The Effect of Protein Mass Modulation on Human Dihydrofolate Reductase

PubMed Central

Francis, Kevin; Sapienza, Paul J.; Lee, Andrew L.; Kohen, Amnon

2016-01-01

Dihydrofolate reductase (DHFR) from Escherichia coli has long served as a model enzyme with which to elucidate possible links between protein dynamics and the catalyzed reaction. Such physical properties of its human counterpart have not been rigorously studied so far, but recent computer-based simulations suggest that these two DHFRs differ significantly in how closely coupled the protein dynamics and the catalyzed C-H→C hydride transfer step are. To test this prediction, two contemporary probes for studying the effect of protein dynamics on catalysis were combined here: temperature dependence of intrinsic kinetic isotope effects (KIEs) that are sensitive to the physical nature of the chemical step, and protein mass-modulation that slows down fast dynamics (femto- to picosecond timescale) throughout the protein. The intrinsic H/T KIEs of human DHFR, like those of E. coli DHFR, are shown to be temperature-independent in the range from 5–45 °C, indicating fast sampling of donor and acceptor distances (DADs) at the reaction’s transition state (or tunneling ready state – TRS). Mass modulation of these enzymes through isotopic labeling with 13C, 15N, and 2H at nonexchangeable hydrogens yield an 11% heavier enzyme. The additional mass has no effect on the intrinsic KIEs of the human enzyme. This finding indicates that the mass-modulation of the human DHFR affects neither DAD distribution nor the DAD’s conformational sampling dynamics. Furthermore, reduction in the enzymatic turnover number and the dissociation rate constant for the product indicate that the isotopic substitution affects kinetic steps that are not the catalyzed C-H→C hydride transfer. The findings are discussed in terms of fast dynamics and their role in catalysis, the comparison of calculations and experiments, and the interpretation of isotopically-modulated heavy enzymes in general. PMID:26813442

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

NASA Astrophysics Data System (ADS)

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

1995-03-01

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

Neutron-rich rare-isotope production from projectile fission of heavy nuclei near 20 MeV/nucleon beam energy

NASA Astrophysics Data System (ADS)

Vonta, N.; Souliotis, G. A.; Loveland, W.; Kwon, Y. K.; Tshoo, K.; Jeong, S. C.; Veselsky, M.; Bonasera, A.; Botvina, A.

2016-12-01

We investigate the possibilities of producing neutron-rich nuclides in projectile fission of heavy beams in the energy range of 20 MeV/nucleon expected from low-energy facilities. We report our efforts to theoretically describe the reaction mechanism of projectile fission following a multinucleon transfer collision at this energy range. Our calculations are mainly based on a two-step approach: The dynamical stage of the collision is described with either the phenomenological deep-inelastic transfer model (DIT) or with the microscopic constrained molecular dynamics model (CoMD). The de-excitation or fission of the hot heavy projectile fragments is performed with the statistical multifragmentation model (SMM). We compared our model calculations with our previous experimental projectile-fission data of 238U (20 MeV/nucleon) + 208Pb and 197Au (20 MeV/nucleon) + 197Au and found an overall reasonable agreement. Our study suggests that projectile fission following peripheral heavy-ion collisions at this energy range offers an effective route to access very neutron-rich rare isotopes toward and beyond the astrophysical r-process path.

Stable Isotopes, Quantum Computing and Consciousness

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2000-10-01

Recent proposals of quantum computing/computers (QC) based on nuclear spins suggest that consciousness (CON) activity may be related (assisted) to subset of C13 atoms incorporated randomly, or quasirandomly, in neural structures. Consider two DNA chains. Even if they are completely identical chemically (same sequence of codons), patterns of 12C and 13C isotopes in them are different (possible origin of personal individuality). Perhaps it is subsystem of nuclear spins of 13C "sublattice" which forms dynamical system capable of QC and on which CON is "spanned". Some issues related to this hypothesis are: (1) existence of CON-driven positional correlations among C13 atoms, (2) motion (hopping) of C13 via enhanced neutron tunneling, cf. quantum "anti Zeno-effect", (3) possible optimization of concentration of QC-active C13 atoms above their standard isotopic abundance, (4) characteristic time-scales for operation of C13-based QC (perrhaps, broad range of scales), (5) reflection of QC dynamics of C13 on CON, (6) possibility that C13-based QC operates "above" level of "regular" CON (perhaps, Jungian sub/super-CON), (7) isotopicity as connector to universal Library of Patterns ("Platonic World"), (8) self-stabilization of coherence in C13 (sub)system. Some of this questions are, in principle, experimentally addressable through shifting of isotopic abundances.

Assessing ecohydrological controls on catchment water storage, flux and age dynamics using tracers in a physically-based, spatially distributed model

NASA Astrophysics Data System (ADS)

Kuppel, S.; Tetzlaff, D.; Maneta, M. P.; Soulsby, C.

2017-12-01

Stable water isotope tracing has been extensively used in a wide range of geographical environments as a means to understand the sources, flow paths and ages of water stored and exiting a landscape via evapotranspiration, surface runoff and/or stream flow. Comparisons of isotopic signatures of precipitation and water in streams, soils, groundwater and plant xylem facilitates the assessment of how plant water use may affect preferential hydrologic pathways, storage dynamics and transit times in the critical zone. While tracers are also invaluable for testing model structure and accuracy, in most cases the measured isotopic signatures have been used to guide the calibration of conceptual runoff models with simplified vegetation and energy balance representation, which lacks sufficient detail to constrain key ecohydrological controls on flow paths and water ages. Here, we use a physically-based, distributed ecohydrological model (EcH2O) which we have extended to track 2H and 18O (including fractionation processes), and water age. This work is part of the "VeWa" project which aims at understanding ecohydrological couplings across climatic gradients in the wider North, where the hydrological implications of projected environmental change are essentially unknown though expected to be high. EcH2O combines a hydrologic scheme with an explicit representation of plant growth and phenology while resolving the energy balance across the soil-vegetation-atmosphere continuum. We focus on a montane catchment in Scotland, where unique long-term, high resolution hydrometric, ecohydrological and isotopic data allows for extensive model testing and projections. Results show the importance of incorporating soil fractionation processes to explain stream isotope dynamics, particularly seasonal enrichment in this humid, energy-limited catchment. This generic process-based approach facilitates analysis of dynamics in isotopes, storage and ages for the different hydrological compartments (canopy to groundwater) and, in particular, the explicit partitioning between soil evaporation and plant transpiration. Our study clearly advances our understanding of dynamics in water storage, flux and age in northern ecosystems, integrating ecohydrology, unsaturated zone, surface water, and groundwater hydrology.

Atomic and Molecular Beam Scattering: Characterizing Structure and Dynamics of Hybrid Organic-Semiconductor Interfaces and Introducing Novel Isotope Separation Techniques

NASA Astrophysics Data System (ADS)

Nihill, Kevin John

This thesis details a range of experiments and techniques that use the scattering of atomic beams from surfaces to both characterize a variety of interfaces and harness mass-specific scattering conditions to separate and enrich isotopic components in a mixture of gases. Helium atom scattering has been used to characterize the surface structure and vibrational dynamics of methyl-terminated Ge(111), thereby elucidating the effects of organic termination on a rigid semiconductor interface. Helium atom scattering was employed as a surface-sensitive, non-destructive probe of the surface. By means of elastic gas-surface diffraction, this technique is capable of providing measurements of atomic spacing, step height, average atomic displacement as a function of surface temperature, gas-surface potential well depth, and surface Debye temperature. Inelastic time-of-flight studies provide highly resolved energy exchange measurements between helium atoms and collective lattice vibrations, or phonons; a collection of these measurements across a range of incident kinematic parameters allowed for a thorough mapping of low-energy phonons (e.g., the Rayleigh wave) across the surface Brillouin zone and subsequent comparison with complementary theoretical calculations. The scattering of molecular beams - here, hydrogen and deuterium from methyl-terminated Si(111) - enables the measurement of the anisotropy of the gas-surface interaction potential through rotationally inelastic diffraction (RID), whereby incident atoms can exchange internal energy between translational and rotational modes and diffract into unique angular channels as a result. The probability of rotational excitations as a function of incident energy and angle were measured and compared with electronic structure and scattering calculations to provide insight into the gas-surface interaction potential and hence the surface charge density distribution, revealing important details regarding the interaction of H2 with an organic-functionalized semiconductor interface. Aside from their use as probes for surface structure and dynamics, atomic beam sources are also demonstrated to enable the efficient separation of gaseous mixtures of isotopes by means of diffraction and differential condensation. In the former method, the kinematic conditions for elastic diffraction result in an incident beam of natural abundance neon diffracting into isotopically distinct angles, resulting in the enrichment of a desired isotope; this purification can be improved by exploiting the difference in arrival times of the two isotopes at a given final angle. In the latter method, the identical incident velocities of coexpanded isotopes lead to minor but important differences in their incident kinetic energies, and thus their probability of adsorbing on a sufficiently cold surface, resulting in preferential condensation of a given isotope that depends on the energy of the incident beam. Both of these isotope separation techniques are made possible by the narrow velocity distribution and velocity seeding effect offered only by high-Mach number supersonic beam sources. These experiments underscore the utility of supersonically expanded atomic and molecular beam sources as both extraordinarily precise probes of surface structure and dynamics and as a means for high-throughput, non-dissociative isotopic enrichment methods.

