vanadium isotope heterogeneity of the early solar system

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Groundwater Recharge Processes Revealed By Multi-Tracers Approach in a Headwater, North China Plain

NASA Astrophysics Data System (ADS)

Sakakibara, K.; Tsujimura, M.; Song, X.; Zhang, J.

2014-12-01

Groundwater recharge variation in space and time is crucial for effective water management especially in arid/ semi-arid regions. In order to reveal comprehensive groundwater recharge processes in a catchment with a large topographical relief and seasonal hydrological variations, intensive field surveys were conducted at 4 times in different seasons in Wangkuai watershed, Taihang Mountains, which is a main groundwater recharge zone of North China Plain. The groundwater, spring, stream water and lake water were sampled, and inorganic solute constituents and stable isotopes of oxygen-18 and deuterium were determined on all water samples. Also, the stream flow rate was observed in stable state condition. The stable isotopic compositions, silica and bicarbonate concentrations in the groundwater show close values as those in the surface water, suggesting main groundwater recharge occurs from surface water at mountain-plain transitional zone throughout a year. Also, the deuterium and oxgen-18 in the Wangkuai reservoir and the groundwater in the vicinity of the reservoir show higher values, suggesting the reservoir water, affected by evaporation effect, seems to have an important role for the groundwater recharge in alluvial plain. For specifying the groundwater recharge area and quantifying groundwater recharge rate from the reservoir, an inversion analysis and a simple mixing model were applied in Wangkuai watershed using stable isotopes of oxygen-18 and deuterium. The model results show that groundwater recharge occurs dominantly at the altitude from 357 m to 738 m corresponding to mountain-plain transitional zone, and groundwater recharge rate by Wangkuai reservoir is estimated to be 2.4 % of total groundwater recharge in Wangkuai watershed.

Experimental investigation on the carbon isotope fractionation of methane during gas migration by diffusion through sedimentary rocks at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Zhang, Tongwei; Krooss, Bernhard M.

2001-08-01

Molecular transport (diffusion) of methane in water-saturated sedimentary rocks results in carbon isotope fractionation. In order to quantify the diffusive isotope fractionation effect and its dependence on total organic carbon (TOC) content, experimental measurements have been performed on three natural shale samples with TOC values ranging from 0.3 to 5.74%. The experiments were conducted at 90°C and fluid pressures of 9 MPa (90 bar). Based on the instantaneous and cumulative composition of the diffused methane, effective diffusion coefficients of the 12CH4 and 13CH4 species, respectively, have been calculated. Compared with the carbon isotopic composition of the source methane (δ13C1 = -39.1‰), a significant depletion of the heavier carbon isotope (13C) in the diffused methane was observed for all three shales. The degree of depletion is highest during the initial non-steady state of the diffusion process. It then gradually decreases and reaches a constant difference (Δ δ = δ13Cdiff -δ13Csource) when approaching the steady-state. The degree of the isotopic fractionation of methane due to molecular diffusion increases with the TOC content of the shales. The carbon isotope fractionation of methane during molecular migration results practically exclusively from differences in molecular mobility (effective diffusion coefficients) of the 12CH4 and 13CH4 entities. No measurable solubility fractionation was observed. The experimental isotope-specific diffusion data were used in two hypothetical scenarios to illustrate the extent of isotopic fractionation to be expected as a result of molecular transport in geological systems with shales of different TOC contents. The first scenario considers the progression of a diffusion front from a constant source (gas reservoir) into a homogeneous ;semi-infinite; shale caprock over a period of 10 Ma. In the second example, gas diffusion across a 100 m caprock sequence is analyzed in terms of absolute quantities and isotope fractionation effects. The examples demonstrate that methane losses by molecular diffusion are small in comparison with the contents of commercial size gas accumulations. The degree of isotopic fractionation is related inversely to the quantity of diffused gas so that strong fractionation effects are only observed for relatively small portions of gas. The experimental data can be readily used in numerical basin analysis to examine the effects of diffusion-related isotopic fractionation on the composition of natural gas reservoirs.

Stable Isotope Tracers of Process in Great Lakes Food Webs

EPA Science Inventory

Stable isotope analyses of biota are now commonly used to discern trophic pathways between consumers and their foods. However, those same isotope data also hold information about processes that influence the physicochemical setting of food webs as well as biological processes ope...

Separation of Platinum from Palladium and Iridium in Iron Meteorites and Accurate High-Precision Determination of Platinum Isotopes by Multi-Collector ICP-MS.

PubMed

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

2017-12-01

This study presents a new measurement procedure for the isolation of Pt from iron meteorite samples. The method also allows for the separation of Pd from the same sample aliquot. The separation entails a two-stage anion-exchange procedure. In the first stage, Pt and Pd are separated from each other and from major matrix constituents including Fe and Ni. In the second stage, Ir is reduced with ascorbic acid and eluted from the column before Pt collection. Platinum yields for the total procedure were typically 50-70%. After purification, high-precision Pt isotope determinations were performed by multi-collector ICP-MS. The precision of the new method was assessed using the IIAB iron meteorite North Chile. Replicate analyses of multiple digestions of this material yielded an intermediate precision for the measurement results of 0.73 for ε 192 Pt, 0.15 for ε 194 Pt and 0.09 for ε 196 Pt (2 standard deviations). The NIST SRM 3140 Pt solution reference material was passed through the measurement procedure and yielded an isotopic composition that is identical to the unprocessed Pt reference material. This indicates that the new technique is unbiased within the limit of the estimated uncertainties. Data for three iron meteorites support that Pt isotope variations in these samples are due to exposure to galactic cosmic rays in space.

Multi-organ autonomic dysfunction in Parkinson disease

PubMed Central

2010-01-01

Both pathologic and clinical studies of autonomic pathways have expanded the concept of Parkinson disease (PD) from a movement disorder to a multi-level widespread neurodegenerative process with non-motor features spanning several organ systems. This review integrates neuropathologic findings and autonomic physiology in PD as it relates to end organ autonomic function. Symptoms, pathology and physiology of the cardiovascular, skin/sweat gland, urinary, gastrointestinal, pupillary and neuroendocrine systems can be probed by autopsy, biopsy and non-invasive electrophysiological techniques in vivo which assess autonomic anatomy and function. There is mounting evidence that PD affects a chain of neurons in autonomic pathways. Consequently, autonomic physiology may serve as a window into non-motor PD progression and allow the development of mechanistically based treatment strategies for several non-motor features of PD. End-organ physiologic markers may be used to inform a model of PD pathophysiology and non-motor progression. PMID:20851033

Isotopic inferences of ancient biochemistries - Carbon, sulfur, hydrogen, and nitrogen

NASA Technical Reports Server (NTRS)

Schidlowski, M.; Hayes, J. M.; Kaplan, I. R.

1983-01-01

In processes of biological incorporation and subsequent biochemical processing sizable isotope effects occur as a result of both thermodynamic and kinetic fractionations which take place during metabolic and biosynthetic reactions. In this chapter a review is provided of earlier work and recent studies on isotope fractionations in the biogeochemical cycles of carbon, sulfur, hydrogen, and nitrogen. Attention is given to the biochemistry of carbon isotope fractionation, carbon isotope fractionation in extant plants and microorganisms, isotope fractionation in the terrestrial carbon cycle, the effects of diagenesis and metamorphism on the isotopic composition of sedimentary carbon, the isotopic composition of sedimentary carbon through time, implications of the sedimentary carbon isotope record, the biochemistry of sulfur isotope fractionation, pathways of the biogeochemical cycle of nitrogen, and the D/H ratio in naturally occurring materials.

Tungsten isotopes in bulk meteorites and their inclusions—Implications for processing of presolar components in the solar protoplanetary disk

PubMed Central

Holst, J. C.; Paton, C.; Wielandt, D.; Bizzarro, M.

2016-01-01

We present high precision, low- and high-resolution tungsten isotope measurements of iron meteorites Cape York (IIIAB), Rhine Villa (IIIE), Bendego (IC), and the IVB iron meteorites Tlacotepec, Skookum, and Weaver Mountains, as well as CI chondrite Ivuna, a CV3 chondrite refractory inclusion (CAI BE), and terrestrial standards. Our high precision tungsten isotope data show that the distribution of the rare p-process nuclide 180W is homogeneous among chondrites, iron meteorites, and the refractory inclusion. One exception to this pattern is the IVB iron meteorite group, which displays variable excesses relative to the terrestrial standard, possibly related to decay of rare 184Os. Such anomalies are not the result of analytical artifacts and cannot be caused by sampling of a protoplanetary disk characterized by p-process isotope heterogeneity. In contrast, we find that 183W is variable due to a nucleosynthetic s-process deficit/r-process excess among chondrites and iron meteorites. This variability supports the widespread nucleosynthetic s/r-process heterogeneity in the protoplanetary disk inferred from other isotope systems and we show that W and Ni isotope variability is correlated. Correlated isotope heterogeneity for elements of distinct nucleosynthetic origin (183W and 58Ni) is best explained by thermal processing in the protoplanetary disk during which thermally labile carrier phases are unmixed by vaporization thereby imparting isotope anomalies on the residual processed reservoir. PMID:27445452

The oxygen isotopes

NASA Astrophysics Data System (ADS)

Alex Brown, B.

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

Separation of the Isotopes of Calcium by Countercurrent Electromigration in Fused Salts. Final Report; SEPARATION DES ISOTOPES DU CALCIUM PAR ELECTROMIGRATION A CONTRE COURANT EN SELS FONDUS

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

Menes, F.; Dirian, G.

1962-12-14

The results obtained up to June 25, 1962, on the separation of Ca isotopes by electromigration in fused salts have been reported in seven progress reports. The data given in these reports are summarized. Later study investigated the improvement of the diaphragm performance using nonclassical methods, preparation of an experiment confirming the performances of the high capacity U tube'' apparatus, and preparation of an installation designed for perfecting the dropping tube'' device. Only preliminary results on these studes are available. (J.S.R.)

Laboratory-based educational and outreach activities in the framework of a CAREER award at the University of Oregon

NASA Astrophysics Data System (ADS)

Bindeman, I. N.

2011-12-01

The Stable Isotope Laboratory at the University of Oregon has been used as a learning and outreach center in the framework of the 09 award entitled "Stable isotope insights into large-volume volcanic eruptions". The PI and other members of the group have actively recruitted undergraduate students, summer session and catalytic outreach undergraduates, and hosted international students, visitors, and collaborators from Russia, Iceland, France, the UK, Australia, and Switzerland. We also integrated closely with the Oregon-wide summer program that brings community college students to the University of Oregon for 2.5 months summer research residence (UCORE). In total we gave supervised five undergraduate students and three UCORE students. Additionally, we recruited undergraduates from U of Chicago, Colorado and Pomona Colleges to spend summers in the lab and in the field. In conjunction with the NSF funded PIRE program, two female graduate and one female undergraduate students participated in fieldwork in Kamchatka, and three Kamchatka undergraduates, and one Moscow graduate student visited the University Oregon. Students performed their own projects or Senior Theses and reported their results locally and at AGU conferences. We developed a management structure in which graduate students, a postdoc, and lab technician co-supervised students and visitors and this exposed them into the supervisory roles, contributed to the project progress, and liberated PI from micromanagement duties. The talk will present our experience with this management concept of a lab-based-learning initiative, which defines roles for each member of the lab. Our outreach activities included public lectures at community colleges by PI and a graduate student, and the topical Penrose conference co-organized by the PI, which attracted many students and visitors who collected their data in the lab. PI has introduced a voluntary fieldtrip as a part of his Volcanoes and Earthquake large enrollment class for non-majors. PI had less success in an attempt to involve non-geoscience majors into an optional satellite class due to the low interest among non-majors to explore geological and volcanological topics. Students in the Isotope Geochemistry and General Geochemistry classes used the Stable Isotope laboratory for their course papers, mostly related to the analyses of carbonate for isotopes of carbon and oxygen (paleoclimate projects), and using oxygen and hydrogen isotopes for sources of precipitation. Overall CAREER award provided excellent chance for multi-dimensional research that cross cut international boundaries, brings new projects in and contributes to the educational development of the PI and his group.

More than who eats who: Discerning ecological processes from stable isotopes data

EPA Science Inventory

Stable isotope analyses of biota are now commonly used to discern trophic pathways between consumers and their foods. However, those same isotope data also hold information about processes that influence the physicochemical setting of food webs as well as biological processes ope...

DANCEing with the Stars: Measuring Neutron Capture on Unstable Isotopes with DANCE

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

Couture, A.; Bond, E.; Bredeweg, T. A.

2009-03-10

Isotopes heavier than iron are known to be produced in stars through neutron capture processes. Two major processes, the slow (s) and rapid (r) processes are each responsible for 50% of the abundances of the heavy isotopes. The neutron capture cross sections of the isotopes on the s process path reveal information about the expected abundances of the elements as well as stellar conditions and dynamics. Until recently, measurements on unstable isotopes, which are most important for determining stellar temperatures and reaction flow, have not been experimentally feasible. The Detector for Advance Neutron Capture Experiments (DANCE) located at the Losmore » Alamos Neutron Science Center (LANSCE) was designed to perform time-of-flight neutron capture measurements on unstable isotopes for nuclear astrophysics, stockpile stewardship, and reactor development. DANCE is a 4-{pi}BaF{sub 2} scintillator array which can perform measurements on sub-milligram samples of isotopes with half-lives as short as a few hundred days. These cross sections are critical for advancing our understanding of the production of the heavy isotopes.« less

How to explain Si isotopes of chert?

NASA Astrophysics Data System (ADS)

Liu, Y.

2016-12-01

The variations of d30Si values in diagenetic chert and chert- associated BIFs over time can be used to reconstruct the environmental conditions of the early Earth, and become a hot topic in the Si isotope society. However, there are several different views of explaining the variation of d30Si values over time. Moreover, there are disputes in explaining the distribution of Si isotope in several main reservoirs in surface systems. Those disagreements are caused by lacking key Si isotope fractionation factors associated with the formation processes of chert and its altered products. There are many unexplained observations about Si isotope distributions in Earth's surface systems (Opfergelt and Delmelle, 2012). For example, the deduced Si isotope equilibrium fractionation factors by Rayleigh model at ambient temperature between clay and the solution D30Siclay-solution = -1.5 ‰ and -2.05 ‰ (Hughes et al., 2013) obviously disagree with common sense, which dictates that stiffer chemical bonds will enrich heavier isotopes, i.e., the precipitated minerals will preferentially incorporate heavy isotopes relative to aqueous H4SiO4 due to their shorter Si-O bonds. Another similar case is the fractionation between quartz and solution. Most field observations suggested that solution will be enriched with heavier Si isotope compared to quartz, conflicting to the fact that quartz is the one with much shorter Si-O bonds than aqueous H4SiO4 (ca. 1.610Å vs. 1.639Å). Here we provide equilibrium and kinetic Si isotope fractionation factors associated with the formation of amorphous quartz and other secondary minerals in polymerization, co-precipitation and adsorption processes. The adsorption processes of silica gel to Fe-hydroxides have been carefully examined. The Si isotope fractionations due to the formation of mono-dentate to quadru-dentate adsorbed Fe-Si complexes have been calculated. These data can explain well the experimental observations (e.g., Zheng et al., 2016) and provide further insights into such processes. With the knowledge of Si isotope fractionations of those processes, we can quantitatively evaluate the net Si isotope fractionation during the chert formation processes and can link the Si isotope composition of chert to that of seawater from now to early Archean.

Progress in the analysis and interpretation of N2O isotopes: Potential and future challenges

NASA Astrophysics Data System (ADS)

Mohn, Joachim; Tuzson, Béla; Zellweger, Christoph; Harris, Eliza; Ibraim, Erkan; Yu, Longfei; Emmenegger, Lukas

2017-04-01

In recent years, research on nitrous oxide (N2O) stable isotopes has significantly advanced, addressing an increasing number of research questions in biogeochemical and atmospheric sciences [1]. An important milestone was the development of quantum cascade laser based spectroscopic devices [2], which are inherently specific for structural isomers (15N14N16O vs. 14N15N16O) and capable to collect real-time data with high temporal resolution, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. In combination with automated preconcentration, optical isotope ratio spectroscopy (OIRS) has been applied to disentangle source processes in suburban, rural and pristine environments [e.g. 3, 4]. Within the European Metrology Research Programme (EMRP) ENV52 project "Metrology for high-impact greenhouse gases (HIGHGAS)", the quality of N2O stable isotope analysis by OIRS, the comparability between laboratories, and the traceability to the international isotope ratio scales have been addressed. An inter-laboratory comparison between eleven IRMS and OIRS laboratories, organised within HIGHGAS, indicated limited comparability for 15N site preference, i.e. the difference between 15N abundance in central (N*NO) and end (*NNO) position [5]. In addition, the accuracy of the NH4NO3 decomposition reaction, which provides the link between 15N site preference and the international 15N/14N scale, was found to be limited by non-quantitative NH4NO3 decomposition in combination with substantially different isotope enrichment factors for both nitrogen atoms [6]. Results of the HIGHGAS project indicate that the following research tasks have to be completed to foster research on N2O isotopes: 1) develop improved techniques to link the 15N and 18O abundance and the 15N site preference in N2O to the international stable isotope ratio scales; 2) provide N2O reference materials, pure and diluted in an air matrix, to improve inter-laboratory compatibility. These tasks will be addressed in the upcoming European Metrology Programme for Innovation and Research (EMPIR) project "Metrology for Stable Isotope Reference Standards (SIRS)" starting in June 2017. Acknowledgement Part of this work has been carried out within the European Metrology Research Programme (EMRP) ENV52 project-HIGHGAS. The EMRP is jointly funded by the EMRP participating countries within EURAMET and the European Union. References [1] S. Toyoda et al., Isotopocule analysis of biologically produced nitrous oxide in various environments, Mass Spectrom. Rev., Doi 10.1002/mas.21459 (2015). [2] J. Mohn et al., Site selective real-time measurements of atmospheric N2O isotopomers by laser spectroscopy, Atmos. Meas. Tech. 5(7), 1601-1609 (2012). [3] B. Wolf et al., First on-line isotopic characterization of N2O above intensively managed grassland, Biogeosci. 12, 2517-2531, (2015). [4] E. Harris et al., Tracking nitrous oxide emission processes at a suburban site with semi-continuous, in-situ measurements of isotopic composition, J. Geophys. Res. Atmos., accepted (2016). [5] J. Mohn et al., Interlaboratory assessment of nitrous oxide isotopomer analysis by isotope ratio mass spectrometry and laser spectroscopy: current status and perspectives, Rapid Commun. Mass Spectrom. 28, 1995-2007 (2014). [6] J. Mohn et al. Reassessment of the NH4NO3 thermal decomposition technique for calibration of the N2O isotopic composition, Rapid Commun. Mass Spectrom. 30, 2487-2496 (2016).

Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

PubMed

Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

2014-02-01

This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

The impact of (n, γ) reaction rate uncertainties of unstable isotopes near N = 50 on the i-process nucleosynthesis in He-shell flash white dwarfs

NASA Astrophysics Data System (ADS)

Denissenkov, Pavel; Perdikakis, Georgios; Herwig, Falk; Schatz, Hendrik; Ritter, Christian; Pignatari, Marco; Jones, Samuel; Nikas, Stylianos; Spyrou, Artemis

2018-05-01

The first-peak s-process elements Rb, Sr, Y and Zr in the post-AGB star Sakurai's object (V4334 Sagittarii) have been proposed to be the result of i-process nucleosynthesis in a post-AGB very-late thermal pulse event. We estimate the nuclear physics uncertainties in the i-process model predictions to determine whether the remaining discrepancies with observations are significant and point to potential issues with the underlying astrophysical model. We find that the dominant source in the nuclear physics uncertainties are predictions of neutron capture rates on unstable neutron rich nuclei, which can have uncertainties of more than a factor 20 in the band of the i-process. We use a Monte Carlo variation of 52 neutron capture rates and a 1D multi-zone post-processing model for the i-process in Sakurai's object to determine the cumulative effect of these uncertainties on the final elemental abundance predictions. We find that the nuclear physics uncertainties are large and comparable to observational errors. Within these uncertainties the model predictions are consistent with observations. A correlation analysis of the results of our MC simulations reveals that the strongest impact on the predicted abundances of Rb, Sr, Y and Zr is made by the uncertainties in the (n, γ) reaction rates of 85Br, 86Br, 87Kr, 88Kr, 89Kr, 89Rb, 89Sr, and 92Sr. This conclusion is supported by a series of multi-zone simulations in which we increased and decreased to their maximum and minimum limits one or two reaction rates per run. We also show that simple and fast one-zone simulations should not be used instead of more realistic multi-zone stellar simulations for nuclear sensitivity and uncertainty studies of convective–reactive processes. Our findings apply more generally to any i-process site with similar neutron exposure, such as rapidly accreting white dwarfs with near-solar metallicities.

Groundwater Recharge and Flow Processes in Taihang Mountains, a Semi-humid Region, North China

NASA Astrophysics Data System (ADS)

Sakakibara, Koichi; Tsujimura, Maki; Song, Xianfang; Zhang, Jie

2015-04-01

Groundwater flow/recharge variations in time and space are crucial for effective water management especially in semi-arid and semi-humid regions. In order to reveal comprehensive groundwater flow/recharge processes in a catchment with a large topographical relief and seasonal hydrological variations, intensive field surveys were undertaken at 4 times in different seasons (June 2011, August 2012, November 2012, February 2014) in the Wangkuai watershed, Taihang mountains, which is a main groundwater recharge area of the North China Plain. The groundwater, spring, stream water and reservoir water were taken, and inorganic solute constituents and stable isotopes of oxygen-18 and deuterium were determined on all water samples. Also, the stream flow rate and the depth of groundwater table were observed. The stable isotopic compositions and inorganic solute constituents in the groundwater are depleted and shown similar values as those of the surface water at the mountain-plain transitional area. Additionally, the groundwater in the vicinity of the Wangkuai Reservoir presents clearly higher stable isotopic compositions and lower d-excess than those of the stream water, indicating the groundwater around the reservoir is affected by evaporation same as the Wangkuai Reservoir itself. Hence, the surface water in the mountain-plain transitional area and Wangkuai Reservoir are principal groundwater recharge sources. An inversion analysis and simple mixing model were applied in the Wangkuai watershed using stable isotopes of oxygen-18 and deuterium to construct a groundwater flow model. The model shows that multi-originated groundwater flows from upstream to downstream along topography with certain mixing. In addition, the groundwater recharge occurs dominantly at the altitude from 421 m to 953 m, and the groundwater recharge rate by the Wangkuai Reservoir is estimated to be 2.4 % of the total groundwater recharge in the Wangkuai watershed. Therefore, the stream water and reservoir water in the mountain-plain transitional area plays an important role of groundwater recharge in semi-arid and semi-humid regions.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

NASA Astrophysics Data System (ADS)

Lauwens, Sara; Costas-Rodríguez, Marta; van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

A manual for a laboratory information management system (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1997-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

A manual for a Laboratory Information Management System (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1998-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study

PubMed Central

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-01-01

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient’s condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about −0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ65Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure. PMID:27468898

Cu isotopic signature in blood serum of liver transplant patients: a follow-up study.

PubMed

Lauwens, Sara; Costas-Rodríguez, Marta; Van Vlierberghe, Hans; Vanhaecke, Frank

2016-07-29

End-stage liver disease (ESLD) is life-threatening and liver transplantation (LTx) is the definitive treatment with good outcomes. Given the essential role of hepatocytes in Cu homeostasis, the potential of the serum Cu isotopic composition for monitoring a patient's condition post-LTx was evaluated. For this purpose, high-precision Cu isotopic analysis of blood serum of ESLD patients pre- and post-LTx was accomplished via multi-collector ICP-mass spectrometry (MC-ICP-MS). The Cu isotopic composition of the ESLD patients was fractionated in favour of the lighter isotope (by about -0.50‰). Post-LTx, a generalized normalization of the Cu isotopic composition was observed for the patients with normal liver function, while it remained light when this condition was not reached. A strong decrease in the δ(65)Cu value a longer term post-LTx seems to indicate the recurrence of liver failure or cancer. The observed trend in favour of the heavier Cu isotopic composition post-LTx seems to be related with the restored biosynthetic capacity of the liver, the restored hepatic metabolism and/or the restored biliary secretion pathways. Thus, Cu isotopic analysis could be a valuable tool for the follow-up of liver transplant patients and for establishing the potential recurrence of liver failure.

Isotope tracing of Hg pollution from artisanal small scale gold mining in an aquatic ecosystem of Amapá, Brazil

NASA Astrophysics Data System (ADS)

Adler Miserendino, R.; Silbergeld, E. K.; Guimarães, J. D.; Ghosh, S.; Bergquist, B. A.

2010-12-01

Artisinal small scale gold mining (ASGM) is a central economic activity throughout the developing world. It is both a poverty driven and poverty alleviating process; however, ASGM leads to extensive pollution of waterways through the use of Hg to extract gold from deposits. There have been many studies conducted in the Amazon showing elevated levels of Hg in fish and sediment downstream of ASGM sites; however, the debate continues about the contribution of Hg from ASGM versus other potential sources of Hg. In this study, we investigate whether Hg stable isotope analysis can be used to trace mercury pollution from an ASGM site through an aquatic ecosystem in Amapá, Brazil. We measured the Hg isotopic composition of sediment cores from two lakes, only one of which was heavily impacted by the use of elemental Hg in ASGM, as well as from grab samples at the AGSM site and upstream and downstream from the AGSM site along the river which connects the polluted lake to the ASGM site. Hg from all samples were trapped via combustion using the Leeman Labs Hydra-C mercury analyzer and analyzed for both mass-independent and mass-dependent signatures using cold vapor multi-collector inductively coupled plasma mass spectrometry (CV-MC-ICP-MS). Detectable variations in the Hg isotopic signatures were apparent across our field sites, suggesting stable isotopic analysis has great potential to trace contamination pathways in waterways. Preliminary data demonstrate Hg from the ASGM site has unique isotopic signatures that are seen downstream. However, the impacted lake sediments do not have the mining signature despite having three times more Hg than the non-impacted lake. Based on this data, it may be possible to trace Hg from ASGM and assess whether it is impacting local ecosystems and food webs. Hair and soil samples will also be discussed. This demonstration is essential for the broader application of these tools for understanding and applying Hg isotopic analysis in other contexts. This information may also be useful to help reduce Hg exposure of highly vulnerable populations exposed to Hg from ASGM through these aquatic networks in Amapá, Brazil.

Zinc isotope evidence for sulfate-rich fluid transfer across subduction zones

PubMed Central

Pons, Marie-Laure; Debret, Baptiste; Bouilhol, Pierre; Delacour, Adélie; Williams, Helen

2016-01-01

Subduction zones modulate the chemical evolution of the Earth's mantle. Water and volatile elements in the slab are released as fluids into the mantle wedge and this process is widely considered to result in the oxidation of the sub-arc mantle. However, the chemical composition and speciation of these fluids, which is critical for the mobility of economically important elements, remain poorly constrained. Sulfur has the potential to act both as oxidizing agent and transport medium. Here we use zinc stable isotopes (δ66Zn) in subducted Alpine serpentinites to decipher the chemical properties of slab-derived fluids. We show that the progressive decrease in δ66Zn with metamorphic grade is correlated with a decrease in sulfur content. As existing theoretical work predicts that Zn-SO42− complexes preferentially incorporate heavy δ66Zn, our results provide strong evidence for the release of oxidized, sulfate-rich, slab serpentinite-derived fluids to the mantle wedge. PMID:27982033

Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

NASA Astrophysics Data System (ADS)

Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

2012-08-01

Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the contribution of different processes to the total N2O flux, apparently because these values were not only governed by individual pathways but eventually also by the spatial distribution of substrates and activity within the aquifers. These observations could be explained by the dynamics of N2O production, reduction and transport in water-saturated systems with heterogenic distribution of microbial activity and by a combination of diffusive and enzymatic isotope effects.

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

PubMed

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

2009-06-01

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

Timing of strain localization in high-pressure low-temperature shear zones: The argon isotopic record

NASA Astrophysics Data System (ADS)

Laurent, Valentin; Scaillet, Stéphane; Jolivet, Laurent; Augier, Romain

2017-04-01

The complex interplay between rheology, temperature and deformation profoundly influences how crustal-scale shear zones form and then evolve across a deforming lithosphere. Understanding early exhumation processes in subduction zones requires quantitative age constraints on the timing of strain localization within high-pressure shear zones. Using both the in situ laser ablation and conventional step-heating 40Ar/39Ar dating (on phengite single grains and populations) methods, this study aims at quantifying the duration of ductile deformation and the timing of strain localization within HP-LT shear zones of the Cycladic Blueschist Unit (CBU, Greece). The rate of this progressive strain localization is unknown, and in general, poorly known in similar geological contexts. Critical to retrieve realistic estimates of rates of strain localization during exhumation, dense 40Ar/39Ar age transects were sampled along shear zones recently identified on Syros and Sifnos islands. There, field observations suggest that deformation progressively localized downward in the CBU during exhumation. In parallel, these shear zones are characterized by different degrees of retrogression from blueschist-facies to greenschist-facies P-T conditions overprinting eclogite-facies record throughout the CBU. Results show straightforward correlations between the degree of retrogression, the finite strain intensity and 40Ar/39Ar ages; the most ductilely deformed and retrograded rocks yielded the youngest 40Ar/39Ar ages. The possible effects of strain localization during exhumation on the record of the argon isotopic system in HP-LT shear zones are addressed. Our results show that strain has localized in shear zones over a 30 Ma long period and that individual shear zones evolve during 7-15 Ma. We also discuss these results at small-scale to see whether deformation and fluid circulations, channelled within shear bands, can homogenize chemical compositions and reset the 40Ar/39Ar isotopic record. This study brings new perspective on the process of strain localization through the dating of structures along strain gradients, especially on possible variation of rates of localisation through the entire exhumation history.

Multi-segmental movement patterns reflect juggling complexity and skill level.

PubMed

Zago, Matteo; Pacifici, Ilaria; Lovecchio, Nicola; Galli, Manuela; Federolf, Peter Andreas; Sforza, Chiarella

2017-08-01

The juggling action of six experts and six intermediates jugglers was recorded with a motion capture system and decomposed into its fundamental components through Principal Component Analysis. The aim was to quantify trends in movement dimensionality, multi-segmental patterns and rhythmicity as a function of proficiency level and task complexity. Dimensionality was quantified in terms of Residual Variance, while the Relative Amplitude was introduced to account for individual differences in movement components. We observed that: experience-related modifications in multi-segmental actions exist, such as the progressive reduction of error-correction movements, especially in complex task condition. The systematic identification of motor patterns sensitive to the acquisition of specific experience could accelerate the learning process. Copyright © 2017 Elsevier B.V. All rights reserved.

Diel variations in carbon isotopic composition and concentration of organic acids and their impact on plant dark respiration in different species.

PubMed

Lehmann, M M; Wegener, F; Werner, R A; Werner, C

2016-09-01

Leaf respiration in the dark and its C isotopic composition (δ(13) CR ) contain information about internal metabolic processes and respiratory substrates. δ(13) CR is known to be less negative compared to potential respiratory substrates, in particular shortly after darkening during light enhanced dark respiration (LEDR). This phenomenon might be driven by respiration of accumulated (13) C-enriched organic acids, however, studies simultaneously measuring δ(13) CR during LEDR and potential respiratory substrates are rare. We determined δ(13) CR and respiration rates (R) during LEDR, as well as δ(13) C and concentrations of potential respiratory substrates using compound-specific isotope analyses. The measurements were conducted throughout the diel cycle in several plant species under different environmental conditions. δ(13) CR and R patterns during LEDR were strongly species-specific and showed an initial peak, which was followed by a progressive decrease in both values. The species-specific differences in δ(13) CR and R during LEDR may be partially explained by the isotopic composition of organic acids (e.g., oxalate, isocitrate, quinate, shikimate, malate), which were (13) C-enriched compared to other respiratory substrates (e.g., sugars and amino acids). However, the diel variations in both δ(13) C and concentrations of the organic acids were generally low. Thus, additional factors such as the heterogeneous isotope distribution in organic acids and the relative contribution of the organic acids to respiration are required to explain the strong (13) C enrichment in leaf dark-respired CO2 . © 2016 German Botanical Society and The Royal Botanical Society of the Netherlands.

Carbon isotope dynamics in the water column and surface sediments of marginal seas

NASA Astrophysics Data System (ADS)

Lipka, Marko; Liu, Bo; Schmiedinger, Iris; Böttcher, Michael E.

2017-04-01

The microbial mineralization of organic matter in marine sediments leads to the accumulation of dissolved inorganic carbon (DIC) and other metabolites into the interstitial waters. Pore water profiles sensitively reflect the zones of dominant biogeochemical processes, net trans-formation rates, and diffusive and advective transport of dissolved species across the sediment-water interface. They are controlled by different factors like sedimentology, bottom water currents and redox conditions, microbial activity, and the availability of electron acceptors/donors. The biogeochemical processes create steep gradients in DIC and its carbon isotope composition. One boundary condition for transport processes in the sediment is defined by the composition of the water column, which is under impact by physical mixing processes (e.g., salinity gradient; sediment-water exchange), biological activity and carbon dioxide exchange at the water-atmosphere interface. We present here the results of detailed biogeochemical investigations of vertical water column and pore water profiles from two brackish marginal seas: the Baltic Sea and the Black Sea. The water column on a transect between the North Sea and the southern Baltic Sea as well within the Black Sea were investigated on three cruises with RV MS Merian (MSM33, MSM50, MSM51). In addition, biogeochemical processes and associated element fluxes across the sediment-water interface were studied in key regions of Baltic Sea and Black Sea using pore water and sediment samples retrieved from sediment cores that were collected with a multi-coring device. Water samples were analyzed for metals, nutrients, and metabolites concentrations as well as stable carbon isotope composition of DIC to allow a modeling of steady-state transformation, volumetric transformation rates and element fluxes. The isotope composition of the dissolved inorganic carbon system shows a gradient between the North and the Baltic Sea, following the salinity during winter time. Element fluxes across the sediment-water interface depend on bottom water redox conditions, sedimentology and organic contents. Advective fluxes induced by sedimentation events, macro zoobenthos and wave action can affect the top sections of the sediment, thereby modifying shallow concentration gradients. By means of non-steady state modelling of pore water profiles we were able to identify the impact of mixing processes and sedimentation events in the oxic part of the Baltic Sea. In the Black Sea, on the other hand, anaerobic processes control the dynamics in DI13C under permanent euxinic conditions. A Keeling plot analysis was performed on pore waters to identify the δ13C of DIC released upon oxidation of DOC or methane. The carbon isotope composition of DIC is found to be a highly sensitive tool for understanding carbon cycling in the water column and sediments. Acknowledgements: The study is supported by BMBF during FONA-SECOS project, DFG (cruises MSM33, MSM50 and MSM51) and Leibniz IOW.

A Multi-Proxy Investigation into the Biomineralization Pathways of Benthic Invertebrate Taxa

NASA Astrophysics Data System (ADS)

DeCorte, I. A.; Liu, Y. W.; Doss, W. C.; Ries, J. B.; Eagle, R.

2016-12-01

Ocean acidification is the result of surface ocean absorption of anthropogenic carbon dioxide emissions and endangers many marine organisms. Decreases in pH and a coupled reduction in CaCO3 saturation state have been shown to disrupt the process of biomineralization within many species of marine calcifiers. Recent studies, however, demonstrate that calcifying organisms respond in diverse ways to changes in pH and CaCO3 saturation state. We examine element ratios (including Sr/Ca, Mg/Ca, Li/Ca, and B/Ca) and boron isotope ratios (δ11B) in 7 macro-invertebrate species (blue crab, shrimp, coralline red algae, pencil urchin, purple urchin, temperate coral, and serpulid worm) and compare results to net calcification rates and experimental seawater carbonate system parameters. Correlations between seawater carbonate chemistry and the elemental compositions of biogenic calcite and aragonite vary widely and are highly taxon-specific, ranging from strongly correlated to no significant response—a finding that is consistent with mounting evidence that many marine calcifying organisms regulate the chemistry of the fluid at their site of calcification. A Rayleigh framework is used to interpret the elemental data. We then analyze δ11B of the same samples as a proxy for pH at their site of calcification. Preliminary results suggest that coralline red algae, shrimp, urchin, serpulid worm and temperate coral taxa elevate pH at the site of calcification relative to the organism's ambient seawater. We plan to utilize a multi-proxy approach to examine the biomineralization pathways that influence elemental and boron isotope fractionation during calcification and precipitation of biogenic aragonite and calcite. A better understanding of these biomineralization pathways will help us to predict the responses of benthic invertebrate taxa to ocean acidification, as well as provide insights into drivers of so-called vital effects on elemental and stable boron isotope fractionation within biogenic carbonates—thereby assessing the fidelity of these proxies for reconstructing paleo-environmental change within a diverse range of marine calcifiers.

Dichloromethane biodegradation in multi-contaminated groundwater: Insights from biomolecular and compound-specific isotope analyses.

PubMed

Hermon, L; Denonfoux, J; Hellal, J; Joulian, C; Ferreira, S; Vuilleumier, S; Imfeld, G

2018-05-31

Dichloromethane (DCM) is a widespread and toxic industrial solvent which often co-occurs with chlorinated ethenes at polluted sites. Biodegradation of DCM occurs under both oxic and anoxic conditions in soils and aquifers. Here we investigated in situ and ex situ biodegradation of DCM in groundwater sampled from the industrial site of Themeroil (France), where DCM occurs as a major co-contaminant of chloroethenes. Carbon isotopic fractionation (ε C ) for DCM ranging from -46 to -22‰ were obtained under oxic or denitrifying conditions, in mineral medium or contaminated groundwater, and for laboratory cultures of Hyphomicrobium sp. strain GJ21 and two new DCM-degrading strains isolated from the contaminated groundwater. The extent of DCM biodegradation (B%) in the aquifer, as evaluated by compound-specific isotope analysis (δ 13 C), ranged from 1% to 85% applying DCM-specific ε C derived from reference strains and those determined in this study. Laboratory groundwater microcosms under oxic conditions showed DCM biodegradation rates of up to 0.1 mM·day -1 , with concomitant chloride release. Dehalogenase genes dcmA and dhlA involved in DCM biodegradation ranged from below 4 × 10 2 (boundary) to 1 × 10 7 (source zone) copies L -1 across the contamination plume. High-throughput sequencing on the 16S rrnA gene in groundwater samples showed that both contaminant level and terminal electron acceptor processes (TEAPs) influenced the distribution of genus-level taxa associated with DCM biodegradation. Taken together, our results demonstrate the potential of DCM biodegradation in multi-contaminated groundwater. This integrative approach may be applied to contaminated aquifers in the future, in order to identify microbial taxa and pathways associated with DCM biodegradation in relation to redox conditions and co-contamination levels. Copyright © 2018 Elsevier Ltd. All rights reserved.