Sulfur isotope biogeochemistry of soils from an episodically flooded coastal wetland, southern Baltic Sea

NASA Astrophysics Data System (ADS)

Fernández Fernández, Luz Eva; Westphal, Julia; Schmiedinger, Iris; Kreuzburg, Matthias; Bahlo, Reiner; Koebsch, Franziska; Böttcher, Michael E.

2017-04-01

Coastal wetlands are under dynamic impact both from fresh water and salt water sources, thereby experiencing temporarily sulfur-excess and -limiting conditions. In the present study, nine up to 10 meter long sediment cores from a recently rewetted fen (Hütelmoor, southern Baltic Sea) which has been under impact by episodic flooding with brackish waters were investigated (isotope) geochemically. The sites are positioned at different distances to the Baltic Sea coastline. The soils were analyzed for the elemental composition (CNS), reactive iron and sedimentary sulfur contents, iron sulfide micro-textures, as well as the stable sulfur isotope composition of inorganic and organic sulfur fractions to understand signal development for the biogeochemical carbon-sulfur cycles in such a dynamic ecosystem. We found evidence for the activity of dissimilatory sulfate-reducing microorganisms and the associated formation of pyrite with different textures (framboids, single euhedral crystals and clusters) and sulfurization of organic matter. Sedimentary sulfur fractions and their stable isotope signatures are controlled by the availability of dissolved organic matter or methane, reactive iron, and in particular dissolved sulfate and thereby from the relative position to the coast line and the given lithology. d34S values in the pyrite fraction vary in a wide range between -21 and +15 per mil versus VCDT, in agreement with spatial and temporal dynamics in the extend of sulfate-limiting conditions during the oxidation of reduced carbon.

Design of multihundredwatt DIPS for robotic space missions

NASA Technical Reports Server (NTRS)

Bents, D. J.; Geng, S. M.; Schreiber, J. G.; Withrow, C. A.; Schmitz, P. C.; Mccomas, Thomas J.

1991-01-01

Design of a dynamic isotope power system (DIPS) general purpose heat source (GPHS) and small free piston Stirling engine (FPSE) is being pursued as a potential lower cost alternative to radioisotope thermoelectric generators (RTG's). The design is targeted at the power needs of future unmanned deep space and planetary surface exploration missions ranging from scientific probes to SEI precursor missions. These are multihundredwatt missions. The incentive for any dynamic system is that it can save fuel which reduces cost and radiological hazard. However, unlike a conventional DIPS based on turbomachinery converions, the small Stirling DIPS can be advantageously scaled to multihundred watt unit size while preserving size and weight competitiveness with RTG's. Stirling conversion extends the range where dynamic systems are competitive to hundreds of watts (a power range not previously considered for dynamic systems). The challenge of course is to demonstrate reliability similar to RTG experience. Since the competative potential of FPSE as an isotope converter was first identified, work has focused on the feasibility of directly integrating GPHS with the Stirling heater head. Extensive thermal modeling of various radiatively coupled heat source/heater head geometries were performed using data furnished by the developers of FPSE and GPHS. The analysis indicates that, for the 1050 K heater head configurations considered, GPHS fuel clad temperatures remain within safe operating limits under all conditions including shutdown of one engine. Based on these results, preliminary characterizations of multihundred watt units were established.

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

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

Chakraborty, Subrata; Davis, Ryan; Ahmed, Musahid

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

Molecular DYNAmics of Soil Organic carbon (DYNAMOS ): a project focusing on soils and carbon through data and modeling

NASA Astrophysics Data System (ADS)

Mendez-Millan, Mercedes

2010-05-01

Here we present the first results of the DynaMOS project whose main issue is the build-up of a new generation of soil carbon model. The modeling will describe together soil organic geochemistry and soil carbon dynamics in a generalized, quantitative representation. The carbon dynamics time scale envisaged here will cover the 1 to 1000 yr range and describe molecule behaviours (i.e.)carbohydrate, peptide, amino acid, lignin, lipids, their products of biodegradation and uncharacterized carbonaceous species of biological origin. Three main characteristics define DYNAMOS model originalities: it will consider organic matter at the molecular scale, integrate back to global scale and account for component vertical movements. In a first step, specific data acquisition will concern the production, fate and age of carbon of individual organic compounds. Dynamic parameters will be acquired by compound-specific carbon isotope analysis of both 13C and 14C, by GC/C/IR-MS and AMS. Sites for data acquisition, model calibration and model validation will be chosen on the base of their isotopic history and environmental constraints: 13C natural labeling (with and without C3/C4 vegetation changes), 13C/15N-labelled litter application in both forest and cropland. They include some long-term experiments owned by the partners themselves plus a worldwide panel of sites. In a second step the depth distribution of organic species, isotopes and ages in soils (1D representation) will be modeled by coupling carbon dynamics and vertical movement. Besides the main objective of providing a robust soil carbon dynamics model, DYNAMOS will assess and model the alteration of the isotopic signature of molecules throughout decay and create a shared database of both already published and new data of compound specific information. Issues of the project will concern different scientific fields: global geochemical cycles by refining the description of the terrestrial carbon cycle and entering the chemical composition of organic matter in carbon models; forestry or agriculture by offering a chemical frame for the management of crop residues or organic wastes; geochronology, paleoecology and paleo climatology by modeling the alteration of isotope signature and the preservation of terrestrial biomarkers.

Estimating wetland connectivity to streams in the Prairie Pothole Region: An isotopic and remote sensing approach

USGS Publications Warehouse

Brooks, J. R.; Mushet, David M.; Vanderhoof, Melanie; Leibowitz, Scott G.; Neff, Brian; Christensen, J. R.; Rosenberry, Donald O.; Rugh, W. D.; Alexander, L.C.

2018-01-01

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding the reliance of stream flow on inputs from wetlands. We used the isotopic evaporation signal in water and remote sensing to examine wetland‐stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie‐pothole wetlands. Pipestem Creek exhibited an evaporated‐water signal that had approximately half the isotopic‐enrichment signal found in most evaporatively enriched prairie‐pothole wetlands. Groundwater adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment, indicating that enriched surface water did not contribute significantly to groundwater discharging into Pipestem Creek. The estimated surface water area necessary to generate the evaporation signal within Pipestem Creek was highly dynamic, varied primarily with the amount of discharge, and was typically greater than the immediate Pipestem Creek surface water area, indicating that surficial flow from wetlands contributed to stream flow throughout the summer. We propose a dynamic range of spilling thresholds for prairie‐pothole wetlands across the watershed allowing for wetland inputs even during low‐flow periods. Combining Landsat estimates with the isotopic approach allowed determination of potential (Landsat) and actual (isotope) contributing areas in wetland‐dominated systems. This combined approach can give insights into the changes in location and magnitude of surface water and groundwater pathways over time. This approach can be used in other areas where evaporation from wetlands results in a sufficient evaporative isotopic signal.