Postglacial Records of Southern Hemisphere Westerly Wind Variability From the New Zealand Subantarctic Auckland Islands

NASA Astrophysics Data System (ADS)

Moy, C. M.; Vandergoes, M.; Gilmer, G. J.; Nichols, J. E.; Dagg, B. J.; Wilson, G. S.; Browne, I. M.; Curtin, L. G.; Aebig, C.; McGlone, M.

2015-12-01

The strength and latitudinal position of the Southern Hemisphere westerly winds (SHWW) play a fundamental role in influencing mid latitude climate and carbon dioxide exchange between the Southern Ocean and the atmosphere. Despite their importance, our understanding of past changes in the SHWW is limited by few paleoclimate records from the modern wind maximum that are often not in agreement. The New Zealand subantarctic Auckland Islands are located within the core of the modern wind belt (50°S) where the ocean-atmospheric linkages between the Antarctic and middle latitudes are strong. In contrast to other subantarctic islands on the Campbell Plateau, the Auckland Islands have protected fjord sub-basins, deep lakes, and peatlands that are advantageous for the development of high-resolution paleoclimate records. We will present ongoing work towards the establishment of multi-proxy and multi-site reconstructions of past SHWW variability from the Auckland Islands. Modern process and paleoclimate results from two research cruises in 2014 and 2015 suggest that in lacustrine and fjord settings, the degree of water column mixing, the stable isotopic composition of n-alkanes and benthic foraminifera, the influx of terrestrial organic matter are good indicators of wind-induced mixing of the water column or precipitation-driven erosion within catchments. In ombrotrophic peatlands, hydrogen isotope ratios of specific organic molecules allow reconstructions of the hydrogen isotope ratios of precipitation, which is related to precipitation source area and the latitudinal position of the SHWW. Using macrofossil counts paired with abundances of leaf wax biomarkers, we are able to estimate the moisture balance at peatland coring sites. Early results indicate an overall strengthening of the SHWW at the Auckland Islands through the Holocene. We will discuss these results within the context of complimentary records developed from New Zealand and southern South America to ultimately obtain a Pacific basin view of Holocene SHWW.

Biogeochemical Signals from Deep Microbial Life in Terrestrial Crust

PubMed Central

Fukuda, Akari; Komatsu, Daisuke D.; Hirota, Akinari; Watanabe, Katsuaki; Togo, Yoko; Morikawa, Noritoshi; Hagiwara, Hiroki; Aosai, Daisuke; Iwatsuki, Teruki; Tsunogai, Urumu; Nagao, Seiya; Ito, Kazumasa; Mizuno, Takashi

2014-01-01

In contrast to the deep subseafloor biosphere, a volumetrically vast and stable habitat for microbial life in the terrestrial crust remains poorly explored. For the long-term sustainability of a crustal biome, high-energy fluxes derived from hydrothermal circulation and water radiolysis in uranium-enriched rocks are seemingly essential. However, the crustal habitability depending on a low supply of energy is unknown. We present multi-isotopic evidence of microbially mediated sulfate reduction in a granitic aquifer, a representative of the terrestrial crust habitat. Deep meteoric groundwater was collected from underground boreholes drilled into Cretaceous Toki granite (central Japan). A large sulfur isotopic fractionation of 20–60‰ diagnostic to microbial sulfate reduction is associated with the investigated groundwater containing sulfate below 0.2 mM. In contrast, a small carbon isotopic fractionation (<30‰) is not indicative of methanogenesis. Except for 2011, the concentrations of H2 ranged mostly from 1 to 5 nM, which is also consistent with an aquifer where a terminal electron accepting process is dominantly controlled by ongoing sulfate reduction. High isotopic ratios of mantle-derived 3He relative to radiogenic 4He in groundwater and the flux of H2 along adjacent faults suggest that, in addition to low concentrations of organic matter (<70 µM), H2 from deeper sources might partly fuel metabolic activities. Our results demonstrate that the deep biosphere in the terrestrial crust is metabolically active and playing a crucial role in the formation of reducing groundwater even under low-energy fluxes. PMID:25517230

Comparative study of isotopic trends in two coastal ecosystems of North Biscay: A multitrophic spatial gradient approach

NASA Astrophysics Data System (ADS)

Mortillaro, J. M.; Schaal, G.; Grall, J.; Nerot, C.; Brind'Amour, A.; Marchais, V.; Perdriau, M.; Le Bris, H.

2014-01-01

In coastal estuarine embayments, retention of water masses due to coastal topography may result in an increased contribution of continental organic matter in food webs. However, in megatidal embayments, the effect of topography can be counterbalanced by the process of tidal mixing. Large amounts of continental organic matter are exported each year by rivers to the oceans. The fate of terrestrial organic matter in food webs of coastal areas and on neighboring coastal benthic communities was therefore evaluated, at multi-trophic levels, from primary producers to primary consumers and predators. Two coastal areas of the French Atlantic coast, differing in the contributions from their watershed, tidal range and aperture degree, were compared using carbon and nitrogen stable isotopes (δ13C and δ15N) during two contrasted periods. The Bay of Vilaine receives large inputs of freshwater from the Vilaine River, displaying 15N enriched and 13C depleted benthic communities, emphasizing the important role played by allochtonous inputs and anthropogenic impact on terrestrial organic matter in the food web. In contrast, the Bay of Brest which is largely affected by tidal mixing, showed a lack of agreement between isotopic gradients displayed by suspended particulate organic matter (SPOM) and suspension-feeders. Discrepancy between SPOM and suspension-feeders is not surprising due to differences in isotopes integration times. We suggest further that such a discrepancy may result from water replenishment due to coastal inputs, nutrient depletion by phytoplankton production, as well as efficient selection of highly nutritive phytoplanktonic particles by primary consumers.

VARIATIONS IN ISOTOPIC ABUNDANCES OF STRONTIUM, CALCIUM, AND ARGON AND RELATED TOPICS. Eleventh Annual Progress Report for 1963

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

None

1963-12-01

Separate abstracts were prepared for twenty-eight of the thirty-three papers. The other papers deal with whole-rock Rb- Sr ages of Ontario norite and micropegmatite and the Southern Rhodesia Great Dyke, Sr isotopes in vein type mineral deposits, whole-rock Rb-- Sr studies of volcanics, and accuracy in Sr / sup 87//Sr/sup 86/ measurements. (D.C.W.)

[Modern research progress of traditional Chinese medicine based on integrative pharmacology].

PubMed

Wang, Ping; Tang, Shi-Huan; Su, Jin; Zhang, Jia-Qi; Cui, Ru-Yi; Xu, Hai-Yu; Yang, Hong-Jun

2018-04-01

Integrative pharmacology (IP) is a discipline that studies the interaction, integration and principle of action of multiple components with the body, emphasizing the integrations of multi-level and multi-link, such as "whole and part", " in vivo and in vitro ", " in vivo process and activity evaluation". After four years of development and practice, the theory and method of IP has received extensive attention and application.In order to better promote the development of IP, this paper systematically reviews the concepts, research contents, research methods and application fields about IP. Copyright© by the Chinese Pharmaceutical Association.

Cosmology on a Mesh

NASA Astrophysics Data System (ADS)

Gill, Stuart P. D.; Knebe, Alexander; Gibson, Brad K.; Flynn, Chris; Ibata, Rodrigo A.; Lewis, Geraint F.

2003-04-01

An adaptive multi grid approach to simulating the formation of structure from collisionless dark matter is described. MLAPM (Multi-Level Adaptive Particle Mesh) is one of the most efficient serial codes available on the cosmological "market" today. As part of Swinburne University's role in the development of the Square Kilometer Array, we are implementing hydrodynamics, feedback, and radiative transfer within the MLAPM adaptive mesh, in order to simulate baryonic processes relevant to the interstellar and intergalactic media at high redshift. We will outline our progress to date in applying the existing MLAPM to a study of the decay of satellite galaxies within massive host potentials.

Pb-Zn-Cd-Hg multi isotopic characterization of the Loire River Basin, France

NASA Astrophysics Data System (ADS)

Millot, R.; Widory, D.; Innocent, C.; Guerrot, C.; Bourrain, X.; Johnson, T. M.

2012-12-01

The contribution of human activities such as industries, agriculture and domestic inputs, becomes more and more significant in the chemical composition (major ions and pollutants such as metals) of the dissolved load of rivers. Furthermore, this influence can also be evidenced in the suspended solid matter known to play an important role in the transport of heavy metals through river systems. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. The Loire River in central France is approximately 1010 km long and drains an area of 117,800 km2. Initially, the Loire upstream flows in a south to north direction originating in the Massif Central, and continues up to the city of Orléans, 650 km from the source. In the upper basin, the bedrock is old plutonic rock overlain by much younger volcanic rocks. The Loire River then follows a general east to west direction to the Atlantic Ocean. The intermediate basin includes three major tributaries flowing into the Loire River from the left bank: the Cher, the Indre and the Vienne rivers; the main stream flows westward and its valley stretches toward the Atlantic Ocean. Here, the Loire River drains the sedimentary series of the Paris Basin, mainly carbonate deposits. The lower Loire basin drains pre-Mesozoic basement of the Armorican Massif and its overlying Mesozoic to Cenozoic sedimentary deposits. The Loire River is one of the main European riverine inputs to the Atlantic ocean. Here we are reporting concentration and isotope data for heavy metals Zn-Cd-Pb-Hg in river waters and suspended sediments from the Loire River Basin. In addition, we also report concentration and isotope data for these metals for the different industrial sources within the Loire Basin, as well as data for biota samples such as mussels and oysters from the Bay of Biscay and North Brittany. These organisms are known to be natural accumulators of metal pollutants. The main objective of this study is to characterize the sources and the behavior of these heavy metals in the aquatic environment, and their spatial distribution using a multi-isotope approach. Each of these isotope systematics on their own reveals important information about their geogenic or anthropogenic origin but, considered together, provide a more integrated understanding of the budgets of these pollutants within the Loire River Basin.

An Integrated Analytical Approach to Obtaining Reliable U-Pb and Hf Isotopic Data from Complex (>3.9 to 3.3 Ga) Zircon from the Acasta Gneiss Complex

NASA Astrophysics Data System (ADS)

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

2014-12-01

The Acasta Gneiss Complex (AGC) of northwestern Canada preserves some of Earth's oldest granitic crust (>4.03 Ga) and thereby contains important insight into crust forming processes on the early Earth. In general, rocks of the AGC have undergone a complex history of metamorphism and deformation (Archean and Paleoproterozoic)1,2, and, as a consequence, the zircons retain a complex history including inheritance, magmatic and metamorphic overgrowths, recrystallization, and multi-stage Pb loss. Previously published Hf isotopic data on zircons show within sample variability in excess of analytical uncertainty2,3,4. In order to assess the meaning and significance of this apparent isotopic variability, we are using two different methods to obtain coupled U-Pb and Lu-Hf isotopic data in zircon from a suite of rocks ranging in age from ca. > 3.9 Ga to 3.3 Ga. To obtain these data from the same volume of zircon, our approach involves: 1) split stream LA-ICPMS for U-Pb and Lu-Hf; 2) mechanical isolation of zircon domains for chemical abrasion and ID-TIMS U-Pb analyses and solution ICPMS for Lu-Hf recovered from U-Pb ion exchange chromatography. The deconvolution of complex histories requires this integrated approach and permits us to take advantage of both high spatial resolution and highest precision measurements to ultimately decipher the age and isotopic composition of discrete domains of multi-phase zircon. We demonstrate our approach with both relatively simple and complex grain populations in an attempt to understand within and between grain heterogeneity. The samples with the simplest zircon systematics have increasingly negative ɛHf from oldest to youngest, consistent with involvement of 4.0 Ga or older crust in later generations; also, none of our samples have been derived solely from strongly depleted sources. The presence of intra-zircon variability within samples from the AGC reflects a complex history of magmatic additions requiring melting/assimilation of older rocks consistent with the inherited zircon record (4.2-4.06 Ga)1,5. [1]Bowring and Williams (1999). CoMP, 134(1), 3-16. [2]Iizuka et al (2007). Precambrian Res, 153(3), 179-208. [3]Amelin et al (2000). Geochim Cosmochim Ac, 64(24), 4205-4225. [4] Guitreau, et al (2012). EPSL, 337, 211-223. [5]Iizuka, et al (2006). Geology, 34(4), 245-248.

A Sr and Mg isotopic study of soil and stream waters along an erosional gradient, Sierra Nevada, California

NASA Astrophysics Data System (ADS)

Rosen, V. B.; Maher, K.; Kouba, C. M.; Weinman, B. A.; Yoo, K.; Mudd, S. M.

2012-12-01

Since chemical weathering rates are proposed to regulate atmospheric CO2 concentrations and by extension global temperature over geologic timescales, understanding the relationship between chemical weathering rates and physical erosion is crucial to accurately interpreting Earth's climate history. The rate of supply of fresh minerals to the weathering zone is known to be an important control on chemical weathering rates. However, the consequences of physical erosion on the isotopic composition of weathering-derived solutes are more difficult to assess. This study capitalizes on a series of granitic hillslope transects with different erosion rates but similar climate, vegetation, and bedrock, in order to assess the consequences of erosion on the Sr and Mg isotopic composition of solutes. Reactive transport model simulations of varying complexity have been used to complement the field measurements and to analyze the sensitivity of fluid isotopic compositions to changes in key parameters such as erosion rate, flow rate, and biological cycling. The three hillslopes in the Feather River Basin, California reflect different degrees of channel erosion at their bases—BRC is a hillslope with active channel incision (60% average slope, below the knickpoint), FTA is a hillslope reflecting the transition between the relict and modern-day incising areas (50% average slope, at the knickpoint), and POMD is a 30% average hillslope in the relict landscape above the knickpoint. We measured the major element compositions, as well as the Sr and Mg isotopic compositions of soil water leaches (deionized water leaches), lysimeters, stream waters, and groundwaters by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The 87Sr/86Sr values of soil and stream waters show minimal variation (0.7042 to 0.7046) as a function of soil depth, erosion rate, or sampling season despite abundant radiogenic biotite in the profiles. These results agree with the reactive transport model predictions at high erosion rates, and suggest that soil residence times and isotopic equilibrium times are too short for biotite weathering to influence the solute isotopic composition. In contrast, model results for δ26Mg of the soil waters and minerals suggest that the Mg isotopic composition of the solute changes as a function of erosion rate because of shorter isotopic equilibrium length scales at higher erosion rates. The isotopic reactive transport modeling, combined with hillslope depth profiles and stream water analyses, provides a useful approach for linking the isotopic composition of solutes to erosion rates. This study may provide insights into past and present riverine isotopic compositions, and contribute to our understanding of how surface processes have influenced past atmospheric conditions.

Multi-mycotoxin stable isotope dilution LC-MS/MS method for Fusarium toxins in beer.

PubMed

Habler, Katharina; Gotthardt, Marina; Schüler, Jan; Rychlik, Michael

2017-03-01

A stable isotope dilution LC-MS/MS multi-mycotoxin method was developed for 12 different Fusarium toxins including modified mycotoxins in beer (deoxynivalenol-3-glucoside, deoxynivalenol, 3-acetyldeoxynivalenol, 15-acetyl-deoxynivalenol, HT2-toxin, T2-toxin, enniatin B, B1, A1, A, beauvericin and zearalenone). As sample preparation and purification of beer a combined solid phase extraction for trichothecenes, enniatins, beauvericin and zearalenone was firstly developed. The validation of the new method gave satisfying results: intra-day and inter-day precision and recoveries were 1-5%, 2-8% and 72-117%, respectively. In total, 61 different organic and conventional beer samples from Germany and all over the world were analyzed by using the newly developed multi-mycotoxin method. In summary, deoxynivalenol, deoxynivalenol-3-glucoside, 3-acetyldeoxynivaleneol and enniatin B were quantified in rather low contents in the investigated beer samples. None of the other monitored Fusarium toxins like 15-acetyldeoxynivalenol, HT2- and T2-toxin, zearalenone, enniatin B1, A1, A or beauvericin were detectable. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemical constraints on the temperature and timing of carbonate formation and lithification in the Nankai Trough, NanTroSEIZE transect

NASA Astrophysics Data System (ADS)

Sample, James C.; Torres, Marta E.; Fisher, Andrew; Hong, Wei-Li; Destrigneville, Christine; Defliese, William F.; Tripati, Aradhna E.

2017-02-01

Information about diagenetic processes and temperatures during burial of sediments entering the subduction zone is important for understanding changes in physical properties and seismic behavior during deformation. The geochemistry of authigenic carbonates from accretionary prisms can serve as proxies for conditions during carbonate cementation and resultant lithification. We report results from the Nankai accretionary prism recovered from Integrated Ocean Drilling Program (IODP) sites C0011 and C0012 and we document continued cementation of deep sediment sections prior to subduction. Elemental and isotope data provide evidence for complex mixing of different isotopic reservoirs in pore waters contributing to carbonate chemical signatures. Carbon stable isotope values exhibit a broad range (δ13CV-PDB = +0.1‰ to -22.5‰) that corresponds to different stages of cement formation during burial. Carbonate formation temperatures from carbonate-clumped isotope geochemistry range from 16 °C to 63 °C at Site C0011 and 8.7 °C to 68 °C at Site C0012. The correspondence between the clumped-isotope temperatures and extrapolations of measured in situ temperatures indicate the carbonate is continuing to form at present. Calculated water isotopic compositions are in some cases enriched in 18O relative to measured interstitial waters suggesting a component of inherited seawater or input from clay-bound water. Low oxygen isotope values and the observed Ba/Ca ratios are also consistent with carbonate cementation at depth. Strontium isotopes of interstitial waters (87Sr/86Sr of 0.7059-0.7069) and carbonates (87Sr/86Sr of 0.70715-0.70891) support formation of carbonates from a mixture of strontium reservoirs including current interstitial waters and relic seawater contemporaneous with deposition. Collectively our data reflect mixed sources of dissolved inorganic carbon and cations that include authigenic phases driven by organic carbon and volcanic alteration reactions. Physical properties of input sediments continue to undergo modification by carbonate cementation at present. Due to ongoing recrystallization, temperatures from carbonate-clumped isotopes reflect the modern geothermal gradient and may serve as useful measures of geothermal gradients in other siliciclastic basins where carbonate cementation occurs. We conclude that clumped-isotope signatures in authigenic carbonates from accretionary prisms are important proxies for the timing and conditions of cementation in active margins. Our results highlight the importance of using multi-proxy approaches to elucidate the history of carbonate cementation, particularly to establish carbonate precipitation at depth and its potential impact on the physical and mechanical properties of the sediment prior to subduction.

Progress in the Early Solar System Chronology: A Sketch of an Ever-Changing Landscape

NASA Technical Reports Server (NTRS)

Amelin, Yuri; Yin, Q.-Z.; Krot, A. N.; Bouvier, A.; Wadhwa, M.; Kleine, T.; Nyquist, L. E.

2011-01-01

The years since the Workshop on the Chronology of Meteorites and the Early Solar System, are marked with ongoing progress in cosmochronology. Rapid improvements in techniques, discovery of new meteorites unlike any previously known, and findings that what was deemed well established constants are actually variables, will be reflected in an updated review of the solar system chronology we are currently preparing. Along with updating the database of meteorite ages, it will involve development of a set of criteria for evaluation of accuracy and consistency of isotopic dates across the entire range of meteorite classes and isotope chronometer systems. Here we present some ideas on what we think is important in meteorite chronology, and invite the cosmochemistry community to discuss them.

Pb isotope geochemistry of Piton de la Fournaise historical lavas

NASA Astrophysics Data System (ADS)

Vlastélic, Ivan; Deniel, Catherine; Bosq, Chantal; Télouk, Philippe; Boivin, Pierre; Bachèlery, Patrick; Famin, Vincent; Staudacher, Thomas

2009-07-01

Variations of Pb isotopes in historical lavas (1927-2007) from Piton de la Fournaise are investigated based on new (116 samples) and published (127 samples) data. Lead isotopic signal exhibits smooth fluctuations (18.87 < 206Pb/ 204Pb < 18.94) on which superimpose unradiogenic spikes ( 206Pb/ 204Pb down to 18.70). Lead isotopes are decoupled from 87Sr/ 86Sr and 143Nd/ 144Nd, which display small and barely significant variations, respectively. No significant change of Pb isotope composition occurred during the longest (> 3 years) periods of inactivity of the volcano (1939-1942, 1966-1972, 1992-1998), supporting previous inferences that Pb isotopic variations occur mostly during and not between eruptions. Intermediate compositions (18.904 < 206Pb/ 204Pb < 18.917) bracket the longest periods of quiescence. In this respect, the highly frequent occurrence of an intermediate composition (18.90 < 206Pb/ 204Pb < 18.91), which clearly defines an isotopic baseline during the most recent densely sampled period (1975-2007), either suggests direct sampling of plume melts or sampling of a voluminous magma reservoir that buffers Pb isotopic composition. Deviations from this prevalent composition occurred during well-defined time periods, namely 1977-1986 (radiogenic signature), 1986-1990 and 1998-2005 (unradiogenic signatures). The three periods display a progressive isotopic drift ending by a rapid return (mostly during a single eruption) to the isotopic baseline. The isotopic gradients could reflect progressive emptying of small magma reservoirs or magma conduits, which are expected to be more sensitive to wall-rock interactions than the main magma chamber. These gradients provide a lower bound ranging from 0.1 to 0.17 km 3 for the size of the shallow magma storage system. The isotopic shifts (March 1986, January 1990 and February 2005) are interpreted as refilling the plumbing system with deep melts that have not interacted with crustal components. The volume of magma erupted between the two major refilling events of March 1986 and February 2005 (0.28 km 3) could provide a realistic estimate of the magma reservoir size. Unradiogenic anomalies appear to be linked, more or less directly, to the eruption of olivine-rich lavas. The related samples have low 206Pb/ 204Pb and 208Pb/ 204Pb but normal 207Pb/ 204Pb, suggesting a recent decrease of U/Pb and Th/Pb, for instance through sequestration of Pb into sulfides. Olivine and sulfides, which are both denser than silicate melts, could be entrained with magma pulses, which give rise to high-flux oceanite eruptions.

Reliable LC-MS quantitative glycomics using iGlycoMab stable isotope labeled glycans as internal standards.

PubMed

Zhou, Shiyue; Tello, Nadia; Harvey, Alex; Boyes, Barry; Orlando, Ron; Mechref, Yehia

2016-06-01

Glycans have numerous functions in various biological processes and participate in the progress of diseases. Reliable quantitative glycomic profiling techniques could contribute to the understanding of the biological functions of glycans, and lead to the discovery of potential glycan biomarkers for diseases. Although LC-MS is a powerful analytical tool for quantitative glycomics, the variation of ionization efficiency and MS intensity bias are influencing quantitation reliability. Internal standards can be utilized for glycomic quantitation by MS-based methods to reduce variability. In this study, we used stable isotope labeled IgG2b monoclonal antibody, iGlycoMab, as an internal standard to reduce potential for errors and to reduce variabililty due to sample digestion, derivatization, and fluctuation of nanoESI efficiency in the LC-MS analysis of permethylated N-glycans released from model glycoproteins, human blood serum, and breast cancer cell line. We observed an unanticipated degradation of isotope labeled glycans, tracked a source of such degradation, and optimized a sample preparation protocol to minimize degradation of the internal standard glycans. All results indicated the effectiveness of using iGlycoMab to minimize errors originating from sample handling and instruments. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Infiltration of meteoric fluids in an extensional detachment shear zone (Kettle dome, WA, USA): How quartz dynamic recrystallization relates to fluid-rock interaction

NASA Astrophysics Data System (ADS)

Quilichini, Antoine; Siebenaller, Luc; Nachlas, William O.; Teyssier, Christian; Vennemann, Torsten W.; Heizler, Matthew T.; Mulch, Andreas

2015-02-01

We document the interplay between meteoric fluid flow and deformation processes in quartzite-dominated lithologies within a ductile shear zone in the footwall of a Cordilleran extensional fault (Kettle detachment system, Washington, USA). Across 150 m of shear zone section, hydrogen isotope ratios (δD) from synkinematic muscovite fish are constant (δD ˜ -130‰) and consistent with a meteoric fluid source. Quartz-muscovite oxygen isotope thermometry indicates equilibrium fractionation temperatures of ˜365 ± 30 °C in the lower part of the section, where grain-scale quartz deformation was dominated by grain boundary migration recrystallization. In the upper part of the section, muscovite shows increasing intragrain compositional zoning, and quartz microstructures reflect bulging recrystallization, solution-precipitation, and microcracking that developed during progressive cooling and exhumation. The preserved microstructural characteristics and hydrogen isotope fingerprints of meteoric fluids developed over a short time interval as indicated by consistent mica 40Ar/39Ar ages ranging between 51 and 50 Ma over the entire section. Pervasive fluid flow became increasingly channelized during detachment activity, leading to microstructural heterogeneity and large shifts in quartz δ18O values on a meter scale. Ductile deformation ended when brittle motion on the detachment fault rapidly exhumed the mylonitic footwall.

Compound Specific Hydrogen Isotope Composition of Type II and III Kerogen Extracted by Pyrolysis-GC-MS-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2013-01-01

The use of Hydrogen (H) isotopes in understanding oil and gas resource plays is in its infancy. Described here is a technique for H isotope analysis of organic compounds pyrolyzed from oil and gas shale-derived kerogen. Application of this technique will progress our understanding. This work complements that of Pernia et al. (2013, this meeting) by providing a novel method for the H isotope analysis of specific compounds in the characterization of kerogen extracted by analytically diverse techniques. Hydrogen isotope analyses were carried out entirely "on-line" utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC Ultra interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make semi-quantitative compositional measurements of the extracted compounds. Kerogen samples from five different basins (type II and III) were dehydrated (heated to 80 C overnight in vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C) which quantitatively forms H2, following a modified method of Burgoyne and Hayes, (1998, Anal. Chem., 70, 5136-5141). Samples ranging from approximately 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. Compounds were separated on a Poraplot Q GC column. Hydrogen isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight compounds. Water (H2O) average deltaD = -215.2 (V-SMOW), ranging from -271.8 for the Marcellus Shale to -51.9 for the Polish Shale. Higher molecular weight compounds like toluene (C7H8) have an average deltaD of -89.7 0/00, ranging from -156.0 for the Barnett Shale to -50.0 for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during formation within each basin. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleo-environmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analysis. More experiments are planned to discern these two or other possible scenarios.

Determining the N and O isotope effects of microbial nitrite reduction: the global N cycle implications of an enzyme-dependent isotope effect

NASA Astrophysics Data System (ADS)

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

2014-12-01

The marine nitrogen (N) cycle is a dynamic system of critical importance, since nitrogen is the limiting nutrient in over half of the world's oceans. Denitrification and anammox, the main N loss processes from the ocean, have different effects on carbon cycling and greenhouse gas emission. Understanding the balance between the two processes is vital to understanding the role of the N cycle in global climate change. One approach for investigating these processes is by using stable isotope analysis to estimate the relative magnitudes of N fluxes, particularly for biologically mediated processes. In order to make the most of the currently available isotope analysis techniques, it is necessary to know the isotope effects for each processes occurring in the environment. Nitrite reduction is an important step in denitrification. Previous work had begun to explore the N isotope effects for nitrite reduction, but no oxygen (O) isotope effect has been measured. Additionally, no consideration has been given to the type of nitrite reductase carrying out the reaction. There are two main types of respiratory nitrite reductase, one that is Cu-based and another that is Fe-based. We performed batch culture experiments with denitrifier strains possessing either a Cu-type or Fe-type nitrite reductase. Both N and O isotope effects for nitrite reduction were determined for each of these experiments by measuring the NO2- concentration, as well as the N and O isotopes of nitrite and applying a Rayleigh fractionation model. Both the N and O isotope effects were found to be significantly different between the two types of enzymes. This enzyme-linked difference in isotope effects emphasizes the importance of microbial community composition within the global N cycle.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

PubMed

Gulson, Brian; Kamenov, George D; Manton, William; Rabinowitz, Michael

2018-04-11

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208 Pb/ 206 Pb and 207 Pb/ 206 Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields

PubMed Central

Gulson, Brian; Manton, William; Rabinowitz, Michael

2018-01-01

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields. PMID:29641487

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

USGS Publications Warehouse

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

2016-01-01

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

Mass-spectrometric mining of Hadean zircons by automated SHRIMP multi-collector and single-collector U/Pb zircon age dating: The first 100,000 grains

NASA Astrophysics Data System (ADS)

Holden, Peter; Lanc, Peter; Ireland, Trevor R.; Harrison, T. Mark; Foster, John J.; Bruce, Zane

2009-09-01

The identification and retrieval of a large population of ancient zircons (>4 Ga; Hadean) is of utmost priority if models of the early evolution of Earth are to be rigorously tested. We have developed a rapid and accurate U-Pb zircon age determination protocol utilizing a fully automated multi-collector ion microprobe, the ANU SHRIMP II, to screen and date these zircons. Unattended data acquisition relies on the calibration of a digitized sample map to the Sensitive High Resolution Ion MicroProbe (SHRIMP) sample-stage co-ordinate system. High precision positioning of individual grains can be produced through optical image processing of a specified mount location. The focal position of the mount can be optimized through a correlation between secondary-ion steering and the spot position on the target. For the Hadean zircon project, sample mounts are photographed and sample locations (normally grain centers) are determined off-line. The sample is loaded, reference points calibrated, and the target positions are then visited sequentially. In SHRIMP II multiple-collector mode, zircons are initially screened (ca. 5 s data acquisition) through their 204Pb corrected 207Pb/206Pb ratio; suitable candidates are then analyzed in a longer routine to obtain better measurement statistics, U/Pb, and concentration data. In SHRIMP I and SHRIMP RG, we have incorporated the automated analysis protocol to single-collector measurements. These routines have been used to analyze over 100,000 zircons from the Jack Hills quartzite. Of these, ca. 7%, have an age greater than 3.8 Ga, the oldest grain being 4372 +/- 6 Ma (2[sigma]), and this age is part of a group of analyses around 4350 Ma which we interpret as the age when continental crust first began to coalesce in this region. In multi-collector mode, the analytical time taken for a single mount with 400 zircons is approximately 6 h; whereas in single-collector mode, the analytical time is ca. 17 h. With this productivity, we can produce significant numbers of zircons for statistically limited studies including correlations between age and morphology, mineral-inclusion paragenesis, as well as isotopic studies including Hf and O isotopic compositions, Pu-Xe, and Sm-Nd isotopes.

Investigating the Relationship Between Soil Water Mobility and Stable Isotope Composition with Implications for the Ecohydrologic Separation Hypothesis

NASA Astrophysics Data System (ADS)

Shuler, J.; McNamara, J. P.; Benner, S. G.; Kohn, M. J.; Evans, S.

2017-12-01

The ecohydrologic separation (ES) hypothesis states that streams and plants return different soil water compartments to the atmosphere and that these compartments bear distinct isotopic compositions that can be used to infer soil water mobility. Recent studies have found isotopic evidence for ES in a variety of ecosystems, though interpretations of these data vary. ES investigations frequently suffer from low sampling frequencies as well as incomplete or missing soil moisture and matric potential data to support assumptions of soil water mobility. We sampled bulk soil water every 2-3 weeks in the upper 1 m of a hillslope profile from May 2016 to July 2017 in a semi-arid watershed outside Boise, ID. Twig samples of three plant species were also collected concurrently. Plant and soil water samples extracted via cryogenic vacuum distillation were analyzed for δ2H and δ18O composition. Soil moisture and soil matric potential sensors were installed at five and four depths in the profile, respectively. Shallow bulk soil water was progressively enriched in both isotopes over the growing season and plotted along a soil evaporation line in a plot of δ2H versus δ18O. Plant water during the growing season plotted below both the Local Meteoric Water Line and soil evaporation line. Plant water isotopic composition could not be traced to any source sampled in this study. Additionally, soil moisture and matric potential data revealed that soils were well-drained and that mobile soil water was unavailable throughout most of the growing season at the depths sampled. Soil water isotopic composition alone failed to predict mobility as observed in soil moisture and matric potential data. These results underscore the need for standard hydrologic definitions for the mobile and immobile compartments of soil water in future studies of the ES hypothesis and ecohydrologic processes in general.

A strong control of the South American SeeSaw on the intra-seasonal variability of the isotopic composition of precipitation in the Bolivian Andes

NASA Astrophysics Data System (ADS)

Vimeux, Françoise; Tremoy, Guillaume; Risi, Camille; Gallaire, Robert

2011-07-01

Water stable isotopes (δ) in tropical regions are a valuable tool to study both convective processes and climate variability provided that local and remote controls on δ are well known. Here, we examine the intra-seasonal variability of the event-based isotopic composition of precipitation (δD Zongo) in the Bolivian Andes (Zongo valley, 16°20'S-67°47'W) from September 1st, 1999 to August 31st, 2000. We show that the local amount effect is a very poor parameter to explain δD Zongo. We thus explore the property of water isotopes to integrate both temporal and spatial convective activities. We first show that the local convective activity averaged over the 7-8 days preceding the rainy event is an important control on δD Zongo during the rainy season (~ 40% of the δD Zongo variability is captured). This could be explained by the progressive depletion of local water vapor by unsaturated downdrafts of convective systems. The exploration of remote convective controls on δD Zongo shows a strong influence of the South American SeeSaw (SASS) which is the first climate mode controlling the precipitation variability in tropical South America during austral summer. Our study clearly evidences that temporal and spatial controls are not fully independent as the 7-day averaged convection in the Zongo valley responds to the SASS. Our results are finally used to evaluate a water isotope enabled atmospheric general circulation model (LMDZ-iso), using the stretched grid functionality to run zoomed simulations over the entire South American continent (15°N-55°S; 30°-85°W). We find that zoomed simulations capture the intra-seasonal isotopic variation and its controls, though with an overestimated local sensitivity, and confirm the role of a remote control on δ according to a SASS-like dipolar structure.

Monitoring induced denitrification during managed aquifer recharge in an infiltration pond

NASA Astrophysics Data System (ADS)

Grau-Martínez, Alba; Folch, Albert; Torrentó, Clara; Valhondo, Cristina; Barba, Carme; Domènech, Cristina; Soler, Albert; Otero, Neus

2018-06-01

Managed aquifer recharge (MAR) is a well-known technique for improving water quality and increasing groundwater resources. Denitrification (i.e. removal of nitrate) can be enhanced during MAR by coupling an artificial recharge pond with a permeable reactive layer (PRL). In this study, we examined the suitability of a multi-isotope approach for assessing the long-term effectiveness of enhancing denitrification in a PRL containing vegetal compost. Batch laboratory experiments confirmed that the PRL was still able to enhance denitrification two years after its installation in the infiltration pond. At the field scale, changes in redox indicators along a flow path and below the MAR-PRL system were monitored over 21 months during recharge and non-recharge periods. Results showed that the PRL was still releasing non-purgeable dissolved organic carbon five years after its installation. Nitrate concentration coupled with isotopic data collected from the piezometer network at the MAR system indicated that denitrification was occurring in the saturated zone immediately beneath the infiltration pond, where recharged water and native groundwater mix. Furthermore, longer operational periods of the MAR-PRL system increased denitrification extent. Multi-isotope analyses are therefore proved to be useful tools in identifying and quantifying denitrification in MAR-PRL systems.

Portable Cavity Ringdown Spectrometer for Methane Isotope Ratio Measurements

NASA Astrophysics Data System (ADS)

Bostrom, G.; Rice, A.; Atkinson, D.

2008-12-01

Close to 45% (244 Tg/yr) of the methange (CH4) in the atmosphere is produced in anaerobic soil conditions (wetlands and rice paddies). Under aerobic soil conditions, bacteria oxidize CH4 to produce CO2 and H2O. Both production and oxidation rates depend on soil composition, nutrient loadings, water content, and plant conditions, but these dependencies are not well characterized. Measurements of CH4 isotope ratios can provide a better understanding of CH4 processes in natural and man- made ecosystems. Here we present progress on the development of a field deployable instrument capable of making precision 13CH4/12CH4 and CH3D/ CH4 isotope ratio measurements of CH4. Moving the instrument out of the lab and into the field will significantly improve the spatial and temporal resolution of data and enhance the study of plant-soil-atmosphere CH4 source and sink processes. Our instrument is a Near-IR (1280-1340 nm) tunable diode laser Cavity Ringdown Spectroscopy (CRDS) system. CRDS is a technique in which the laser injects energy into a high finesse cavity by tuning to one of the cavity resonant modes, resulting in a buildup of energy. At some threshold intra-cavity intensity the injection is stopped, and the intensity decays exponentially due to losses such as absorption by molecules. If the laser is tuned to an absorption line of a sample gas, the concentration of the molecule is proportional to the decay constant (according to the Beer-Lambert law)--scanning over a frequency range produces an absorption spectrum. Currently our system has a resolution of 150 MHz scanning over a 30 GHz (0.2 nm) region, allowing us to resolve peaks at pressures of 100 torr. Using combinations of CH4 standard (natural isotopic abundance) and a 99% pure 13CH4 standard, we identified several lines in the CH4 HITRAN Database that we attribute to 13CH4. We use these and 12CH4 lines within the same region to measure 13CH4 concentration, 12CH4 concentration, and the isotope ratio (13C/12C and D/H). We present our lab-based prototype system, including our latest isotope ratio performance and measurement precision. In addition, we present the way forward to achieve both our target precision and portability.

Materials and Methods for Streamlined Laboratory Analysis of Environmental Samples, FY 2016 Report

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

Addleman, Raymond S.; Naes, Benjamin E.; McNamara, Bruce K.