Molybdenum isotope fractionation during complexation with organic matter in the Critical Zone

NASA Astrophysics Data System (ADS)

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

2016-12-01

Molybdenum (Mo) is a micronutrient and a redox sensitive trace metal that also forms strong complexes with organic matter (OM). The fractionation of Mo in sediments associated with adsorption onto both iron (Fe) and manganese (Mn) (oxyhydr)oxides under oxic conditions and sulfide phases under euxinic conditions has been used to constrain redox conditions in the ocean. Additionally, Mo isotope dynamics in terrestrial systems can shed light on the pedogenic mechanisms driving the riverine Mo isotopic composition and how atmospheric inputs alter the trace metal budget and isotopic composition of soils. As a result of these studies, it has been hypothesized that multiple mechanisms are responsible for fractionating Mo isotopes. In particular, Mo fractionation during adsorption onto OM is unknown, despite the fact this mechanism is 3x to more than 20x greater than adsorption onto Fe- and Mn- (oxyhydr)oxides across a range of soil types from Oregon, Iceland, and Hawaii1-3 (Marks et al., 2015; Siebert et al., 2015; King et al., 2016). In this study, we measured Mo adsorption and isotopic fractionation onto insolubilized humic acid (IHA), a proxy for OM, as a function of both adsorption time (2-170 h) and pH (2-7). Preliminary results suggest that for the time series experiment, Mo adsorption onto IHA increased from 35% to 64% and a plateau was reached after 24 hours. The average Mo isotope fractionation between the solution and the IHA was Δ98Mosolution-IHA = 1.8 ± 0.3‰. For the pH series experiment, the average Mo isotope fractionation was Δ98Mosolution-IHA = 2.0 ± 0.2‰. Next, we compared the Mo isotopic composition of foliage, O-horizon, and surface soil from 12 sites in the Oregon Coast Range to better understand the impact of OM on Mo isotope dynamics in natural samples. The potential isotopic offset between dissolved and adsorbed Mo onto OM is of the same order of magnitude and direction as fractionation onto Fe- and Mn- (oxyhydr)oxides such as ferrihydrite, hematite, and birnessite which have Δ98Mosolution-oxide values of 1.1‰, 2.2‰, and 1.8‰, respectively (Goldberg et al., 2009; Wasylenki et al., 2011). These results have important implications for the interpretation of the sedimentary Mo record, its use as a paleoredox tracer, and its potential to record changes in the terrestrial weathering environment.

High-precision optical measurements of 13C/12C isotope ratios in organic compounds at natural abundance

PubMed Central

Zare, Richard N.; Kuramoto, Douglas S.; Haase, Christa; Tan, Sze M.; Crosson, Eric R.; Saad, Nabil M. R.

2009-01-01

A continuous-flow cavity ring-down spectroscopy (CRDS) system integrating a chromatographic separation technique, a catalytic combustor, and an isotopic 13C/12C optical analyzer is described for the isotopic analysis of a mixture of organic compounds. A demonstration of its potential is made for the geochemically important class of short-chain hydrocarbons. The system proved to be linear over a 3-fold injection volume dynamic range with an average precision of 0.95‰ and 0.67‰ for ethane and propane, respectively. The calibrated accuracy for methane, ethane, and propane is within 3‰ of the values determined using isotope ratio mass spectrometry (IRMS), which is the current method of choice for compound-specific isotope analysis. With anticipated improvements, the low-cost, portable, and easy-to-use CRDS-based instrumental setup is poised to evolve into a credible challenge to the high-cost and complex IRMS-based technique. PMID:19564619

Geological controls on isotopic signatures of streamflow: results from a nested catchment experiment in Luxembourg (Europe)

NASA Astrophysics Data System (ADS)

Pfister, Laurent; McDonnell, Jeffrey J.; Hissler, Christophe; Martinez-Carreras, Nuria; Gourdol, Laurent; Klaus, Julian; François Iffly, Jean; Barnich, François; Stewart, Mike K.

2014-05-01

Controls of geology and topography on hydrological metrics, like summer low flow (Grant and Tague, 2004) or dynamic storage (Sayama et al., 2011), have been identified in nested catchment experiments. However, most tracer-based studies on streamflow generation have been carried out in small (10 km2) homogenous catchments (Klaus and McDonnell, 2013). The controlling effects of catchment physiography on how catchments store and release water, and how this eventually controls stream isotope behaviour over a large range of scale are poorly understood. Here, we present results from a nested catchment analysis in the Alzette River basin (Luxembourg, Europe). Our hydro-climatological network consists of 16 recording streamgauges and 21 pluviographs. Catchment areas range from 0.47 to 285 km2, with clean and mixed combinations of distinct geologies ranging from schists to marls, sandstone, dolomite and limestone. Our objective was to identify geological controls on (i) winter runoff ratios, (ii) maximum storage and (iii) isotopic signatures in streamflow. For each catchment we determined average runoff ratios from winter season precipitation-discharge double-mass curves. Maximum catchment storage was based on the dynamic storage change approach of Sayama et al. (2011). Changes in isotopic signatures of streamflow were documented along individual catchment flow duration curves. We found strong correlations between average winter runoff ratios, maximum storage and the prevailing geological settings. Catchments with impermeable bedrock (e.g. marls or schists) were characterised by small storage potential and high average filling ratios. As a consequence, these catchments also exhibited the highest average runoff ratios. In catchments underlain by permeable bedrock (e.g. sandstone), storage potential was significantly higher and runoff ratios were considerably smaller. The isotopic signatures of streamflow showed large differences between catchments. In catchments dominated by permeable bedrock, isotopic signatures of streamflow remained stable throughout the entire flow duration curve consistent with a large storage and mixing potential. On less permeable bedrock substrate, we have observed that isotopic signatures in streamflow were much more variable, due to reduced storage volume and comparatively smaller mixing potential. Other metrics such as catchment size and flowpath length exerted a smaller secondary control on isotopic signatures of streamflow in the Alzette River sub-basins. Tague, C., Grant, G.E., 2004. A geological framework for interpreting the low-flow regimes of Cascade streams, Willamette River Basin, Oregon. Water Resources Research, 40(4), doi:10.1029/2003WR002629 Sayama, T., McDonnell, J.J., Dhakal, A., Sullivan, K., 2011. How much water can a watershed store ? Hydrological Processes 25, 3899-3908. Klaus, J., McDonnell, J.J., 2013. Hydrograph separation using stable isotopes: Review and evaluation. Journal of Hydrology 505, 47-64.

Isotope hydrology and baseflow geochemistry in natural and human-altered watersheds in the Inland Pacific Northwest, USA.

PubMed

Sánchez-Murillo, Ricardo; Brooks, Erin S; Elliot, William J; Boll, Jan

2015-01-01

This study presents a stable isotope hydrology and geochemical analysis in the inland Pacific Northwest (PNW) of the USA. Isotope ratios were used to estimate mean transit times (MTTs) in natural and human-altered watersheds using the FLOWPC program. Isotope ratios in precipitation resulted in a regional meteoric water line of δ(2)H = 7.42·δ(18)O + 0.88 (n = 316; r(2) = 0.97). Isotope compositions exhibited a strong temperature-dependent seasonality. Despite this seasonal variation, the stream δ(18)O variation was small. A significant regression (τ = 0.11D(-1.09); r(2) = 0.83) between baseflow MTTs and the damping ratio was found. Baseflow MTTs ranged from 0.4 to 0.6 years (human-altered), 0.7 to 1.7 years (mining-altered), and 0.7 to 3.2 years (forested). Greater MTTs were represented by more homogenous aqueous chemistry whereas smaller MTTs resulted in more dynamic compositions. The isotope and geochemical data presented provide a baseline for future hydrological modelling in the inland PNW.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber.

PubMed

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-12-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

Past Asian Monsoon circulation from multiple tree-ring proxies and models (Invited)

NASA Astrophysics Data System (ADS)

Anchukaitis, K. J.; Herzog, M.; Hernandez, M.; Martin-Benito, D.; Gagen, M.; LeGrande, A. N.; Ummenhofer, C.; Buckley, B.; Cook, E. R.

2013-12-01

The Asian monsoon can be characterized in terms of precipitation variability as well as features of regional atmospheric circulation across a range of spatial and temporal scales. While multicentury time series of tree-ring widths at hundreds of sites across Asia provide estimates of past rainfall, the oxygen isotope ratios of annual rings at some of these sites can reveal broader regional atmosphere-ocean dynamics. Here we present a replicated, multicentury stable isotope series from Vietnam that integrates the influence of monsoon circulation on water isotopes. Stronger (weaker) monsoon flow over Indochina is associated with lower (higher) oxygen isotope values in our long-lived tropical conifers. Ring width and isotopes show particular coherence at multidecadal time scales, and together allow past precipitation amount and circulation strength to be disentangled. Combining multiple tree-ring proxies with simulations from isotope-enabled and paleoclimate general circulation models allows us to independently assess the mechanisms responsible for proxy formation and to evaluate how monsoon rainfall is influenced by ocean-atmosphere interactions at timescales from interannual to multidecadal.

Using "isotopic spike" from tropical storm to understand water exchange on large scale: case study of Hurricane Rafael in the Lesser Antilles archipelago, October 2012.

PubMed

Lambs, Luc; Bompy, Félix; Dulormne, Maguy

2018-01-03

Studies of wetland eco-hydrology in tropical coastal area are scarce, and the use of water stable isotopes can be of great help. Key constraints for their analysis are (i) the small difference in δ 18 O values between seawater and old evaporated freshwater, and (ii) the fact that the presence of old brackish water limits the determination of the water origin and dynamic. The water of tropical storms displays distinctively depleted heavy stable isotopes, in comparison with usual tropical rainfall without strong convective thunderstorms. During tropical storms, such as Hurricane Rafael in mid-October 2012, the rainfall δ 18 O signal can be decreased by many units. This effect is called an "isotopic spike", and it could be used as a temporal marker of the water fluxes. Water samples, with δ 18 O values as low as = -8.9 ‰, were collected in the islands of Guadeloupe and Saint-Martin during Hurricane Rafael, whereas the usual range of groundwater or mean rainfall δ 18 O values is around -2.8 ± 0.5 ‰, as measured from 2009 to 2012. These water "isotopic spikes" allow us to show a surface fresh water uptake by mangrove trees in Guadeloupe, and in Saint-Martin, to calculate the water renewal of the salt ponds and pools. The "isotopic spikes" generated by tropical storms, are generally used to track back past storm events, as recorded in trees and stalagmites. Here, the propagation of isotopic spike is followed to improve the understanding of the freshwater circulation and the water dynamic within coastal ecosystems influenced by seawater. This article is protected by copyright. All rights reserved.

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

Trajectory Calculations for Bergman Cyclization Predict H/D Kinetic Isotope Effects Due to Nonstatistical Dynamics in the Product.

PubMed

Doubleday, Charles; Boguslav, Mayla; Howell, Caronae; Korotkin, Scott D; Shaked, David

2016-06-22

An unusual H/D kinetic isotope effect (KIE) is described, in which isotopic selectivity arises primarily from nonstatistical dynamics in the product. In DFT-based quasiclassical trajectories of Bergman cyclization of (Z)-3-hexen-1,5-diyne (1) at 470 K, the new CC bond retains its energy, and 28% of nascent p-benzyne recrosses back to the enediyne on a vibrational time scale. The competing process of intramolecular vibrational redistribution (IVR) in p-benzyne is too slow to prevent this. Deuteration increases the rate of IVR, which decreases the fraction of recrossing and increases the yield of statistical (trapable) p-benzyne, 2. Trapable yields for three isotopomers of 2 range from 72% to 86%. The resulting KIEs for Bergman cyclization differ substantially from KIEs predicted by transition state theory, which suggests that IVR in this reaction can be studied by conventional KIEs. Leakage of vibrational zero point energy (ZPE) into the reaction coordinate was probed by trajectories in which initial ZPE in the CH/CD stretching modes was reduced by 25%. This did not change the predicted KIEs.

Vibrationally-Resolved Kinetic Isotope Effects in the Proton-Transfer Dynamics of Ground-State Tropolone

NASA Astrophysics Data System (ADS)

Chew, Kathryn; Vealey, Zachary; Vaccaro, Patrick

2015-06-01

The vibrational and isotopic dependence of the hindered (tunneling-mediated) proton-transfer reaction taking place in the ground electronic state ( X1{A}1) of monodeuterated tropolone (TrOD) has been explored under ambient (bulk-gas) conditions by applying two-color variants of resonant four-wave mixing (RFWM) spectroscopy in conjunction with polarization-resolved detection schemes designed to alleviate spectral complexity and facilitate rovibrational assignments. Full rotation-tunneling analyses of high-resolution spectral profiles acquired for the fundamental and first-overtone bands of a reaction-promoting O-D\\cdotsO deformation/ring-breathing mode, νb{36}(a1), were performed, thereby extracting refined structural and dynamical information that affords benchmarks for the quantitative interpretation of tunneling-induced signatures found in long-range scans of X1{A}1 vibrational levels residing below Etilde{X}vib = 1700 wn}. Observed kinetic isotope effects, which reflect changes in both reaction kinematics and vibrational displacements, will be discussed, with high-level quantum-chemical calculations serving to elucidate state-resolved propensities for proton transfer in TrOH and TrOD.

Measuring Long-Range 13C– 13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance [Measuring Long Range 13C– 13C Correlations on Surface under Natural Abundance Using DNP-enhanced Solid-state NMR

DOE PAGES

Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek

2017-10-13

Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C– 13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.

Measuring Long-Range 13C– 13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance [Measuring Long Range 13C– 13C Correlations on Surface under Natural Abundance Using DNP-enhanced Solid-state NMR

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

Kobayashi, Takeshi; Slowing, Igor I.; Pruski, Marek

Here, we report that spatial (<1 nm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C– 13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution.

Molecular DYNAmics of Soil Organic carbon (DYNAMOS *): a project focusing on soils and carbon through data and modeling

NASA Astrophysics Data System (ADS)

Hatté, C.; Balesdent, J.; Derenne, S.; Derrien, D.; Dignac, M.; Egasse, C.; Ezat, U.; Gauthier, C.; Mendez-Millan, M.; Nguyen Tu, T.; Rumpel, C.; Sicre, M.; Zeller, B.

2009-12-01

Here we present the first results of the DynaMOS project whose main issue is the build-up of a new generation of soil carbon model. The modeling will describe together soil organic geochemistry and soil carbon dynamics in a generalized, quantitative representation. The carbon dynamics time scale envisaged here will cover the 1 to 1000 yr range and described molecules will be carbohydrate, peptide, amino acid, lignin, lipids, their products of biodegradation and uncharacterized carbonaceous species of biological origin. Three main characteristics define DYNAMOS model originalities: it will consider organic matter at the molecular scale, integrate back to global scale and account for component vertical movements. In a first step, specific data acquisition will concern the production, fate and age of carbon of individual organic compounds. Dynamic parameters will be acquired by compound-specific carbon isotope analysis of both 13C and 14C, by GC/C/IR-MS and AMS. Sites for data acquisition, model calibration and model validation will be chosen on the base of their isotopic history and environmental constraints: 13C natural labeling (with and without C3/C4 vegetation changes), 13C/15N-labelled litter application in both forest and cropland. They include some long-term experiments owned by the partners themselves plus a worldwide panel of sites. In a second step the depth distribution of organic species, isotopes and ages in soils (1D representation) will be modeled by coupling carbon dynamics and vertical movement. Besides the main objective of providing a robust soil carbon dynamics model, DYNAMOS will assess and model the alteration of the isotopic signature of molecules throughout decay and create a shared database of both already published and new data of compound specific information. Issues of the project will concern different scientific fields: global geochemical cycles by refining the description of the terrestrial carbon cycle and entering the chemical composition of organic matter in carbon models; forestry or agriculture by offering a chemical frame for the management of crop residues or organic wastes; geochronology, paleoecology and paleo climatology by modeling the alteration of isotope signature and the preservation of terrestrial biomarkers. (*) funded by the French National Agency of Research (ANR): ANR-07-Blan-0222-01, http://dynamos.lsce.ipsl.fr

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes

NASA Astrophysics Data System (ADS)

Mazzuca, James W.; Haut, Nathaniel K.