The International Atomic Energy Agency (IAEA) relies upon laboratory analysis of environmental samples (typically referred to as “swipes”) collected during on-site inspections of safeguarded facilities to support the detection and deterrence of undeclared activities. Unfortunately, chemical processing and assay of the samples is slow and expensive. A rapid, effective, and simple extraction process and analysis method is needed to provide certified results with improved timeliness at reduced costs (principally in the form of reduced labor), while maintaining or improving sensitivity and efficacy. To address these safeguard needs the Pacific Northwest National Laboratory (PNNL) explored and demonstrated improved methods for environmentalmore » sample (ES) analysis. Improvements for both bulk and particle analysis were explored. To facilitate continuity and adoption, the new sampling materials and processing methods will be compatible with existing IAEA protocols for ES analysis. PNNL collaborated with Oak Ridge National Laboratory (ORNL), which performed independent validation of the new bulk analysis methods and compared performance to traditional IAEA’s Network of Analytical Laboratories (NWAL) protocol. ORNL efforts are reported separately. This report describes PNNL’s FY 2016 progress, which was focused on analytical application supporting environmental monitoring of uranium enrichment plants and nuclear fuel processing. In the future the technology could be applied to other safeguard applications and analytes related to fuel manufacturing, reprocessing, etc. PNNL’s FY 2016 efforts were broken into two tasks and a summary of progress, accomplishments and highlights are provided below. Principal progress and accomplishments on Task 1, Optimize Materials and Methods for ICP-MS Environmental Sample Analysis, are listed below. • Completed initial procedure for rapid uranium extraction from ES swipes based upon carbonate-peroxide chemistry (delivered to ORNL for evaluation). • Explored improvements to carbonate-peroxide rapid uranium extraction chemistry. • Evaluated new sampling materials and methods (in collaboration with ORNL). • Demonstrated successful ES extractions from standard and novel swipes for a wide range uranium compounds of interest including UO 2F 2 and UO 2(NO 3) 2, U 3O 8 and uranium ore concentrate. • Completed initial discussions with commercial suppliers of PTFE swipe materials. • Submitted one manuscript for publication. Two additional drafts are being prepared. Principal progress and accomplishments on Task 2, Optimize Materials and Methods for Direct SIMS Environmental Sample Analysis, are listed below. • Designed a SIMS swipe sample holder that retrofits into existing equipment and provides simple, effective, and rapid mounting of ES samples for direct assay while enabling automation and laboratory integration. • Identified preferred conductive sampling materials with better performance characteristics. • Ran samples on the new PNNL NWAL equivalent Cameca 1280 SIMS system. • Obtained excellent agreement between isotopic ratios for certified materials and direct SIMS assay of very low levels of LEU and HEU UO 2F 2 particles on carbon fiber sampling material. Sample activities range from 1 to 500 CPM (uranium mass on sample is dependent upon specific isotope ratio but is frequently in the subnanogram range). • Found that the presence of the UF molecular ions, as measured by SIMS, provides chemical information about the particle that is separate from the uranium isotopics and strongly suggests that those particles originated from an UF6 enrichment activity. • Submitted one manuscript for publication. Another manuscript is in preparation.« less

Improved precision and accuracy in quantifying plutonium isotope ratios by RIMS

DOE PAGES

Isselhardt, B. H.; Savina, M. R.; Kucher, A.; ...

2015-09-01

Resonance ionization mass spectrometry (RIMS) holds the promise of rapid, isobar-free quantification of actinide isotope ratios in as-received materials (i.e. not chemically purified). Recent progress in achieving this potential using two Pu test materials is presented. RIMS measurements were conducted multiple times over a period of two months on two different Pu solutions deposited on metal surfaces. Measurements were bracketed with a Pu isotopic standard, and yielded absolute accuracies of the measured 240Pu/ 239Pu ratios of 0.7% and 0.58%, with precisions (95% confidence intervals) of 1.49% and 0.91%. In conclusion, the minor isotope 238Pu was also quantified despite the presencemore » of a significant quantity of 238U in the samples.« less

Laboratory studies of refractory metal oxide smokes

NASA Technical Reports Server (NTRS)

Nuth, Joseph A.; Nelson, R. N.; Donn, Bertram

1989-01-01

Studies of the properties of refractory metal oxide smokes condensed from a gas containing various combinations of SiH4, Fe(CO)5, Al(CH3)3, TiCl4, O2 and N2O in a hydrogen carrier stream at 500 K greater than T greater than 1500 K were performed. Ultraviolet, visible and infrared spectra of pure, amorphous SiO(x), FeO(x), AlO(x) and TiO(x) smokes are discussed, as well as the spectra of various co-condensed amorphous oxides, such as FE(x)SiO(y) or Fe(x)AlO(y). Preliminary studies of the changes induced in the infrared spectra of iron-containing oxide smokes by vacuum thermal annealing suggest that such materials become increasingly opaque in the near infrared with increased processing: hydration may have the opposite effect. More work on the processing of these materials is required to confirm such a trend: this work is currently in progress. Preliminary studies of the ultraviolet spectra of amorphous Si2O3 and MgSiO(x) smokes revealed no interesting features in the region from 200 to 300 nm. Studies of the ultraviolet spectra of both amorphous, hydrated and annealed SiO(x), TiO(x), AlO(x) and FeO(x) smokes are currently in progress. Finally, data on the oxygen isotopic composition of the smokes produced in the experiments are presented, which indicate that the oxygen becomes isotopically fractionated during grain condensation. Oxygen in the grains is as much as 3 percent per amu lighter than the oxygen in the original gas stream. The authors are currently conducting experiments to understand the mechanism by which fractionation occurs.

The Antarctic ice core chronology (AICC2012): an optimized multi-parameter and multi-site dating approach for the last 120 thousand years

NASA Astrophysics Data System (ADS)

Veres, D.; Bazin, L.; Landais, A.; Toyé Mahamadou Kele, H.; Lemieux-Dudon, B.; Parrenin, F.; Martinerie, P.; Blayo, E.; Blunier, T.; Capron, E.; Chappellaz, J.; Rasmussen, S. O.; Severi, M.; Svensson, A.; Vinther, B.; Wolff, E. W.

2012-12-01

The deep polar ice cores provide reference records commonly employed in global correlation of past climate events. However, temporal divergences reaching up to several thousand years (ka) exist between ice cores over the last climatic cycle. In this context, we are hereby introducing the Antarctic Ice Core Chronology 2012 (AICC2012), a new and coherent timescale developed for four Antarctic ice cores, namely Vostok, EPICA Dome C (EDC), EPICA Dronning Maud Land (EDML) and Talos Dome (TALDICE), alongside the Greenlandic NGRIP record. The AICC2012 time scale has been constructed using the Bayesian tool Datice (Lemieux-Dudon et al., 2010) that combines glaciological inputs and data constraints, including a wide range of relative and absolute gas and ice stratigraphic markers. We focus here on the last 120 ka, whereas the companion paper by Bazin et al., (2012) focuses on the interval 120-800 ka. Compared to previous timescales, AICC2012 presents an improved timing for the last glacial inception respecting the glaciological constraints of all analyzed records. Moreover, with the addition of numerous new stratigraphic markers and improved calculation of the lock-in depth (LID) based on δ15N data employed as the Datice background scenario, the AICC2012 presents a new timing for the bipolar sequence of events over Marine Isotope Stage 3 associated with the see-saw mechanism, with maximum differences of about 500 yr with respect to the previous Datice-derived chronology of Lemieux-Dudon et al. (2010), hereafter denoted LD2010. Our improved scenario confirms the regional differences for the millennial scale variability over the last glacial period: while the EDC isotopic record (events of triangular shape) displays peaks roughly at the same time as the NGRIP abrupt isotopic increases, the EDML isotopic record (events characterized by broader peaks or even extended periods of high isotope values) reached the isotopic maximum several centuries before.

Vitamin B12 effects on chlorinated methanes-degrading microcosms: Dual isotope and metabolically active microbial populations assessment.

PubMed

Rodríguez-Fernández, Diana; Torrentó, Clara; Guivernau, Miriam; Viñas, Marc; Hunkeler, Daniel; Soler, Albert; Domènech, Cristina; Rosell, Mònica

2018-04-15

Field-derived anoxic microcosms were used to characterize chloroform (CF) and carbon tetrachloride (CT) natural attenuation to compare it with biostimulation scenarios in which vitamin B 12 was added (B 12 /pollutant ratio of 0.01 and 0.1) by means of by-products, carbon and chlorine compound-specific stable-isotope analysis, and the active microbial community through 16S rRNA MiSeq high-throughput sequencing. Autoclaved slurry controls discarded abiotic degradation processes. B 12 catalyzed CF and CT biodegradation without the accumulation of dichloromethane, carbon disulphide, or CF. The carbon isotopic fractionation value of CF (ƐC CF ) with B 12 was -14±4‰, and the value for chlorine (ƐCl CF ) was -2.4±0.4‰. The carbon isotopic fractionation values of CT (ƐC CT ) were -16±6 with B 12 , and -13±2‰ without B 12 ; and the chlorine isotopic fractionation values of CT (ƐCl CT ) were -6±3 and -4±2‰, respectively. Acidovorax, Ancylobacter, and Pseudomonas were the most metabolically active genera, whereas Dehalobacter and Desulfitobacterium were below 0.1% of relative abundance. The dual C-Cl element isotope slope (Λ=Δδ 13 C/Δδ 37 Cl) for CF biodegradation (only detected with B 12 , 7±1) was similar to that reported for CF reduction by Fe(0) (8±2). Several reductive pathways might be competing in the tested CT scenarios, as evidenced by the lack of CF accumulation when B 12 was added, which might be linked to a major activity of Pseudomonas stutzeri; by different chlorine apparent kinetic isotope effect values and Λ which was statistically different with and without B 12 (5±1 vs 6.1±0.5), respectively. Thus, positive B 12 effects such as CT and CF degradation catalyst were quantified for the first time in isotopic terms, and confirmed with the major activity of species potentially capable of their degradation. Moreover, the indirect benefits of B 12 on the degradation of chlorinated ethenes were proved, creating a basis for remediation strategies in multi-contaminant polluted sites. Copyright © 2017 Elsevier B.V. All rights reserved.

Tracing cadmium, zinc and lead sources in bivalves from the coasts of western Canada and the USA using isotopes

NASA Astrophysics Data System (ADS)

Shiel, Alyssa E.; Weis, Dominique; Orians, Kristin J.

2012-01-01

Environmental monitoring and remediation require techniques to identify the source and fate of metals emissions. The measurement of heavy metal isotopic signatures, made possible by the advent of the MC-ICP-MS, is a powerful new geochemical tool, which may be used to trace the source of these metals in the environment. In a multi-tracer study, Cd, Zn and Pb isotopic compositions (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are used to distinguish between natural and anthropogenic sources of these metals in bivalves collected from western Canada (British Columbia), Hawaii, and the USA East Coast. Variability in the δ 114/110Cd values of bivalves (-1.20‰ to -0.09‰) is attributed to differences in the relative contributions of Cd from natural and anthropogenic sources between sites. Cadmium isotopic compositions (δ 114/110Cd = -0.69‰ to -0.09‰) identify high Cd levels in B.C. oysters as primarily natural (i.e., upwelling of Cd rich intermediate waters in the North Pacific), with some variability attributed to anthropogenic sources (e.g., mining and smelting). Variability in the δ 66/64Zn values exhibited by the B.C. bivalves is relatively small (0.28-0.36‰). Despite the low Pb levels found in B.C. oysters, Pb isotopes are used to identify emissions from industrial processes and the consumption of unleaded gasoline and diesel fuel as significant metal sources. Although the Cd concentrations of the USA East Coast bivalves are primarily lower than those of B.C. oysters, their relatively light Cd isotopic compositions (δ 114/110Cd = -1.20‰ to -0.54‰) indicate the significance of anthropogenic Cd sources and are attributed to the high prevalence of industry on this coast. The δ 114/110Cd values of USA East Coast bivalves include the lightest ever reported, with the exception of values reported for extraterrestrial materials. In addition, the Pb isotopic compositions of bivalves from the USA East Coast indicate Pb emissions from the combustion of coal are an important source of Pb, consistent with the high consumption of coal for power production on this coast. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb "fingerprinting" techniques.

Method and apparatus for separation of heavy and tritiated water

DOEpatents

Lee, Myung W.

2001-01-01

The present invention is a bi-thermal membrane process for separating and recovering hydrogen isotopes from a fluid containing hydrogen isotopes, such as water and hydrogen gas. The process in accordance with the present invention provides counter-current cold and hot streams of the fluid separated with a thermally insulating and chemically transparent proton exchange membrane (PEM). The two streams exchange hydrogen isotopes through the membrane: the heavier isotopes migrate into the cold stream, while the lighter isotopes migrate into the hot stream. The heavy and light isotopes are continuously withdrawn from the cold and hot streams respectively.

Compound-specific carbon isotope analysis of instantaneous gas generated from shaly coal during hydrous pyrolysis

NASA Astrophysics Data System (ADS)

Tsai, Wen-Yu; Sun, Chih-Hsien; Huang, Wuu-Liang

2010-05-01

Isotopes of natural gases have provided important information for indicating their maturation, origins and influencing factors during the generation processes. In order to distinguish compositions of gas generated at different intervals of maturities, the present study investigates the variation of compound-specific carbon isotope (CSI) ratios of hydrocarbon gases from a shaly coal by instantaneous hydrous pyrolysis, during which the earlier generated gas was evacuated before the start of next maturation stage. The experiments were conducted at ten different maturity stages (0.65 to 2.02 % Ro) from a terrestrial shaly coal with 0.48 % Ro. The gas products were analyzed by GC-IR-MS. The results show that, in general, the δ13C values of methane (C1), ethane (C2), propane (C3) slightly increase, then decrease and finally increase with increasing maturities. This reverse phenomenon indicates the heterogeneous and complex compositions of the kerogen. The isotope compositions of gases exhibit three distinct clusters in natural gas plot of δ13C values versus 1/n (where n is carbon number of the gaseous molecule), corresponding to three different groups of maturity stages. By linking the same maturity stage of δ13C values, all lines show nearly parallel in each group with consistently reverse trend of δ13C3 < δ13C2 > δ13C1. These three distinct clusters were also observed in the cross plotting of iC4/nC4 versus iC5/nC5 isomer ratios. This may imply that the kerogen is composed of three discrete structural domains which were progressively cracked at three major groups of maturity stages. The reverse trend was inconsistent with data for gas collected cumulatively in most prior pyrolysis experiments and the linear relationship predicted from kinetic isotope effect (KIE) model. Although the non-linear relationship or reverse trend, δ13C3 < δ13C2, was also reported for some natural gases, it was interpreted as a result of mixing from different source rocks or other processes. Our results, however, suggest that this non-linear relationship or reverse phenomenon can also be attributed to the mixing of gases generated from different maturity stages solely from a single source formation. Therefore, our results provide a new interpretation for the variation of isotope data of the cumulative and instantaneous gases in hydrous pyrolysis experiments and isotope variation in natural gas.

37Cl/35Cl isotope ratio analysis in perchlorate by ion chromatography/multi collector -ICPMS: Analytical performance and implication for biodegradation studies.

PubMed

Zakon, Yevgeni; Ronen, Zeev; Halicz, Ludwik; Gelman, Faina

2017-10-01

In the present study we propose a new analytical method for 37 Cl/ 35 Cl analysis in perchlorate by Ion Chromatography(IC) coupled to Multicollector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). The accuracy of the analytical method was validated by analysis of international perchlorate standard materials USGS-37 and USGS -38; analytical precision better than ±0.4‰ was achieved. 37 Cl/ 35 Cl isotope ratio analysis in perchlorate during laboratory biodegradation experiment with microbial cultures enriched from the contaminated soil in Israel resulted in isotope enrichment factor ε 37 Cl = -13.3 ± 1‰, which falls in the range reported previously for perchlorate biodegradation by pure microbial cultures. The proposed analytical method may significantly simplify the procedure for isotope analysis of perchlorate which is currently applied in environmental studies. Copyright © 2017. Published by Elsevier Ltd.

Tracing Cd, Zn and Pb pollution sources in bivalves using isotopes

NASA Astrophysics Data System (ADS)

Shiel, A. E.; Weis, D. A.; Orians, K. J.

2010-12-01

In a multi-tracer study, Cd, Zn and Pb isotopes (MC-ICP-MS) and elemental concentrations (HR-ICP-MS) are evaluated as tools to distinguish between natural and anthropogenic sources of these metals in bivalves from western Canada (British Columbia), the eastern USA, Hawaii and France. High Cd concentrations found in BC oysters have elicited economic and health concerns. The source of these high Cd levels is unknown but thought to be largely natural. High Cd levels in BC oysters are largely attributed to the natural upwelling of Cd-rich intermediate waters in the North Pacific as the δ114/110Cd (-0.69 to -0.09‰) and δ66/64Zn (0.28 to 0.36‰) values of BC oysters fall within the range reported for North Pacific seawater. Different contributions from anthropogenic sources account for the variability of Cd isotopic compositions of BC oysters; the lightest of these oysters are from the BC mainland. These oysters also have Pb isotopic compositions that reflect primarily anthropogenic sources (e.g., leaded and unleaded automotive gasoline and smelting of Pb ores, potentially historical). On the contrary, USA East Coast bivalves exhibit relatively light Cd isotopic compositions (δ114/110Cd = -1.20 to -0.54‰; lighter than reported for North Atlantic seawater) due to the high prevalence of industry on this coast. The Pb isotopic compositions of these bivalves indicate contributions from the combustion of coal. The large variability of environmental health among coastal areas in France is reflected in the broad range of Cd isotopic compositions exhibited by French bivalves (δ114/110Cd = -1.08 to -0.20‰). Oysters and mussels from the Marennes-Oléron basin and Gironde estuary have the lightest Cd isotopic compositions of the French oysters consistent with significant historical Cd emissions from the now-closed proximal Zn smelter. In these bivalves, significant declines in the Cd levels between 1984/7 and 2004/5 are not accompanied by a significant shift in the Cd isotopic composition toward natural values. The Mediterranean samples have isotopic compositions within error of the lighter end of the range reported for Mediterranean seawater. The Zn isotopic compositions of French oysters and mussels (δ66/64Zn = 0.39 to 0.46‰) are identical to those reported for North Atlantic seawater, with the exception of the much heavier compositions of oysters (δ66/64Zn = 1.03 to 1.15‰) from the polluted Gironde estuary. In agreement with Cd and Zn isotopic compositions, the Pb isotopic compositions of the French bivalves indicate primarily industrial (as opposed to automotive) sources; this is consistent with the collection of most of the French bivalve samples in 2004, after the complete phase-out of leaded gasoline in France. This study demonstrates the effective use of Cd and Zn isotopes to trace anthropogenic sources in the environment and the benefit of combining these tools with Pb isotope “fingerprinting” techniques to identify processes contributing metals. Use of these new geochemical tools requires site-specific knowledge of potential metal sources and their isotopic compositions.

MicroRNAs and the metabolic hallmarks of aging.

PubMed

Victoria, Berta; Nunez Lopez, Yury O; Masternak, Michal M

2017-11-05

Aging, the natural process of growing older, is characterized by a progressive deterioration of physiological homeostasis at the cellular, tissue, and organismal level. Metabolically, the aging process is characterized by extensive changes in body composition, multi-tissue/multi-organ insulin resistance, and physiological declines in multiple signaling pathways including growth hormone, insulin/insulin-like growth factor 1, and sex steroids regulation. With this review, we intend to consolidate published information about microRNAs that regulate critical metabolic processes relevant to aging. In certain occasions we uncover relationships likely relevant to aging, which has not been directly described before, such as the miR-451/AMPK axis. We have also included a provocative section highlighting the potential role in aging of a new designation of miRNAs, namely fecal miRNAs, recently discovered to regulate intestinal microbiota in mammals. Copyright © 2016. Published by Elsevier B.V.

Laser resonance ionization spectroscopy on lutetium for the MEDICIS project

NASA Astrophysics Data System (ADS)

Gadelshin, V.; Cocolios, T.; Fedoseev, V.; Heinke, R.; Kieck, T.; Marsh, B.; Naubereit, P.; Rothe, S.; Stora, T.; Studer, D.; Van Duppen, P.; Wendt, K.

2017-11-01

The MEDICIS-PROMED Innovative Training Network under the Horizon 2020 EU program aims to establish a network of early stage researchers, involving scientific exchange and active cooperation between leading European research institutions, universities, hospitals, and industry. Primary scientific goal is the purpose of providing and testing novel radioisotopes for nuclear medical imaging and radionuclide therapy. Within a closely linked project at CERN, a dedicated electromagnetic mass separator system is presently under installation for production of innovative radiopharmaceutical isotopes at the new CERN-MEDICIS laboratory, directly adjacent to the existing CERN-ISOLDE radioactive ion beam facility. It is planned to implement a resonance ionization laser ion source (RILIS) to ensure high efficiency and unrivaled purity in the production of radioactive ions. To provide a highly efficient ionization process, identification and characterization of a specific multi-step laser ionization scheme for each individual element with isotopes of interest is required. The element lutetium is of primary relevance, and therefore was considered as first candidate. Three two-step excitation schemes for lutetium atoms are presented in this work, and spectroscopic results are compared with data of other authors.