2018-06-01

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber

PubMed Central

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-01-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ57Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ57Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ57Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted. PMID:26620121

Theoretical description of quantum mechanical permeation of graphene membranes by charged hydrogen isotopes.

PubMed

Mazzuca, James W; Haut, Nathaniel K

2018-06-14

It has been recently shown that in the presence of an applied voltage, hydrogen and deuterium nuclei can be separated from one another using graphene membranes as a nuclear sieve, resulting in a 10-fold enhancement in the concentration of the lighter isotope. While previous studies, both experimental and theoretical, have attributed this effect mostly to differences in vibrational zero point energy (ZPE) of the various isotopes near the membrane surface, we propose that multi-dimensional quantum mechanical tunneling of nuclei through the graphene membrane influences this proton permeation process in a fundamental way. We perform ring polymer molecular dynamics calculations in which we include both ZPE and tunneling effects of various hydrogen isotopes as they permeate the graphene membrane and compute rate constants across a range of temperatures near 300 K. While capturing the experimentally observed separation factor, our calculations indicate that the transverse motion of the various isotopes across the surface of the graphene membrane is an essential part of this sieving mechanism. An understanding of the multi-dimensional quantum mechanical nature of this process could serve to guide the design of other such isotopic enrichment processes for a variety of atomic and molecular species of interest.

Ecohydrology of permafrost-affected boreal forest ecosystems: sources of water utilized by plants and fluxed by ecosystems

NASA Astrophysics Data System (ADS)

Cable, J. M.; Ogle, K.; Cable, B.; Welker, J. M.

2010-12-01

The interior Alaskan boreal forest ecosystem is underlain by permafrost and thus has complex soil moisture and soil thermal properties, and this complexity is further amplified by its dry climate with low snow in winter and minimal summer rain. This combination of climate, cryosphere, and hydrology characteristics impact vegetation ecophysiological and ecohydrological processes, such as the distribution of plant-available water sources and the temporal dynamics of evapotranspiration (ET). As a major component of ET, plant transpiration is typically sustained throughout a variety of climatic conditions. The water sources (rain, thawing ground ice, etc) supporting plant transpiration are relatively unquantified, particularly on a seasonal time scale. In this study, we ask: what are the seasonal dynamics of plant water use in the boreal forest, and how are the trends at the plant scale translated into ecosystem-level water fluxes? Thus, the objective of this study was to characterize the spatial and temporal dynamics of boreal plant water use and water flux throughout the growing season. To do this, we measured the stable isotope (δ18O and δD) composition of water from precipitation, ground ice, soils, plants, and vapor from 5 heights in the ecosystem during the growing season in a boreal system near Fairbanks, Alaska underlain by permafrost. We analyzed the plant water, soil water, and vapor isotope data in a Bayesian framework to quantify the plant water uptake profiles and to explore the implications of shifting water sources for ecosystem ET. The vapor isotope data (across all heights) ranged from -216 to -190 ‰ (δD) and -27 to -21 ‰ (δ18O) in late July to slightly more depleted in late August, with values ranging from -232 to -203 ‰ (δD) and -29 to -20 ‰ (δ18O). Diurnal trends are such that the isotope composition of vapor became more enriched over the day as ET rates increased, and vapor at the 0.25 m height was generally more enriched relative to the 6 m height. Plant and soil isotope sampling from prior years shows that dwarf birch (B. nana, the dominant shrub in the ecosystem sampled by the vapor analyzer) gets about 50% of its water from surface, rain-fed soil layers and 50% of its water from deeper soil layers (fed by thawing ground ice). This is one of the first studies to show the patterns of boreal ecosystem water isotopes at diurnal (vapor) and seasonal (plant) scales. Understanding the isotopic composition of water vapor from northern ecosystems is paramount to advancing estimates of biosphere-atmosphere interactions and the nature of ecohydrologic feedbacks to the changing state of the North.

A Novel Method for Relative Quantitation of N-Glycans by Isotopic Labeling Using 18O-Water

PubMed Central

Tao, Shujuan; Orlando, Ron

2014-01-01

Quantitation is an essential aspect of comprehensive glycomics study. Here, a novel isotopic-labeling method is described for N-glycan quantitation using 18O-water. The incorporation of the 18O-labeling into the reducing end of N-glycans is simply and efficiently achieved during peptide-N4-(N-acetyl-β-glucosaminyl) asparagine amidase F release. This process provides a 2-Da mass difference compared with the N-glycans released in 16O-water. A mathematical calculation method was also developed to determine the 18O/16O ratios from isotopic peaks. Application of this method to several standard glycoprotein mixtures and human serum demonstrated that this method can facilitate the relative quantitation of N-glycans over a linear dynamic range of two orders, with high accuracy and reproducibility. PMID:25365792

Carbon dioxide photolysis from 150 to 210 nm: singlet and triplet channel dynamics, UV-spectrum, and isotope effects.

PubMed

Schmidt, Johan A; Johnson, Matthew S; Schinke, Reinhard

2013-10-29

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ~167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ~0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues ((12)C(16)O2, (12)C(17)O(16)O, (12)C(18)O(16)O, (13)C(16)O2, and (13)C(18)O(16)O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of (17)O containing CO2 more efficient.

Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects

PubMed Central

Schmidt, Johan A.; Johnson, Matthew S.; Schinke, Reinhard

2013-01-01

We present a first principles study of the carbon dioxide (CO2) photodissociation process in the 150- to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + singlet channel threshold at ∼167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ∼0.5 nm without scaling the intensity. The observed structure in the 150- to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the and potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. The cross-sections of individual CO2 isotopologues (12C16O2, 12C17O16O, 12C18O16O, 13C16O2, and 13C18O16O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on mass-independent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of 17O containing CO2 more efficient. PMID:23776249

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

USGS Publications Warehouse

Scholl, Martha A.; Murphy, Sheila F.

2014-01-01

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

Characterization of 3-Dimensional PET Systems for Accurate Quantification of Myocardial Blood Flow.

PubMed

Renaud, Jennifer M; Yip, Kathy; Guimond, Jean; Trottier, Mikaël; Pibarot, Philippe; Turcotte, Eric; Maguire, Conor; Lalonde, Lucille; Gulenchyn, Karen; Farncombe, Troy; Wisenberg, Gerald; Moody, Jonathan; Lee, Benjamin; Port, Steven C; Turkington, Timothy G; Beanlands, Rob S; deKemp, Robert A

2017-01-01

Three-dimensional (3D) mode imaging is the current standard for PET/CT systems. Dynamic imaging for quantification of myocardial blood flow with short-lived tracers, such as 82 Rb-chloride, requires accuracy to be maintained over a wide range of isotope activities and scanner counting rates. We proposed new performance standard measurements to characterize the dynamic range of PET systems for accurate quantitative imaging. 82 Rb or 13 N-ammonia (1,100-3,000 MBq) was injected into the heart wall insert of an anthropomorphic torso phantom. A decaying isotope scan was obtained over 5 half-lives on 9 different 3D PET/CT systems and 1 3D/2-dimensional PET-only system. Dynamic images (28 × 15 s) were reconstructed using iterative algorithms with all corrections enabled. Dynamic range was defined as the maximum activity in the myocardial wall with less than 10% bias, from which corresponding dead-time, counting rates, and/or injected activity limits were established for each scanner. Scatter correction residual bias was estimated as the maximum cavity blood-to-myocardium activity ratio. Image quality was assessed via the coefficient of variation measuring nonuniformity of the left ventricular myocardium activity distribution. Maximum recommended injected activity/body weight, peak dead-time correction factor, counting rates, and residual scatter bias for accurate cardiac myocardial blood flow imaging were 3-14 MBq/kg, 1.5-4.0, 22-64 Mcps singles and 4-14 Mcps prompt coincidence counting rates, and 2%-10% on the investigated scanners. Nonuniformity of the myocardial activity distribution varied from 3% to 16%. Accurate dynamic imaging is possible on the 10 3D PET systems if the maximum injected MBq/kg values are respected to limit peak dead-time losses during the bolus first-pass transit. © 2017 by the Society of Nuclear Medicine and Molecular Imaging.

A comparison of radioisotope Brayton and Stirling systems for lunar surface mobile power

NASA Astrophysics Data System (ADS)

Harty, Richard B.

A study was performed by the Rocketdyne Division of Rockwell International on a 2.5-kWe modular dynamic isotope power system (DIPS) using a Stirling power conversion system. The results of this study were compared with similar results performed under the DIPS program using a Brayton power conversion system. The application considered was for lunar mobile power sources in the power range of 2.5 kWe to 15 kWe. The study indicated that the Stirling power module has 20 percent lower mass and 40 percent lower radiator area than the Brayton module. However, the study also revealed that because the Stirling power module requires a complex heat pipe arrangement to transport heat from the isotope to the Stirling heater head and a pumped NaK heat rejection loop, the Stirling module is much more difficult to integrate with the isotope heat source and heat rejection system.

Attomole quantitation of protein separations with accelerator mass spectrometry

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

Vogel, J S; Grant, P G; Buccholz, B A

2000-12-15

Quantification of specific proteins depends on separation by chromatography or electrophoresis followed by chemical detection schemes such as staining and fluorophore adhesion. Chemical exchange of short-lived isotopes, particularly sulfur, is also prevalent despite the inconveniences of counting radioactivity. Physical methods based on isotopic and elemental analyses offer highly sensitive protein quantitation that has linear response over wide dynamic ranges and is independent of protein conformation. Accelerator mass spectrometry quantifies long-lived isotopes such as 14C to sub-attomole sensitivity. We quantified protein interactions with small molecules such as toxins, vitamins, and natural biochemicals at precisions of 1-5% . Micro-proton-induced-xray-emission quantifies elemental abundancesmore » in separated metalloprotein samples to nanogram amounts and is capable of quantifying phosphorylated loci in gels. Accelerator-based quantitation is a possible tool for quantifying the genome translation into proteome.« less

Proxy system modeling of tree-ring isotope chronologies over the Common Era

NASA Astrophysics Data System (ADS)

Anchukaitis, K. J.; LeGrande, A. N.

2017-12-01

The Asian monsoon can be characterized in terms of both precipitation variability and atmospheric circulation across a range of spatial and temporal scales. While multicentury time series of tree-ring widths at hundreds of sites across Asia provide estimates of past rainfall, the oxygen isotope ratios of annual rings may reveal broader regional hydroclimate and atmosphere-ocean dynamics. Tree-ring oxygen isotope chronologies from Monsoon Asia have been interpreted to reflect a local 'amount effect', relative humidity, source water and seasonality, and winter snowfall. Here, we use an isotope-enabled general circulation model simulation from the NASA Goddard Institute for Space Science (GISS) Model E and a proxy system model of the oxygen isotope composition of tree-ring cellulose to interpret the large-scale and local climate controls on δ 18O chronologies. Broad-scale dominant signals are associated with a suite of covarying hydroclimate variables including growing season rainfall amounts, relative humidity, and vapor pressure deficit. Temperature and source water influences are region-dependent, as are the simulated tree-ring isotope signals associated with the El Nino Southern Oscillation (ENSO) and large-scale indices of the Asian monsoon circulation. At some locations, including southern coastal Viet Nam, local precipitation isotope ratios and the resulting simulated δ 18O tree-ring chronologies reflect upstream rainfall amounts and atmospheric circulation associated with monsoon strength and wind anomalies.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

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.

Arctic Ocean Cyclostratigraphy: An Alternative to Marine Oxygen Isotope curves as measures of Cryospheric and Sea-Level History

NASA Astrophysics Data System (ADS)

Cronin, T. M.; Marzen, R.; O'Regan, M.; Dwyer, G. S.

2016-12-01

The stable isotope compositions of biogenic carbonates have been used for paleoceanographic and paleoclimatic reconstructions for decades, and produced some of the most iconic records in the field. However, we still lack a fully mechanistic understanding of the stable isotope proxies, especially the biological overprint on the environmental signals termed "vital effects". A ubiquitous feature of stable isotope vital effects in marine calcifying organisms is a strong correlation between δ18O and δ13C in a range of values that are depleted from equilibrium. Two mechanisms have been proposed to explain this correlation, one based on kinetic isotope effects during CO2(aq)-HCO3- inter-conversion, the other based on equilibrium isotope exchange during pH dependent speciation of the dissolved inorganic carbon pool. Neither mechanism explains all the stable isotope features observed in biogenic carbonates. Here we present a fully kinetic model of biomineralization and its isotope effects using deep sea corals as a test organism. A key component of our model is the consideration of the enzyme carbonic anhydrase in catalyzing the CO2(aq)-HCO3- inter-conversion reactions in the extracellular calcifying fluid (ECF). We find that the amount of carbonic anhydrase not only modulates the carbonate chemistry of the calcifying fluid, but also helps explain the slope of the δ18O-δ13C correlation. With this model, we are not only able to fit deep sea coral data, but also explain the stable isotope vital effects of other calcifying organisms. This fully kinetic model of stable isotope vital effects and the underlying calcification dynamics may also help us better understand mechanisms of other paleoceanographic tracers in biogenic carbonates, including boron isotopes and trace metal proxies.

Optimization and application of ICPMS with dynamic reaction cell for precise determination of 44Ca/40Ca isotope ratios.

PubMed

Boulyga, Sergei F; Klötzli, Urs; Stingeder, Gerhard; Prohaska, Thomas

2007-10-15

An inductively coupled plasma mass spectrometer with dynamic reaction cell (ICP-DRC-MS) was optimized for determining (44)Ca/(40)Ca isotope ratios in aqueous solutions with respect to (i) repeatability, (ii) robustness, and (iii) stability. Ammonia as reaction gas allowed both the removal of (40)Ar+ interference on (40)Ca+ and collisional damping of ion density fluctuations of an ion beam extracted from an ICP. The effect of laboratory conditions as well as ICP-DRC-MS parameters such a nebulizer gas flow rate, rf power, lens potential, dwell time, or DRC parameters on precision and mass bias was studied. Precision (calculated using the "unbiased" or "n - 1" method) of a single isotope ratio measurement of a 60 ng g(-1) calcium solution (analysis time of 6 min) is routinely achievable in the range of 0.03-0.05%, which corresponded to the standard error of the mean value (n = 6) of 0.012-0.020%. These experimentally observed RSDs were close to theoretical precision values given by counting statistics. Accuracy of measured isotope ratios was assessed by comparative measurements of the same samples by ICP-DRC-MS and thermal ionization mass spectrometry (TIMS) by using isotope dilution with a (43)Ca-(48)Ca double spike. The analysis time in both cases was 1 h per analysis (10 blocks, each 6 min). The delta(44)Ca values measured by TIMS and ICP-DRC-MS with double-spike calibration in two samples (Ca ICP standard solution and digested NIST 1486 bone meal) coincided within the obtained precision. Although the applied isotope dilution with (43)Ca-(48)Ca double-spike compensates for time-dependent deviations of mass bias and allows achieving accurate results, this approach makes it necessary to measure an additional isotope pair, reducing the overall analysis time per isotope or increasing the total analysis time. Further development of external calibration by using a bracketing method would allow a wider use of ICP-DRC-MS for routine calcium isotopic measurements, but it still requires particular software or hardware improvements aimed at reliable control of environmental effects, which might influence signal stability in ICP-DRC-MS and serve as potential uncertainty sources in isotope ratio measurements.

Diffuse migratory connectivity in two species of shrubland birds: evidence from stable isotopes

USGS Publications Warehouse

Knick, Steven T.; Leu, Matthias; Rotenberry, John T.; Hanser, Steven E.; Fesenmyer, Kurt

2014-01-01

Connecting seasonal ranges of migratory birds is important for understanding the annual template of stressors that influence their populations. Brewer’s sparrows (Spizella breweri) and sagebrush sparrows (Artemisiospiza nevadensis) share similar sagebrush (Artemisia spp.) habitats for breeding but have different population trends that might be related to winter location. To link breeding and winter ranges, we created isoscapes of deuterium [stable isotope ratio (δ) of deuterium; δ2H] and nitrogen (δ15N) for each species modeled from isotope ratios measured in feathers of 264 Brewer’s and 82 sagebrush sparrows and environmental characteristics at capture locations across their breeding range. We then used feather δ2Hf and δ15Nf measured in 1,029 Brewer’s and 527 sagebrush sparrows captured on winter locations in southwestern United States to assign probable breeding ranges. Intraspecies population mixing from across the breeding range was strong for both Brewer’s and sagebrush sparrows on winter ranges. Brewer’s sparrows but not sagebrush sparrows were linked to more northerly breeding locations in the eastern part of their winter range. Winter location was not related to breeding population trends estimated from US Geological Survey Breeding Bird Survey routes for either Brewer’s or sagebrush sparrows. Primary drivers of population dynamics are likely independent for each species; Brewer’s and sagebrush sparrows captured at the same winter location did not share predicted breeding locations or population trends. The diffuse migratory connectivity displayed by Brewer’s and sagebrush sparrows measured at the coarse spatial resolution in our analysis also suggests that local environments rather than broad regional characteristics are primary drivers of annual population trends.