Anthropogenic climate change has driven Lake Superior productivity beyond the range of Holocene variability

NASA Astrophysics Data System (ADS)

OBeirne, M. D.; Werne, J. P.; Hecky, R. E.; Johnson, T. C.; Katsev, S.; Reavie, E. D.

2013-12-01

Recent studies have noted that changes in Lake Superior's physical, chemical and biological processes are apparent - including a warming of the surface waters at a rate twice as great as the surrounding airshed in the last 20 years. These changes are often difficult to perceive as cause for concern when not placed within a historical context. In this study, bulk C and N abundance and stable isotope composition was determined on sediments from three piston and corresponding gravity cores, representing a record of lake-wide paleoproductivity trends spanning the Holocene. These data are compared with the same measurements on eight multi-cores sampled at high resolution spanning the past ~200 years, which allows for the historical comparison with recent (1800 A.D. to present) productivity trends. Throughout the Holocene, Lake Superior experienced a slow, steady increase in productivity consistent with conventional lake ontogeny. During the last 200 years, however, the Lake Superior basin has undergone biogeochemical changes that are unique in the context of the Holocene. Lake-wide sedimentary bulk organic carbon data indicate increasing primary production between 1900 and present, as indicated by a ~2‰ increase in δ13Corg. In contrast,δ15Norg values, which increased throughout the Holocene, become progressively 15N-depleted after 1900, likely due to atmospheric deposition of NOx from fossil fuel combustion. The most recent increases in primary productivity are likely a response to increasing water temperatures, leading to longer ice-free periods as previously documented in Lake Superior.

An efficient multi-resolution GA approach to dental image alignment

NASA Astrophysics Data System (ADS)

Nassar, Diaa Eldin; Ogirala, Mythili; Adjeroh, Donald; Ammar, Hany

2006-02-01

Automating the process of postmortem identification of individuals using dental records is receiving an increased attention in forensic science, especially with the large volume of victims encountered in mass disasters. Dental radiograph alignment is a key step required for automating the dental identification process. In this paper, we address the problem of dental radiograph alignment using a Multi-Resolution Genetic Algorithm (MR-GA) approach. We use location and orientation information of edge points as features; we assume that affine transformations suffice to restore geometric discrepancies between two images of a tooth, we efficiently search the 6D space of affine parameters using GA progressively across multi-resolution image versions, and we use a Hausdorff distance measure to compute the similarity between a reference tooth and a query tooth subject to a possible alignment transform. Testing results based on 52 teeth-pair images suggest that our algorithm converges to reasonable solutions in more than 85% of the test cases, with most of the error in the remaining cases due to excessive misalignments.

A comparison of representations for discrete multi-criteria decision problems☆

PubMed Central

Gettinger, Johannes; Kiesling, Elmar; Stummer, Christian; Vetschera, Rudolf

2013-01-01

Discrete multi-criteria decision problems with numerous Pareto-efficient solution candidates place a significant cognitive burden on the decision maker. An interactive, aspiration-based search process that iteratively progresses toward the most preferred solution can alleviate this task. In this paper, we study three ways of representing such problems in a DSS, and compare them in a laboratory experiment using subjective and objective measures of the decision process as well as solution quality and problem understanding. In addition to an immediate user evaluation, we performed a re-evaluation several weeks later. Furthermore, we consider several levels of problem complexity and user characteristics. Results indicate that different problem representations have a considerable influence on search behavior, although long-term consistency appears to remain unaffected. We also found interesting discrepancies between subjective evaluations and objective measures. Conclusions from our experiments can help designers of DSS for large multi-criteria decision problems to fit problem representations to the goals of their system and the specific task at hand. PMID:24882912

Measurements of rare isotopes of U and Th by MC-ICP-MS using a 1013 ohm resistor

NASA Astrophysics Data System (ADS)

Pythoud, M.; Edwards, R. L.; Cheng, H.; Lu, Y.; Zhang, P.; Nissen, J.; Berry, A. E.

2016-12-01

We have tested a 1013 ohm resistor on a Thermo-Scientific Neptune Plus, a multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS), for the measurement of rare isotopes of uranium (U) and thorium (Th). In nature, the isotopic disequilibrium among U-series nuclides provides the potential to date materials and time processes over the last 700,000 years. Using gravimetric standards and a Minnesota stalagmite, we demonstrate the reproducibility of δ234U and 230Th dates with uncertainties at the 1-‰ to sub-‰ level (2σ), with relatively small samples. Compared to traditional secondary electron multiplier (SEM) techniques, measurement times decrease from > 1 hour to < 5 min for U and from tens of min to < 2 min for Th, with comparable or better precision. The characteristics of the new amplifier design and typical instrumental conditions allow for 234U and 230Th sample loads as small as 1-2 pg, a reduction in sample size close to an order of magnitude over cup measurements with 1011 ohm resistors. The main sources of error include the amplifier noise, uncertainty in the characterization of the tailing effect, and in some cases, counting statistics. Importantly, our overall characterization suggests that this new method forms the basis for future and further improvements on instrumental precision.

The oxygen isotopes

NASA Astrophysics Data System (ADS)

Brown, B. Alex

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

Carbon isotope exchange between CO2 and CH4 in hydrothermal fluids from the Tuscan-Roman and Campanian degassing systems (central-southern Italy)

NASA Astrophysics Data System (ADS)

Tassi, F.; Fiebig, J.; Nocentini, M.; Vaselli, O.

2010-12-01

The carbon isotope composition in CO2 and CH4 are commonly used as exploration tools and diagnostic indicators to investigate the origin of endogenous gases. At temperature <200 °C both proportions and isotope ratios of these two gases are considered to be largely controlled by processes (i.e. bacterial activity, thermal hydrolysis, and cracking of organic matter) that are mainly dictated by kinetics. Recent investigations on abiogenic generation of CH4 suggest that at temperatures as low as 100 °C, CH4 production from CO2 has halftimes in the order of 1 year. The present work is based on the d13C-CO2 and d13C-CH4 values of more than 83 gas discharges from the Tuscan-Roman and Campanian degassing systems (central-southern Italy). The main aims are to i) investigate the processes regulating the chemical and isotopic compositions of CO2 and CH4 and ii) verify the use of the CO2-CH4 carbon isotopic equilibrium for evaluating the temperature of deep hydrothermal reservoirs. Our results show that the d13C-CH4 values, with few exceptions related to local production of biogenic CH4 at shallow depth, are > -40 ‰ V-PDB. The most intriguing feature of the measured d13C-CH4 values is that they progressively decrease from the peri-Tyrrhenian area, where productive geothermal systems and active volcanoes are located, to East, i.e. approaching the CH4-rich reservoirs that mark the Adriatic side of the Italian peninsula. The d13C-CO2 values are substantially spanning from a thermometamorphic to a mantle degassing CO2 and do not show any preferential spatial distribution. Secondary carbon isotope fractionation caused by interaction with relatively shallow aquifers may contribute to the scatter of d13C-CO2 values, considering the high solubility of CO2 in liquid water. However, the CO2-CH4 isotopic compositions of fluids from the high temperature geothermal systems characterizing the Tyrrhenian coast of central-southern Italy, i.e. Larderello, Mt. Amiata, Manziana and Phlegrean Fields, provide apparent equilibrium temperatures in the range of those directly measured in production wells and/or estimated on the basis of the CH4-CO2 chemical geothermometer. These results are consistent with the fact that the carbon isotopic equilibrium in the CO2-CH4 system has to be preceded by that of the chemical exchange because the latter has a kinetic rate 400 times faster than the isotopic partitioning. The observed agreement between measured and/or inferred aquifer temperatures with apparent carbon isotopic equilibration supports recent findings that CO2 and CH4 can attain carbon isotopic equilibrium in high-enthalpy hydrothermal systems. The d13C-CH4 values of gas discharges located eastward, toward the Appennine sedimentary chain, are likely produced by mixing of high temperature fluids from the geothermal areas and a relatively cold deep aquifer characterized by biogenic CH4: The higher distance from the geothermal-volcanic systems, the higher fraction of low temperature fluids.

Object recognition through a multi-mode fiber

NASA Astrophysics Data System (ADS)

Takagi, Ryosuke; Horisaki, Ryoichi; Tanida, Jun

2017-04-01

We present a method of recognizing an object through a multi-mode fiber. A number of speckle patterns transmitted through a multi-mode fiber are provided to a classifier based on machine learning. We experimentally demonstrated binary classification of face and non-face targets based on the method. The measurement process of the experimental setup was random and nonlinear because a multi-mode fiber is a typical strongly scattering medium and any reference light was not used in our setup. Comparisons between three supervised learning methods, support vector machine, adaptive boosting, and neural network, are also provided. All of those learning methods achieved high accuracy rates at about 90% for the classification. The approach presented here can realize a compact and smart optical sensor. It is practically useful for medical applications, such as endoscopy. Also our study indicated a promising utilization of artificial intelligence, which has rapidly progressed, for reducing optical and computational costs in optical sensing systems.

The new high-resolution IRMS MAT253 ULTRA at Utrecht University

NASA Astrophysics Data System (ADS)

Röckmann, Thomas; Hofmann, Magdalena; Paul, Dipayan; Popa, Elena; Adnew, Getachew

2017-04-01

In 2016, the new high-resolution, multi-collector isotope ratio mass spectrometer MAT253 ULTRA [1] was installed at Utrecht University. This instrument is designed to reach a mass resolving power of 20,000 to 40,000 (M/ΔM). The ion currents are detected with a variable multi-collector unit that allows to register up to 9 ion currents simultaneously with Faraday cups and ion counters. The width of the entrance slit can be varied between 5 and 250μm so that the instrument can be operated under low, medium and high mass resolution, and an optimum balance between resolution and sensitivity can be selected for the respective applications. The central field of application of the new IRMS at Utrecht University is the measurement of multiply substituted isotopologues (clumped isotopes) in atmospheric trace compounds (e.g. 13CDH3, 13C18O16O, 18O18O, 15N14N18O) [1-7]. It is known from thermodynamics that the zero point energy of a chemical bond usually decreases when multiple heavy isotopes clump together in a molecule, and this effect depends on temperature [7]. Therefore, the abundance of clumped isotopes can be used as temperature indicator under thermodynamical equilibrium conditions. However, in the atmosphere, many reactions are controlled kinetically. It has been shown recently for a few examples that negative clumping signatures (anti-clumping) can be produced under non-equilibrium conditions [3,4]. In addition, based on purely statistical reasons, anti-clumping signatures will be produced in any molecule that contains indistinguishable atoms, which originate from isotopically distinct reservoir [5,6]. Thus, the investigation of multiply substituted isotopologues is expected to generate novel isotope signatures that can complement conventional stable isotope analysis in atmospheric science. We will present data on the performance of the MAT 253 ULTRA instrument and first scientific applications to atmospheric research. 1. Eiler, J.M., et al., A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spect., 2013. 335: 45- 56. 2. Young, E.D., et al., A large-radius high-mass-resolution multiple-collector isotope ratio mass spectrometer for analysis of rare isotopologues of O2, N2, CH4 and other gases, Int. J. Mass Spect., 2016. 401: 1-10. 3. Wang, D.T., et al., Nonequilibrium clumped isotope signals in microbial methane, Science, 2015. 348: 428-431. 4. Yeung, L.Y., et al., Biological signatures in clumped isotopes of O2, Science, 2015. 348: 431-434. 5. Yeung, L.Y., Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Act., 2016: doi:10.1016/j.gca.2015.09.020. 6. Röckmann, T., et al., Statistical clumped isotope signatures Scientific reports, 2016. 6: 31947; doi: 10.1038/srep31947. 7. Wang, Z.G., et al., Equilibrium thermodynamics of multiply substituted isotopologues of molecular gases, Geochim. Cosmochim. Act., 2004. 68: 4779-4797.

Hemorrhagic fever of bunyavirus etiology: disease models and progress towards new therapies.

PubMed

Gowen, Brian B; Hickerson, Brady T

2017-03-01

A growing number of bunyaviruses are known to cause viral hemorrhagic fever (VHF), a severe febrile illness which can progress to hypovolemic shock and multi-organ failure and is characterized by hematologic abnormalities and vascular leak. At present, there are no approved vaccines or antiviral therapies to effectively prevent or treat VHF caused by pathogenic bunyaviruses. Advances in the modeling of bunyaviral infections have facilitated efforts towards the development of novel post-exposure prophylactic and therapeutic countermeasures, several of which may some day be approved for human use. Here, we review recent progress in animal models of severe bunyaviral infections essential to this mission, as well as promising antivirals and biologicals that are at various stages of the development process.

Multi-Target Tracking via Mixed Integer Optimization

DTIC Science & Technology

2016-05-13

solving these two problems separately, however few algorithms attempt to solve these simultaneously and even fewer utilize optimization. In this paper we...introduce a new mixed integer optimization (MIO) model which solves the data association and trajectory estimation problems simultaneously by minimizing...Kalman filter [5], which updates the trajectory estimates before the algorithm progresses forward to the next scan. This process repeats sequentially

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous study by Stetson et al. (ES&T, 2009, 43:7331-7336). In order to further elucidate the Hg isotope signatures of the New Idria samples, we performed a three-step sequential extraction procedure to separate different Hg pools. The calcine samples exhibited a higher proportion of leachable Hg phases compared with the unrefined ore waste samples. The most soluble Hg pool (HAc/HCl, pH 2) had a significantly heavier MDF and more negative MIF signature than the bulk calcine samples, suggesting that the dissolution of more soluble Hg phases from calcine materials results in an enhanced flux of leached Hg which is isotopically distinct from the original ore. Moreover, this finding demonstrates that the Hg isotope fractionation during the ore roasting cannot be solely explained by a kinetic Rayleigh-type process which removes light Hg isotopes, but must additionally involve the formation of isotopically heavy secondary Hg phases in the calcine. The analysis of additional samples will enable us to test this hypothesis and to gain further insights into the applicability of stable Hg isotope ratios as source and process tracers in Hg-contaminated environments.

Oxygen-isotope composition of ground water and secondary minerals in Columbia Plateau basalts: implications for the paleohydrology of the Pasco Basin

USGS Publications Warehouse

Hearn, P.P.; Steinkampf, W.C.; Horton, D.G.; Solomon, G.C.; White, L.D.; Evans, J.R.

1989-01-01

Concentrations of 18O and deuterium in ground waters beneath the Hanford Reservation, Washington State, suggest that the meteoric waters recharging the basalt aquifers have been progressively depleted in these isotopes since at least Pleistocene time. This conclusion is supported by oxygen-isotope analyses of low-temperature secondary minerals filling vugs and fractures in the basalts, which are used to approximate the 18O content of ground water at the time the mineral assemblage formed. A fossil profile of ??18O values projected for ground water in a 1500 m vertical section beneath the reservation suggests that the vertical mixing of shallow and deep ground water indicated by present-day hydrochemical data was also occurring during Neogene time. These data also suggest that a unidirectional depletion of 18O and deuterium recorded in Pleistocene ground waters may have extended considerably further back in time. This shift is tentatively attributed to the orographic depletion of 18O associated with the progressive uplift of the Cascade Range since the middle Miocene. -Authors

Progress update on cryogenic system for ARIEL E-linac at TRIUMF

NASA Astrophysics Data System (ADS)

Koveshnikov, A.; Bylinskii, I.; Hodgson, G.; Yosifov, D.

2014-01-01

TRIUMF is involved in a major upgrade. The Advanced Rare IsotopeE Laboratory (ARIEL) has become a fully funded project in July 2010. A 10 mA 50 MeV SRF electron linac (e-linac) operating CW at 1.3 GHz is the key component of this initiative. This machine will serve as a second independent photo-fission driver for Rare Isotope Beams (RIB) production at TRIUMF's Isotope Separator and Accelerator (ISAC) facility. The cryogens delivery system requirements are driven by the electron accelerator cryomodule design [1, 2]. Since commencement of the project in 2010 the cryogenic system of e-linac has moved from the conceptual design phase into engineering design and procurement stage. The present document summarizes the progress in cryogenic system development and construction. Current status of e-linac cryogenic system including details of LN2 storage and delivery systems, and helium subatmospheric (SA) system is presented. The first phase of e-linac consisting of two cryomodules, cryogens storage, delivery, and distribution systems, and a 600 W class liquid helium cryoplant is scheduled for installation and commissioning by year 2014.

Alchemy in the underworld - recent progress and future potential of organic geochemistry applied to speleothems.

NASA Astrophysics Data System (ADS)

Blyth, Alison

2016-04-01

Speleothems are well used archives for chemical records of terrestrial environmental change, and the integration of records from a range of isotopic, inorganic, and organic geochemical techniques offers significant power in reconstructing both changes in past climates and identifying the resultant response in the overlying terrestrial ecosystems. The use of organic geochemistry in this field offers the opportunity to recover new records of vegetation change (via biomarkers and compound specific isotopes), temperature change (via analysis of glycerol dialkyl glycerol tetraethers, a compound group derived from microbes and varying in structure in response to temperature and pH), and changes in soil microbial behaviour (via combined carbon isotope analysis). However, to date the use of organic geochemical techniques has been relatively limited, due to issues relating to sample size, concerns about contamination, and unanswered questions about the origins of the preserved organic matter and rates of transport. Here I will briefly review recent progress in the field, and present a framework for the future research needed to establish organic geochemical analysis in speleothems as a robust palaeo-proxy approach.

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.

The Multi-GNSS Experiment (MGEX) of the International GNSS Service (IGS) - Achievements, prospects and challenges

NASA Astrophysics Data System (ADS)

Montenbruck, Oliver; Steigenberger, Peter; Prange, Lars; Deng, Zhiguo; Zhao, Qile; Perosanz, Felix; Romero, Ignacio; Noll, Carey; Stürze, Andrea; Weber, Georg; Schmid, Ralf; MacLeod, Ken; Schaer, Stefan

2017-04-01

Over the past five years, the International GNSS Service (IGS) has made continuous efforts to extend its service from GPS and GLONASS to the variety of newly established global and regional navigation satellite systems. This report summarizes the achievements and progress made in this period by the IGS Multi-GNSS Experiment (MGEX). The status and tracking capabilities of the IGS monitoring station network are presented and the multi-GNSS products derived from this resource are discussed. The achieved performance is assessed and related to the current level of space segment and user equipment characterization. While the performance of orbit and clock products for BeiDou, Galileo, and QZSS still lags behind the legacy GPS and GLONASS products, continued progress has been made since launch of the MGEX project and already enables use of the new constellations for precise point positioning, atmospheric research and other applications. Directions for further research are identified to fully integrate the new constellations into routine GNSS processing. Furthermore, the active support of GNSS providers is encouraged to assist the scientific community in the generation of fully competitive products for the new constellations.

The role of stable isotopes in understanding rainfall interception processes: a review

EPA Science Inventory

The isotopic composition of water transmitted by the canopy as throughfall or stemflow reflects important hydrologic processes occurring in the canopy. A synthesis of the literature shows that complex spatiotemporal variations of isotopic composition are created by canopy interce...

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

USGS Publications Warehouse

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

2000-01-01

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

Iron Isotopic Fractionation in Igneous Systems: Looking for Anharmonicity

NASA Astrophysics Data System (ADS)

Dauphas, N.; Roskosz, M.; Hu, M. Y.; Neuville, D. R.; Alp, E. E.; Hu, J.; Heard, A.; Zhao, J.