Nitrogen cycle dynamics in the Late Cretaceous Greenhouse

NASA Astrophysics Data System (ADS)

Junium, Christopher K.; Meyers, Stephen R.; Arthur, Michael A.

2018-01-01

Great attention has been paid to the origin of anomalously low nitrogen isotope values during the Late Cretaceous. Nitrogen isotope values are often as low as - 3 ‰ and are typically less than + 2 ‰, even in relatively organic matter-lean sediments. Here we evaluate nitrogen isotope variability during a relatively quiescent phase of the Late Cretaceous Greenhouse, between Oceanic Anoxic Events 2 and 3, using the black shales of Demerara Rise (DR). Selection of this site allows us to isolate some of the factors that control nitrogen cycle dynamics and contribute to low nitrogen isotope values. New N-isotope measurements from ODP Site 1259 reveal δ15N values that range from + 0.2 ‰ to -3.5‰ and oscillate by 1.5‰ to 3‰ over 1.6 million years (Ma). Temporal calibration of our data using a new astronomical time scale reveals a strong ∼100 thousand year (ka) eccentricity cyclicity in δ15N. We attribute this cyclicity to oscillations in the position of the intertropical convergence zone (ITCZ) over DR that modulate upwelling intensity, chemocline depth and the degree of 15N-depletion. We also recognize a statistically significant correlation (p = 0.0022) between the TEX86 indices and δ15N, with the lowest δ15N corresponding to the highest TEX86 indices. This relationship suggests that the activity and ecology of ammonia oxidizing Thaumarchaeota and the δ15N of dissolved inorganic nitrogen utilized by primary producers are linked. We therefore interpret the observed variability in the δ15N data and TEX86 indices as primarily reflecting fluctuation of upwelling intensity and chemocline depth, and the significant inverse relationship between these data sets suggests that caution should be exercised when interpreting the TEX86 in terms of temperature in similar paleoenvironmental settings.

Tracking Movement of Plant Carbon Through Soil to Water by Lignin Phenol Stable Carbon Isotope Composition in a Small Agricultural Watershed

NASA Astrophysics Data System (ADS)

Crooker, K.; Filley, T.; Six, J.; Frey, J.

2005-12-01

Few studies integrate land cover, soil physical structure, and aquatic physical fractions when investigating the fate of agricultural carbon in watersheds. In crop systems that involve rotations of soy (a C3 plant) and corn (a C4 plant) the large intrinsic differences in stable carbon isotope values and lignin plus cutin chemistry enable tracking of plant carbon movement from soil fractions to DOM and overland flow during precipitation events. In a small (~3Km2) agricultural basin in central Indiana, we studied plant carbon dynamics in a soy/corn agricultural rotation (2004-2005) to determine the relative inputs of these two plants to soil fractions and the resultant contributions to dissolved, colloidal, and particulate organic matter when mobilized. Using bulk isotope values the fraction of carbon derived from corn in macroaggregates (>250 micron), microaggregates (53-250 mm), and silts plus clays (<53 mm) ranged from 39, 49, to 42%, respectively. Unlike bulk analyses, compound specific isotope analysis of lignin in the soil fractions revealed a wide range of relative inputs among the monomers with cinnamyl phenols being almost exclusively (~ 93%) derived from corn. Syringyl phenols ranged from 75-56% corn and vanillyl phenols ranged from 37-40% corn carbon. The relative input among the fractions mirrors closely the comparative plant chemistry abundances between soy and corn. During export of DOM from the land to the stream the relative abundance of plant source varied with discharge (0.05-1.8 m3/sec) as increases in flow increased the relative export of corn-derived C from the fields. Over the full range of flows lignin phenols varied from 0.05 to 82% corn-derived with the greatest relative corn input for cinnamyl and syringyl carbon. The trend with stream discharge indicates a progressive movement of particulate corn residues with overland flow. Ongoing studies look to resolve contributions of algae, bacteria and terrestrial plants to soil fractions and their mobilized components.

Indian Summer Monsoon dynamics during Termination II and MIS 5e

NASA Astrophysics Data System (ADS)

Magiera, Matthias; Erhardt, Andrea M.; Hartland, Adam; Kwiecien, Ola; Cheng, Hai; Immenhauser, Adrian; Turchyn, Alexandra; Breitenbach, Sebastian F. M.

2017-04-01

The interpretation of speleothem oxygen isotope ratios (δ18O) as proxy for Indian Summer Monsoon (ISM) dynamics is ambiguous, due to multiple influencing factors. Here we combine δ18O and calcium isotope δ44Ca analyses with elemental data to delineate regional shifts in moisture source, local rainfall amount, and changes in ISM intensity and length during Termination II and MIS 5e. Oxygen isotope ratios reflect a mixed signal of moisture source dynamics and rainfall amount; δ44Ca and Mg/Ca ratios are interpreted as proxies for local effective moisture and prior calcite precipitation (PCP) in the epikarst. The age of stalagmite MAW-3 from Mawmluh Cave, NE India, is constraint by six U-series dates. 108 samples, obtained at 0.4 mm resolution from the 70 mm long speleothem sample, have been analysed for δ18O, δ44Ca and Mg/Ca. Oxygen isotope ratios were measured on a ThermoFisher Scientific MAT 253 at Ruhr-University Bochum. Elemental ratios were measured on a quadrupole ICP-MS at Waikato University. Calcium isotope ratios were analyzed on a ThermoFisher Scientific Triton at University of Cambridge. MAW-3 grew from 136 kyrs BP to 96 kyrs BP, covering Termination II and MIS 5e. Oxygen isotope values are high (ca. +0.91 ‰) during Termination II, reach a minimum during MIS 5e (-3.5 ‰), and rise again to -0.2 ‰ at the end of MIS 5e. Calcium isotope ratios range from -0.32 ‰ to -0.70 ‰ and show a positive correlation (R2= 0.7) with δ18O. High δ18O values during Termination II reflect reduced atmospheric circulation and/or a proximal moisture source (Bay of Bengal), implying lowered ISM intensity. A positive correlation of δ18O with δ44Ca suggests concurrent changes of moisture source location and local rainfall amount, with a proximal moisture source and reduced effective rainfall during periods of weak ISM. Elevated Mg/Ca ratios at such intervals corroborate PCP occurrence, which reflects dry conditions. The beginning of MIS 5e (ca. 132 kyrs BP) is marked by a rapid change to lower δ18O and δ44Ca, suggesting increased local infiltration with increasing ISM rainfall, and a concurrent change to a more distal moisture source. The MAW-3 multi-proxy record compares well with reconstructions from China and northern India, the latter being more depleted, due to Rayleigh fractionation. We suggest that multi-proxy analyses of δ18O, δ44Ca and Mg/Ca greatly help to delineate regional circulation pattern and local effective moisture dynamics in monsoonal settings.

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

PubMed

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

2017-11-01

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

Informational Aspects of Isotopic Diversity in Biology and Medicine

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2004-10-01

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

Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate

PubMed Central

Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

2014-01-01

The dynamics of nitrate (NO−3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO−3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO−3-use mechanisms. The concentration and natural isotopes of tissue NO−3 can offer insights into the plant NO−3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO−3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO−3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO−3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO−3 in plants, and discuss the implications of NO−3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO−3 and plant ecophysiological functions in interspecific and intra-plant NO−3 variations. We introduce N and O isotope systematics of NO−3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ18O and Δ17O); and isotope mass-balance calculations to constrain sources and reduction of NO−3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ18O-NO−3 variation, and summarize the uncertainties in using tissue NO−3 parameters to interpret plant NO−3 utilization. PMID:25101106

Nitrate dynamics in natural plants: insights based on the concentration and natural isotope abundances of tissue nitrate.