2017-12-01

Igneous rocks display variations in their Fe isotopic compositions that can be used to trace partial melting, magma differentiation, the origin of mineral zoning, and metasomatic processes. While tremendous progress has been made in our understanding of how iron isotopes can be fractionated at equilibrium or during diffusion, significant work remains to be done to establish equilibrium fractionation factors between phases relevant to igneous petrology. A virtue of iron isotope systematics is that iron possesses a Mössbauer isotope, 57Fe, and one can use the method of NRIXS to measure the force constant of iron bonds, from which beta-factors can be calculated. These measurements are done at a few synchrotron beamlines around the world, such as sector 3ID of the APS (Argonne). Tremendous insights have already been gained by applying this technique to Earth science materials. It was shown for instance that significant equilibrium fractionation exists between Fe2+ and Fe3+ at magmatic temperature, that the iron isotopic fractionation resulting from core formation must be small, and that iron isotopic fractionation is influenced by the polymerization of the melt. Combining NRIXS and ab initio studies, there are approximately 130 geologically-relevant solids and aqueous species for which beta-factors have been reported. A potential limitation of applying published NRIXS data to igneous petrology is that all the force constants have been measured at room temperature and the beta-factors are extrapolated to magmatic temperatures assuming that the systems are harmonic, which has never been demonstrated. One way to test this critical assumption is to measure the apparent force constant of iron bonds at various temperatures, so that the interatomic potential of iron bonds can be probed. A further virtue of NRIXS is that the data also allows us to derive the mean square displacement. If significant anharmonicity is present, it should be manifested as a decrease in the apparent force constant with increasing temperature and increasing mean square displacement. We have measured the Fe force constant of basalt glass and olivine using a wire furnace. At the conference, we will report on these experiments and will discuss some implications for igneous petrology.

Subducted slab-plume interaction traced by magnesium isotopes in the northern margin of the Tarim Large Igneous Province

NASA Astrophysics Data System (ADS)

Cheng, Zhiguo; Zhang, Zhaochong; Xie, Qiuhong; Hou, Tong; Ke, Shan

2018-05-01

Incorporation of subducted slabs may account for the geochemical and isotopic variations of large igneous provinces (LIPs). However, the mechanism and process by which subducted slabs are involved into magmas is still highly debated. Here, we report a set of high resolution Mg isotopes for a suite of alkaline and Fe-rich rocks (including basalts, mafic-ultramafic layered intrusions, diabase dykes and mantle xenoliths in the kimberlitic rocks) from Tarim Large Igneous Province (TLIP). We observed that δ26 Mg values of basalts range from -0.29 to - 0.45 ‰, -0.31 to - 0.42 ‰ for mafic-ultramafic layered intrusions, -0.28 to - 0.31 ‰ for diabase dykes and -0.29 to - 0.44 ‰ for pyroxenite xenoliths from the kimberlitic rocks, typically lighter than the normal mantle source (- 0.25 ‰ ± 0.04, 2 SD). After carefully precluding other possibilities, we propose that the light Mg isotopic compositions and high FeO contents should be ascribed to the involvement of recycled sedimentary carbonate rocks and pyroxenite/eclogite. Moreover, from basalts, through layered intrusions to diabase dykes, (87Sr/86Sr)i values and δ18OV-SMOW declined, whereas ε (Nd) t and δ26 Mg values increased with progressive partial melting of mantle, indicating that components of carbonate rock and pyroxenite/eclogite in the mantle sources were waning over time. In combination with the previous reported Mg isotopes for carbonatite, nephelinite and kimberlitic rocks in TLIP, two distinct mantle domains are recognized for this province: 1) a lithospheric mantle source for basalts and mafic-ultramafic layered intrusions which were modified by calcite/dolomite and eclogite-derived high-Si melts, as evidenced by enriched Sr-Nd-O and light Mg isotopic compositions; 2) a plume source for carbonatite, nephelinite and kimberlitic rocks which were related to magnesite or periclase/perovskite involvement as reflected by depleted Sr-Nd-O and extremely light Mg isotopes. Ultimately, our study suggests that subducted slabs could make important contributions to LIP generation, and establishes a potential linkage between plate tectonics and mantle plume.

Iron isotopic composition of blood serum in anemia of chronic kidney disease.

PubMed

Anoshkina, Yulia; Costas-Rodríguez, Marta; Speeckaert, Marijn; Van Biesen, Wim; Delanghe, Joris; Vanhaecke, Frank

2017-05-24

Chronic kidney disease (CKD) is a general term for disorders that affect the structure and function of the kidneys. Iron deficiency (ID) and anemia occur in the vast majority of CKD patients, most of whom are elderly. However, establishing the cause of anemia in CKD, and therefore making an informed decision concerning the corresponding therapeutic treatment, is still a challenge. High-precision Fe isotopic analysis of blood serum samples of CKD patients with and without ID/anemia was performed via multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) for such a purpose. Patients with CKD and/or iron disorders showed a heavier serum Fe isotopic composition than controls. Many clinical parameters used for the diagnosis and follow-up of anemia correlated significantly with the serum Fe isotopic composition. In contrast, no relation was observed between the serum Fe isotopic composition and the estimated glomerular filtration rate as a measure of kidney function. Among the CKD patients, the serum Fe isotopic composition was substantially heavier in the occurrence of ID anemia, while erythropoietin-related anemia did not exert this effect. The Fe isotopic composition can thus be useful for distinguishing these different types of anemias in CKD patients, i.e. ID anemia vs. erythropoietin-related anemia.

Small scale denitrification variability in riparian zones: Results from a high-resolution dataset

NASA Astrophysics Data System (ADS)

Gassen, Niklas; Knöller, Kay; Musolff, Andreas; Popp, Felix; Lüders, Tillmann; Stumpp, Christine

2017-04-01

Riparian zones are important compartments at the interface between groundwater and surface water where biogeochemical processes like denitrification are often enhanced. Nitrate loads of either groundwater entering a stream through the riparian zone or streamwater infiltrating into the riparian zone can be substantially reduced. These processes are spatially and temporally highly variable, making it difficult to capture solute variabilities, estimate realistic turnover rates and thus to quantify integral mass removal. A crucial step towards a more detailed characterization is to monitor solutes on a scale which adequately resemble the highly heterogeneous distribution and on a scale where processes occur. We measured biogeochemical parameters in a spatial high resolution within a riparian corridor of a German lowland river system over the course of one year. Samples were taken from three newly developed high-resolution multi-level wells with a maximum vertical resolution of 5 cm and analyzed for major ions, DOC and N-O isotopes. Sediment derived during installation of the wells was analyzed for specific denitrifying enzymes. Results showed a distinct depth zonation of hydrochemistry within the shallow alluvial aquifer, with a 1 m thick zone just below the water table with lower nitrate concentrations and EC values similar to the nearby river. Conservative parameters were consistent inbetween the three wells, but nitrate was highly variable. In addition, spots with low nitrate concentrations showed isotopic and microbial evidence for higher denitrification activities. The depth zonation was observed throughout the year, with stronger temporal variations of nitrate concentrations just below the water table compared to deeper layers. Nitrate isotopes showed a clear seasonal trend of denitrification activities (high in summer, low in winter). Our dataset gives new insight into river-groundwater exchange processes and shows the highly heterogeneous distribution of denitrification in riparian zones, both in time and space. With these new insights, we are able to improve our understanding of spatial scaling of denitrification processes. This leads to a better prediction and improved management strategies for buffer mechanisms in riparian zones.

Distribution of p-process 174Hf in early solar system materials and the origin of nucleosynthetic Hf and W isotope anomalies in Ca-Al rich inclusions

NASA Astrophysics Data System (ADS)

Peters, Stefan T. M.; Münker, Carsten; Pfeifer, Markus; Elfers, Bo-Magnus; Sprung, Peter

2017-02-01

Some nuclides that were produced in supernovae are heterogeneously distributed between different meteoritic materials. In some cases these heterogeneities have been interpreted as the result of interaction between ejecta from a nearby supernova and the nascent solar system. Particularly in the case of the oldest objects that formed in the solar system - Ca-Al rich inclusions (CAIs) - this view is confirm the hypothesis that a nearby supernova event facilitated or even triggered solar system formation. We present Hf isotope data for bulk meteorites, terrestrial materials and CAIs, for the first time including the low-abundance isotope 174Hf (∼0.16%). This rare isotope was likely produced during explosive O/Ne shell burning in massive stars (i.e., the classical "p-process"), and therefore its abundance potentially provides a sensitive tracer for putative heterogeneities within the solar system that were introduced by supernova ejecta. For CAIs and one LL chondrite, also complementary W isotope data are reported for the same sample cuts. Once corrected for small neutron capture effects, different chondrite groups, eucrites, a silicate inclusion of a IAB iron meteorite, and terrestrial materials display homogeneous Hf isotope compositions including 174Hf. Hafnium-174 was thus uniformly distributed in the inner solar system when planetesimals formed at the <50 ppm level. This finding is in good agreement with the evidently homogeneous distributions of p-process isotopes 180W, 184Os and possibly 190Pt between different iron meteorite groups. In contrast to bulk meteorite samples, CAIs show variable depletions in p-process 174Hf with respect to the inner solar system composition, and also variable r-process (or s-process) Hf and W contributions. Based on combined Hf and W isotope compositions, we show that CAIs sampled at least one component in which the proportion of r- and s-process derived Hf and W deviates from that of supernova ejecta. The Hf and W isotope anomalies in CAIs are therefore best explained by selective processing of presolar carrier phases prior to CAI formation, and not by a late injection of supernova materials. Likewise, other isotope anomalies in additional elements in CAIs relative to the bulk solar system may reflect the same process. The isotopic heterogeneities between the first refractory condensates may have been eradicated partially during CAI formation, because W isotope anomalies in CAIs appear to decrease with increasing W concentrations as inferred from time-integrated 182W/184W. Importantly, the 176Lu-176Hf and 182Hf-182W chronometers are not significantly affected by nucleosynthetic heterogeneity of Hf isotopes in bulk meteorites, but may be affected in CAIs.

Progress in the Development of Metamorphic Multi-Junction III-V Space-Solar Cells at Essential Research Incorporated

NASA Technical Reports Server (NTRS)

Sinharoy, Samar; Patton, Martin O.; Valko, Thomas M., Sr.; Weizer, Victor G.

2002-01-01

Theoretical calculations have shown that highest efficiency III-V multi-junction solar cells require alloy structures that cannot be grown on a lattice-matched substrate. Ever since the first demonstration of high efficiency metamorphic single junction 1.1 eV and 1.2 eV InGaAs solar cells by Essential Research Incorporated (ERI), interest has grown in the development of multi-junction cells of this type using graded buffer layer technology. ERI is currently developing a dual-junction 1.6 eV InGaP/1.1 eV InGaAs tandem cell (projected practical air-mass zero (AM0), one-sun efficiency of 28%, and 100-sun efficiency of 37.5%) under a Ballistic Missile Defense Command (BMDO) SBIR Phase II program. A second ongoing research effort at ERI involves the development of a 2.1 eV AlGaInP/1.6 eV InGaAsP/1.2 eV InGaAs triple-junction concentrator tandem cell (projected practical AM0 efficiency of 36.5% under 100 suns) under a SBIR Phase II program funded by the Air Force. We are in the process of optimizing the dual-junction cell performance. In case of the triple-junction cell, we have developed the bottom and the middle cell, and are in the process of developing the layer structures needed for the top cell. A progress report is presented in this paper.

Constraining N2O emissions since 1940 by firn air isotope measurements in both hemispheres

NASA Astrophysics Data System (ADS)

Prokopiou, Markella; Martinerie, Patricia; Sapart, Celia; Witrant, Emmanuel; Monteil, Guillaume; Ishijima, Kentaro; Kaiser, Jan; Levin, Ingeborg; Sowers, Todd; Blunier, Thomas; Etheridge, David; Dlugokencky, Ed; van de Wal, Roderik; Röckmann, Thomas

2017-04-01

N2O is currently the 3rd most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290±1) nmol mol-1 in 1940 to (322±1) nmol mol-1 in 2008 the isotopic δ values of atmospheric N2O decreased by (- 2.2±0.2) ‰ for δ15Nav, (- 1.0±0.3) ‰ for δ18O, (- 1.3±0.6) ‰ for δ15Nα, and (- 2.8±0.6) ‰ for δ15Nβover the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to be 123 a. Adopting this lifetime results in total average source isotopic signatures of (- 7.6±0.8) ‰ (vs. Air-N2) for δ15Nav, (32.2±0.2) ‰ (vs. VSMOW) for δ18O, (- 3.0±1.9) ‰ (vs. Air-N2) for δ15Nα, and (- 11.7±2.3) ‰ (vs. Air-N2) for δ15Nβ over the investigated period. δ15Navand δ15Nβ show some temporal variability while the other source isotopic signatures remain unchanged. The 15N site-preference (= δ15Nα - δ15Nβ) can be used to reveal further information on the source emission origins. Based on the changes in the isotopes we conclude that the main contribution to N2O changes in the atmosphere since 1940 is from soils, with agricultural soils being the principal anthropogenic component, which is in line with previous studies.

Using Multi-Isotope Tracer Methods to Understand the Sources of Nitrate in Aerosols, Fog and River Water in Podocarpus National Forest, Ecuador

NASA Astrophysics Data System (ADS)

Brothers, L. A.; Dominguez, G.; Fabian, P.; Thiemens, M. H.

2008-12-01

The eastern slopes of the Andean rainforests of Ecuador possess some of the highest plant biodiversity found on the planet; however, these ecosystems are in jeopardy because region is experiences one of the highest deforestation rates in South America. This rainforest characterized by high acidity and low nutrient soils and experiences natural process which are both destabilizing and stabilizing to biodiversity rendering this a unique, though sensitive environment. There is increased concern that anthropogenic activities especially biomass burning are affecting the rainforests and could lead to higher extinction rates, changes in the biodiversity and far reaching effects on the global troposphere. Measurements of nitrate and sulfate in rain and fog water have shown periods of elevated concentrations in the Podocarpus National Park near Loja, Ecuador. These high episodes contribute to annual deposition rates that are comparable to polluted regions of North America and Europe. Significant anthropogenic sources such as large scale industry or a major city, near this forest are lacking. It is believed that the majority of the nitrate and sulfate pollution is due to the large amount of biomass burning during the dry season in the Amazon Basin. In recent years it has been shown that large amount of dust is transported across the Atlantic from Africa which reaches South America. Concentration measurements do not elucidate the source of high nitrate and sulfate pollution; however, by measuring all three stable isotopes of oxygen in nitrate and sulfate from fog and river water provides a new way to examine the impacts of biomass burning on the region. By using stable isotope techniques atmospheric nitrate and sulfate can be resolved from terrestrial sources. This provides a unique way to trace the contributions from the biomass burning and farming sources. Current research at the field station, Estación Científica San Francisco in the Podocarpus National Forest monitors sulfate and nitrate concentrations in rain and fog water by standard methods to investigate water and nutrient pathways along with data from satellite and ground based remote sensing, observations and numerical models. We hope to pair this with a multi-isotope tracer method and NOAA Hysplit Back trajectories, and satellite imagery for information about the number of fires burning in the region to help identify sources of the high nitrate deposition.

Introducing the Precision Isotope Ratio Mass Spectrometer: Novel Innovations in Multi-Collector Arrays for Isotopologues and Isotopomers in Organic Molecule Gas Analysis

NASA Astrophysics Data System (ADS)

Kasson, A.

2016-12-01

In January 2016, elementar Analysensysteme, GmbH (Germany), in conjunction with their daughter company, Isoprime Ltd. (United Kingdom) released the Precision isotope ratio mass spectrometer. The Precision is the newest light element IRMS on the market and adds some unique hardware and software functionalities to the basic core of stable isotopic research previously unseen. Although this system is designed to make the typical bulk and compound specific measurements that functioning stable isotope laboratories have been accustomed to, it has been designed to make complicated measurements of isotopologues, isotopomers and clumped isotopes much more turnkey and user friendly. Here we focus on some datasets that have been collected from three different beta test sites and highlight the functional use of the new hardware in conjunction with ionOS operating software. As part of those highlights, the improved precision, accuracy and ion optics of the Precision IRMS will be demonstrated. In addition, we intend to show that the reprocessing functions on the ionOS software package are not only beneficial to users of just the Precision IRMS, but to the entire stable isotope community as a whole.

Rapid 3D NMR using the filter diagonalization method: application to oligosaccharides derivatized with 13C-labeled acetyl groups

NASA Astrophysics Data System (ADS)

Armstrong, Geoffrey S.; Cano, Kristin E.; Mandelshtam, Vladimir A.; Shaka, A. J.; Bendiak, Brad

2004-09-01

Rapid 3D NMR spectroscopy of oligosaccharides having isotopically labeled acetyl "isotags" was made possible with high resolution in the indirect dimensions using the filter diagonalization method (FDM). A pulse sequence was designed for the optimal correlation of acetyl methyl protons, methyl carbons, and carbonyl carbons. The multi-dimensional nature of the FDM, coupled with the advantages of constant-time evolution periods, resulted in marked improvements over Fourier transform (FT) and mirror-image linear prediction (MI-LP) processing methods. The three methods were directly compared using identical data sets. A highly resolved 3D spectrum was achieved with the FDM using a very short experimental time (28 min).

Rapid 3D NMR using the filter diagonalization method: application to oligosaccharides derivatized with 13C-labeled acetyl groups.

PubMed

Armstrong, Geoffrey S; Cano, Kristin E; Mandelshtam, Vladimir A; Shaka, A J; Bendiak, Brad

2004-09-01

Rapid 3D NMR spectroscopy of oligosaccharides having isotopically labeled acetyl "isotags" was made possible with high resolution in the indirect dimensions using the filter diagonalization method (FDM). A pulse sequence was designed for the optimal correlation of acetyl methyl protons, methyl carbons, and carbonyl carbons. The multi-dimensional nature of the FDM, coupled with the advantages of constant-time evolution periods, resulted in marked improvements over Fourier transform (FT) and mirror-image linear prediction (MI-LP) processing methods. The three methods were directly compared using identical data sets. A highly resolved 3D spectrum was achieved with the FDM using a very short experimental time (28 min).

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis

PubMed Central

Brennecka, Gregory A.; Borg, Lars E.; Wadhwa, Meenakshi

2013-01-01

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium–aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy. PMID:24101483

Evidence for supernova injection into the solar nebula and the decoupling of r-process nucleosynthesis.

PubMed

Brennecka, Gregory A; Borg, Lars E; Wadhwa, Meenakshi

2013-10-22

The isotopic composition of our Solar System reflects the blending of materials derived from numerous past nucleosynthetic events, each characterized by a distinct isotopic signature. We show that the isotopic compositions of elements spanning a large mass range in the earliest formed solids in our Solar System, calcium-aluminum-rich inclusions (CAIs), are uniform, and yet distinct from the average Solar System composition. Relative to younger objects in the Solar System, CAIs contain positive r-process anomalies in isotopes A < 140 and negative r-process anomalies in isotopes A > 140. This fundamental difference in the isotopic character of CAIs around mass 140 necessitates (i) the existence of multiple sources for r-process nucleosynthesis and (ii) the injection of supernova material into a reservoir untapped by CAIs. A scenario of late supernova injection into the protoplanetary disk is consistent with formation of our Solar System in an active star-forming region of the galaxy.

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.

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Pernia, Denet; Evans, Michael; Fu, Qi; Bissada, Kadry K.; Curiale, Joseph A.; Niles, Paul B.

2014-01-01

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas- and liquids-rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC-separated products was sent to a DSQ II quadrupole MS to make qualitative and semi-quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II-S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis-GC-MS-TC-IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from 0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = -215.2 per mille (V-SMOW), ranging from - 271.8 per mille for the Marcellus Shale to -51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of -89.7 per mille, ranging from -156.0 per mille for the Barnett Shale to -50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas-water or oil-water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H-bearing compounds play in terrestrial shale paleo-environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Fractionation of stable isotopes in perchlorate and nitrate during in situ biodegradation in a sandy aquifer

USGS Publications Warehouse

Hatzinger, P.B.; Böhlke, J.K.; Sturchio, N.C.; Gu, B.; Heraty, L.J.; Borden, R.C.

2009-01-01

Environmental context. Perchlorate (ClO4-) and nitrate (NO3-) are common co-contaminants in groundwater, with both natural and anthropogenic sources. Each of these compounds is biodegradable, so in situ enhanced bioremediation is one alternative for treating them in groundwater. Because bacteria typically fractionate isotopes during biodegradation, stable isotope analysis is increasingly used to distinguish this process from transport or mixing-related decreases in contaminant concentrations. However, for this technique to be useful in the field to monitor bioremediation progress, isotope fractionation must be quantified under relevant environmental conditions. In the present study, we quantify the apparent in situ fractionation effects for stable isotopes in ClO4- (Cl and O) and NO3- (N and O) resulting from biodegradation in an aquifer. Abstract. An in situ experiment was performed in a shallow alluvial aquifer in Maryland to quantify the fractionation of stable isotopes in perchlorate (Cl and O) and nitrate (N and O) during biodegradation. An emulsified soybean oil substrate that was previously injected into this aquifer provided the electron donor necessary for biological perchlorate reduction and denitrification. During the field experiment, groundwater extracted from an upgradient well was pumped into an injection well located within the in situ oil barrier, and then groundwater samples were withdrawn for the next 30 h. After correction for dilution (using Br- as a conservative tracer of the injectate), perchlorate concentrations decreased by 78% and nitrate concentrations decreased by 82% during the initial 8.6 h after the injection. The observed ratio of fractionation effects of O and Cl isotopes in perchlorate (18O/37Cl) was 2.6, which is similar to that observed in the laboratory using pure cultures (2.5). Denitrification by indigenous bacteria fractionated O and N isotopes in nitrate at a ratio of ???0.8 (18O/15N), which is within the range of values reported previously for denitrification. However, the magnitudes of the individual apparent in situ isotope fractionation effects for perchlorate and nitrate were appreciably smaller than those reported in homogeneous closed systems (0.2 to 0.6 times), even after adjustment for dilution. These results indicate that (1) isotope fractionation factor ratios (18O/37Cl, 18O/15N) derived from homogeneous laboratory systems (e.g. pure culture studies) can be used qualitatively to confirm the occurrence of in situ biodegradation of both perchlorate and nitrate, but (2) the magnitudes of the individual apparent values cannot be used quantitatively to estimate the in situ extent of biodegradation of either anion. ?? CSIRO 2009.

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.

ESARR: enhanced situational awareness via road sign recognition

NASA Astrophysics Data System (ADS)

Perlin, V. E.; Johnson, D. B.; Rohde, M. M.; Lupa, R. M.; Fiorani, G.; Mohammad, S.

2010-04-01

The enhanced situational awareness via road sign recognition (ESARR) system provides vehicle position estimates in the absence of GPS signal via automated processing of roadway fiducials (primarily directional road signs). Sign images are detected and extracted from vehicle-mounted camera system, and preprocessed and read via a custom optical character recognition (OCR) system specifically designed to cope with low quality input imagery. Vehicle motion and 3D scene geometry estimation enables efficient and robust sign detection with low false alarm rates. Multi-level text processing coupled with GIS database validation enables effective interpretation even of extremely low resolution low contrast sign images. In this paper, ESARR development progress will be reported on, including the design and architecture, image processing framework, localization methodologies, and results to date. Highlights of the real-time vehicle-based directional road-sign detection and interpretation system will be described along with the challenges and progress in overcoming them.

Iron isotope fractionation during hydrothermal ore deposition and alteration

NASA Astrophysics Data System (ADS)

Markl, Gregor; von Blanckenburg, Friedhelm; Wagner, Thomas

2006-06-01

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ56Fe between -2.3‰ and +1.3‰. Primary hematite ( δ56Fe: -0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe ( δ56Fe: -0.5‰) leached from the crystalline basement. Occasional input of CO 2-rich waters resulted in precipitation of isotopically light siderite ( δ56Fe: -1.4 to -0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.

Tracking ENSO with tropical trees: Progress in stable isotope dendroclimatology

NASA Astrophysics Data System (ADS)

Evans, M. N.; Poussart, P. F.; Saleska, S. R.; Schrag, D. P.

2002-12-01

The terrestrial tropics remain an important gap in the growing proxy network used to characterize past ENSO behavior. Here we describe a strategy for development of proxy estimates of paleo-ENSO, via proxy rainfall estimates derived from stable isotope (δ18O) measurements made on tropical trees. The approach applies a new model of oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brand, 1996) to develop proxy chronological, rainfall and growth rate estimates from tropical trees, even those lacking annual rings. The promise and pitfalls of the approach are illustrated in pilot datasets from the US, Costa Rica, Brazil, and Peru, which show isotopic cycles of 4-6 per mil, and interannual anomalies of up to 8 per mil. Together with the mature ENSO proxies (corals, extratropical tree-rings, varved sediments, and ice cores), replicated and well-dated stable isotope chronologies from tropical trees may eventually improve our understanding of ENSO history over the past several hundred years.

Metal stable isotopes in low-temperature systems: A primer

USGS Publications Warehouse

Bullen, T.D.; Eisenhauer, A.

2009-01-01

Recent advances in mass spectrometry have allowed isotope scientists to precisely determine stable isotope variations in the metallic elements. Biologically infl uenced and truly inorganic isotope fractionation processes have been demonstrated over the mass range of metals. This Elements issue provides an overview of the application of metal stable isotopes to low-temperature systems, which extend across the borders of several science disciplines: geology, hydrology, biology, environmental science, and biomedicine. Information on instrumentation, fractionation processes, data-reporting terminology, and reference materials presented here will help the reader to better understand this rapidly evolving field.

Analysis of multi lobe journal bearings with surface roughness using finite difference method

NASA Astrophysics Data System (ADS)

PhaniRaja Kumar, K.; Bhaskar, SUdaya; Manzoor Hussain, M.

2018-04-01

Multi lobe journal bearings are used for high operating speeds and high loads in machines. In this paper symmetrical multi lobe journal bearings are analyzed to find out the effect of surface roughnessduring non linear loading. Using the fourth order RungeKutta method, time transient analysis was performed to calculate and plot the journal centre trajectories. Flow factor method is used to evaluate the roughness and the finite difference method (FDM) is used to predict the pressure distribution over the bearing surface. The Transient analysis is done on the multi lobe journal bearings for threedifferent surface roughness orientations. Longitudinal surface roughness is more effective when compared with isotopic and traverse surface roughness.

Organic Matter Polymerization by Disulfide Bonding Near the Chemocline in Cariaco Basin

NASA Astrophysics Data System (ADS)

Raven, M. R.; Adkins, J. F.; Sessions, A. L.

2013-12-01

The preservation of organic carbon in sediments as kerogen is an essential pathway in the global carbon cycle, but the chemical reactions involved in kerogen formation remain poorly understood. Previous researchers have found that many sediments deposited under euxinic conditions contain sulfur-bearing non-polar lipids as well as disulfide bonds among lipid and carbohydrate monomers. It remains unclear, however, when during organic matter decomposition and diagenesis these different sulfur-bearing structures form, and how different environmental conditions affect the extent of organic matter sulfurization. We investigate organic sulfurization processes armed with a technique for measuring the sulfur-isotopic compositions of individual organosulfur compounds by coupled gas chromatography - inductively coupled plasma mass spectrometry. Organic compounds were extracted from sediments and water column sediment traps from Cariaco Basin, a euxinic basin in the Caribbean Sea. We measured the sulfur-isotopic compositions of both non-polar lipids and of derivatized disulfide-bound compounds from eight sediment trap profiles and a six-meter-long sediment core. In Cariaco Basin, lipid sulfurization processes appear to begin near the chemocline and continue in sediments on timescales of thousands of years. Slow diagenetic sulfurization in sediments produces lipid monomers with sulfur atoms in ring structures that are 34S-depleted relative to coexisting dissolved sulfide. Lipid monomers become progressively enriched in 34S over time, indicating ongoing formation coinciding with an increase in the amount of total sulfur in bulk kerogen. One of the most abundant monomers observed in Cariaco sediments, a phytol-related thiophene, is also produced intermittently near the chemocline. Phytol thiophene δ34S values in sediment traps are similar to those observed in shallow Cariaco sediments except during occasional ';enrichment events,' when phytol thiophene δ34S values increase to as high as -2‰. In contrast, disulfide bonding appears to affect both lipids and carbohydrates and occur exclusively at the chemocline on very short timescales of days to weeks. In both the water column and the sediments, the sulfur isotope ratios of disulfide-bound monosaccharides are dramatically 34S-enriched relative to dissolved sulfide at the chemocline (~-30‰), ranging from -11‰ to +9‰. Disulfide-bound phytenes, which likely derive from the same precursor compounds as phytol thiophenes, were observed in only a few of the sediment trap extracts and have sulfur-isotopic compositions near +4.5‰. These 34S-enriched compositions indicate that the source of sulfur for rapid disulfide bonding may be an intermediate sulfur species that is not in isotopic equilibrium with dissolved sulfide. Significantly, δ34S values for disulfide-bound compounds in Cariaco Basin appear to be set at the chemocline and stable during subsequent diagenesis, opening the possibility that organic sulfur isotopes may archive information about environmental conditions at the chemocline in low-maturity sediments. Disulfide bonding does not, however, appear to be the major process driving slower diagenetic sulfur incorporation into kerogen. Compound-specific organic sulfur isotope analysis makes it possible to distinguish the products of different lipid and carbohydrate sulfurization processes for the first time.

Cu isotopes in marine black shales record the Great Oxidation Event

PubMed Central

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

2016-01-01

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

Thin and thick targets for radioactive ion beam production at SPIRAL1 facility

NASA Astrophysics Data System (ADS)

Jardin, P.; Bajeat, O.; Delahaye, P.; Dubois, M.; Kuchi, V.; Maunoury, L.

2018-05-01

The upgrade of the Système de Production d'Ions Radioactifs Accélérés en Ligne (SPIRAL1) facility will deliver its new Radioactive Ion Beams (RIB) by summer 2017. The goal of the upgrade is an improvement of the performances of the installation in terms of isotopes species and ion charge states [1]. Ion beams are produced using the Isotope Separator On Line Method, consisting in an association of a primary beam of stable ions, a hot target and an ion source. The primary beam impinges on the material of the target. Radioactive isotopes are produced by nuclear reactions and propagate up to the source, where they are ionized and accelerated to create a RIB. One advantage of SPIRAL1 driver is the variety of its available primary beams, from carbon to uranium with energies up to 95 MeV/A. Within the SPIRAL1 upgrade, they will be combined with targets made of a large choice of materials, extending in this way the number of possible nuclear reactions (fusion-evaporation, transfer, fragmentation) for producing a wider range of isotopes, up to regions of the nuclide chart still scarcely explored. Depending on the reaction process, on the collision energy and on the primary beam power, thin and thick targets are used. As their functions can be different, their design must cope with specific constraints which will be described. After a presentation of the goals of present and future SPIRAL1 Target Ion Source System, the main target features, studies and designs under progress are presented.

Chlorine in Lunar Basalts

NASA Technical Reports Server (NTRS)

Barnes, J. J.; Anand, M.; Franchi, I. A.

2017-01-01

In the context of the lunar magma ocean (LMO) model, it is anticipated that chlorine (and other volatiles) should have been concentrated in the late-stage LMO residual melts (i.e., the dregs enriched in incompatible elements such as K, REEs, and P, collectively called KREEP, and in its primitive form - urKREEP, [1]), given its incompatibility in mafic minerals like olivine and pyroxene, which were the dominant phases that crystallized early in the cumulate pile of the LMO (e.g., [2]). When compared to chondritic meteorites and terrestrial rocks (e.g., [3-4]), lunar samples often display heavy chlorine isotope compositions [5-9]. Boyce et al. [8] found a correlation between delta Cl-37 (sub Ap) and bulk-rock incompatible trace elements (ITEs) in lunar basalts, and used this to propose that early degassing of Cl (likely as metal chlorides) from the LMO led to progressive enrichment in remaining LMO melt in Cl-37over Cl-35- the early degassing model. Barnes et al. [9] suggested that relatively late degassing of chlorine from urKREEP (to yield delta Cl-37 (sub urKREEP greater than +25 per mille) followed by variable mixing between KREEPy melts and mantle cumulates (characterized by delta Cl-370 per mille) could explain the majority of Cl isotope data from igneous lunar samples. In order to better understand the processes involved in giving rise to the heavy chlorine isotope compositions of lunar samples, we have performed an in situ study of chlorine isotopes and abundances of volatiles in lunar apatite from a diverse suite of lunar basalts spanning a range of geochemical types.

Compound-Specific Isotope Analysis of Amino Acids for Stardust-Returned Samples

NASA Technical Reports Server (NTRS)

Cook, Jamie; Elsila, Jamie E.; Stern J. C.; Glavin, D. P.; Dworkin, J. P.

2008-01-01

Significant portions of the early Earth's prebiotic organic inventory , including amino acids, could have been delivered to the Earth's sur face by comets and their fragments. Analysis of comets via spectrosc opic observations has identified many organic molecules, including me thane, ethane, arnmonia, cyanic acid, formaldehyde, formamide, acetal ehyde, acetonitrile, and methanol. Reactions between these identifie d molecules could allow the formation of more complex organics such a s amino acids. Isotopic analysis could reveal whether an extraterrest rial signature is present in the Stardust-exposed amines and amino ac ids. Although bulk isotopic analysis would be dominated by the EACA contaminant's terrestrial signature, compoundspecific isotope analysi s (CSIA) could determine the signature of each of the other individua l amines. Here, we report on progress made towards CSIA of the amino acids glycine and EACA in Stardustreturned samples.

Comparative study of radiation, chemical, and aging effects on viral transformation. Annual progress report, 1975

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

Coggin, J.H. Jr.

Progress is reported on the following research projects: evaluation of isotopic antiglobulin test (IAT) to detect tumor associated antigens using antisera induced by x-irradiated tumor cells; development of cytotoxic antibody for embryonic antigens (EA); acrylamide gel cell culture assay for transformation; and evaluation of 3-MCA induced sarcomas for TSTA and cross-reacting antigens. (HLW)

Experimental evaporation of hyperacid brines: Effects on chemical composition and chlorine isotope fractionation

NASA Astrophysics Data System (ADS)

Rodríguez, Alejandro; van Bergen, Manfred J.; Eggenkamp, H. G. M.

2018-02-01

Hyperacid brines from active volcanic lakes are some of the chemically most complex aqueous solutions on Earth. Their compositions provide valuable insights into processes of elemental transfer from a magma body to the surface and interactions with solid rocks and the atmosphere. This paper describes changes in chemical and δ37Cl signatures observed in a 1750 h isothermal evaporation experiment on hyperacid (pH 0.1) sulphate-chloride brine water from the active lake of Kawah Ijen volcano (Indonesia). Although gypsum was the only evaporite mineral identified in the evolving brine, decreasing Si concentrations may ultimately result in amorphous silica precipitation. Geochemical simulations predict the additional formation of elemental sulphur at lower water activities (aH2O ≤ 0.65) that were not reached in the experiment. Absence of other sulphates and halides despite the high load of dissolved elements (initial TDS ca. 100 g/kg) can be attributed to increased solubility of metals, promoted by extensive formation of complexes between the variety of cations and the major anions (HSO4-, Cl-, F-) present. Chlorine deviations from a conservative behaviour point to losses of gaseous hydrogen chloride (HCl(g)) and consequently an increase in Br/Cl ratios. Chlorine isotope fractionation that accompanied the escape of HCl(g) showed a marked change in sign and magnitude in the course of progressive evaporation of the brine. The calculated factor of fractionation between HCl(g) and dissolved Cl for the initial interval (before 500 h) is positive (1000lnαHCl(g)-Cldiss. = + 1.55 ± 0.49‰to + 3.37 ± 1.11‰), indicating that, at first, the escaping HCl(g) was isotopically heavier than the dissolved Cl remaining in the brine. Conversely, fractionation shifted to the opposite direction in the subsequent interval (1000lnαHCl(g)-Cldiss. = 5.67 ± 0.17‰to - 5.64 ± 0.08‰), in agreement with values reported in literature. It is proposed that Cl isotopic fractionation in highly acidic brines is controlled by the distribution of dissolved chlorine species, which changes from Cl- to HClo dominance with the progressive pH decline. The Kawah Ijen lake acquired its extreme composition through influx of sulphur and halogen-rich magmatic gas components and extensive rock dissolution. If hyperacid brines with comparable chemical composition existed on Mars, evaporation processes up to the extent reported here (aH2O = 0.85), were likely accompanied by losses of gaseous HCl. The resulting changes in Cl isotope compositions, Br/Cl, S/Cl and other ratios in the residual brine might be potentially recorded in assemblages of halogen-bearing secondary evaporation minerals. Also, volcanic-hydrothermal brines as these would extend the stability of liquid water on the Martian surface down to a temperature of -90 °C.

Molybdenum isotope fractionation during acid leaching of a granitic uranium ore

NASA Astrophysics Data System (ADS)

Migeon, Valérie; Bourdon, Bernard; Pili, Eric; Fitoussi, Caroline

2018-06-01

As an attempt to prevent illicit trafficking of nuclear materials, it is critical to identify the origin and transformation of uranium materials from the nuclear fuel cycle based on chemical and isotope tracers. The potential of molybdenum (Mo) isotopes as tracers is considered in this study. We focused on leaching, the first industrial process used to release uranium from ores, which is also known to extract Mo depending on chemical conditions. Batch experiments were performed in the laboratory with pH ranging from 0.3 to 5.5 in sulfuric acid. In order to span a large range in uranium and molybdenum yields, oxidizers such as nitric acid, hydrogen peroxide and manganese dioxide were also added. An enrichment in heavy Mo isotopes is produced in the solution during leaching of a granitic uranium ore, when Mo recovery is not quantitative. At least two Mo reservoirs were identified in the ore: ∼40% as Mo oxides soluble in water or sulfuric acid, and ∼40% of Mo hosted in sulfides soluble in nitric acid or hydrogen peroxide. At pH > 1.8, adsorption and/or precipitation processes induce a decrease in Mo yields with time correlated with large Mo isotope fractionations. Quantitative models were used to evaluate the relative importance of the processes involved in Mo isotope fractionation: dissolution, adsorption, desorption, precipitation, polymerization and depolymerization. Model best fits are obtained when combining the effects of dissolution/precipitation, and adsorption/desorption onto secondary minerals. These processes are inferred to produce an equilibrium isotope fractionation, with an enrichment in heavy Mo isotopes in the liquid phase and in light isotopes in the solid phase. Quantification of Mo isotope fractionation resulting from uranium leaching is thus a promising tool to trace the origin and transformation of nuclear materials. Our observations of Mo leaching are also consistent with observations of natural Mo isotope fractionation taking place during chemical weathering in terrestrial environments where the role of secondary processes such as adsorption is significant.