PubMed

Liu, Xue-Yan; Koba, Keisuke; Makabe, Akiko; Liu, Cong-Qiang

2014-01-01

The dynamics of nitrate (NO(-) 3), a major nitrogen (N) source for natural plants, has been studied mostly through experimental N addition, enzymatic assay, isotope labeling, and genetic expression. However, artificial N supply may not reasonably reflect the N strategies in natural plants because NO(-) 3 uptake and reduction may vary with external N availability. Due to abrupt application and short operation time, field N addition, and isotopic labeling hinder the elucidation of in situ NO(-) 3-use mechanisms. The concentration and natural isotopes of tissue NO(-) 3 can offer insights into the plant NO(-) 3 sources and dynamics in a natural context. Furthermore, they facilitate the exploration of plant NO(-) 3 utilization and its interaction with N pollution and ecosystem N cycles without disturbing the N pools. The present study was conducted to review the application of the denitrifier method for concentration and isotope analyses of NO(-) 3 in plants. Moreover, this study highlights the utility and advantages of these parameters in interpreting NO(-) 3 sources and dynamics in natural plants. We summarize the major sources and reduction processes of NO(-) 3 in plants, and discuss the implications of NO(-) 3 concentration in plant tissues based on existing data. Particular emphasis was laid on the regulation of soil NO(-) 3 and plant ecophysiological functions in interspecific and intra-plant NO(-) 3 variations. We introduce N and O isotope systematics of NO(-) 3 in plants and discuss the principles and feasibilities of using isotopic enrichment and fractionation factors; the correlation between concentration and isotopes (N and O isotopes: δ(18)O and Δ(17)O); and isotope mass-balance calculations to constrain sources and reduction of NO(-) 3 in possible scenarios for natural plants are deliberated. Finally, we offer a preliminary framework of intraplant δ(18)O-NO(-) 3 variation, and summarize the uncertainties in using tissue NO(-) 3 parameters to interpret plant NO(-) 3 utilization.

Titanium isotopes and rare earth patterns in CAIs: Evidence for thermal processing and gas-dust decoupling in the protoplanetary disk

NASA Astrophysics Data System (ADS)

Davis, Andrew M.; Zhang, Junjun; Greber, Nicolas D.; Hu, Jingya; Tissot, François L. H.; Dauphas, Nicolas

2018-01-01

Titanium isotopic compositions (mass-dependent fractionation and isotopic anomalies) were measured in 46 calcium-, aluminum-rich inclusions (CAIs) from the Allende CV chondrite. After internal normalization to 49Ti/47Ti, we found that ε50Ti values are somewhat variable among CAIs, and that ε46Ti is highly correlated with ε50Ti, with a best-fit slope of 0.162 ± 0.030 (95% confidence interval). The linear correlation between ε46Ti and ε50Ti extends the same correlation seen among bulk solar objects (slope 0.184 ± 0.007). This observation provides constraints on dynamic mixing of the solar disk and has implications for the nucleosynthetic origin of titanium isotopes, specifically on the possible contributions from various types of supernovae to the solar system. Titanium isotopic mass fractionation, expressed as δ‧49Ti, was measured by both sample-standard bracketing and double-spiking. Most CAIs are isotopically unfractionated, within a 95% confidence interval of normal, but a few are significantly fractionated and the range δ‧49Ti is from ∼-4 to ∼+4. Rare earth element patterns were measured in 37 of the CAIs. All CAIs with significant titanium mass fractionation effects have group II and related REE patterns, implying kinetically controlled volatility fractionation during the formation of these CAIs.

Fragment distribution in 78,86Kr+181Ta reactions

NASA Astrophysics Data System (ADS)

Zhang, Dong-Hong; Zhang, Feng-Shou

2018-05-01

Within the framework of the isospin-dependent quantum molecular dynamics model, along with the GEMINI model, the 86Kr+181Ta reaction at 80, 120 and 160 MeV/nucleon and the 78Kr+181Ta reaction at 160 MeV/nucleon are studied, and the production cross sections of the generated fragments are calculated. More inter-mediate and large mass fragments can be produced in the reactions with a large range of impact parameter. The production cross sections of nuclei such as the isotopes of Si and P generally decrease with increasing incident energy. Isotopes near the neutron drip line are produced more in the neutron-rich system 86Kr+181Ta. Supported by Youth Research Foundation of Shanxi Datong University (2016Q10)

Efficacy of passive sampler collection for atmospheric NO2 isotopes under simulated environmental conditions.

PubMed

Coughlin, Justin G; Yu, Zhongjie; Elliott, Emily M

2017-07-30

Nitrogen oxides or NO x (NO x = NO + NO 2 ) play an important role in air quality, atmospheric chemistry, and climate. The isotopic compositions of anthropogenic and natural NO 2 sources are wide-ranging, and they can be used to constrain sources of ambient NO 2 and associated atmospheric deposition of nitrogen compounds. While passive sample collection of NO 2 isotopes has been used in field studies to determine NO x source influences on atmospheric deposition, this approach has not been evaluated for accuracy or precision under different environmental conditions. The efficacy of NO 2 passive sampler collection for NO 2 isotopes was evaluated under varied temperature and relative humidity (RH) conditions in a dynamic flux chamber. The precision and accuracy of the filter NO 2 collection as nitrite (NO 2 - ) for isotopic analysis were determined using a reference NO 2 gas tank and through inter-calibration with a modified EPA Method 7. The bacterial denitrifer method was used to convert 20 μM of collected NO 2 - or nitrate (NO 3 - ) into N 2 O and was carried out on an Isoprime continuous flow isotope ratio mass spectrometer. δ 15 N-NO 2 values determined from passive NO 2 collection, in conditions of 11-34 °C, 1-78% RH, have an overall accuracy and precision of ±2.1 ‰, and individual run precision of ±0.6 ‰. δ 18 O-NO 2 values obtained from passive NO 2 sampler collection, under the same conditions, have an overall precision of ± 1.3 ‰. Suitable conditions for passive sampler collection of NO 2 isotopes are in environments ranging from 11 to 34 °C and 1 to 78% RH. The passive NO 2 isotope measurement technique provides an accurate method to determine variations in atmospheric δ 15 N-NO 2 values and a precise method for determining atmospheric δ 18 O-NO 2 values. The ability to measure NO 2 isotopes over spatial gradients at the same temporal resolution provides a unique perspective on the extent and seasonality of fluctuations in atmospheric NO 2 isotopic compositions. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

A reconnaissance study of oxygen, hydrogen and strontium isotopes in geochemically diverse lakes, Western Nebraska, USA

USGS Publications Warehouse

Gosselin, D.C.; Nabelek, P.E.; Peterman, Z.E.; Sibray, S.

1997-01-01

Reconnaissance ??18O,, ??D, and ??87Sr data for fifteen lakes in the Western Lakes Region of the Sand Hills of Nebraska indicate dynamic hydrologic systems. The rather narrow range of ??87Sr from lake water (1.1 to 2.1) and groundwater (0.9 to 1.7) indicates that the groundwater is generally unradiogenic. Groundwater residence times and relatively unradiogenic volcanic ash within the dune sediments control the ??87Sr values. Based on the mutual variations of ??18O and ??D, the lakes can be divided into three groups. In Group 1, both ??18O and ??D values increase from spring to fall. The ??18O and ??D values in Group 2 decreased from spring to fall. Group 3 are ephemeral lakes that went dry some time during 1992. The data and isotopic modeling show that variations in the ratio of evaporation relative to groundwater inflow, local humidity conditions, and the ??(a) has substantial influence on the isotopic composition. In addition, isotopic behavior in ephemeral hakes can be rather unusual because of the changing activities of water and mineral precipitation and redissolution. The annual and interannual isotopic variability of these lakes which is reflected in the paleonvironmental indicators may be the rule rather than the exception in these types of systems.

Hydrological connectivity of perched aquifers and regional aquifers in semi-arid environments: a case study from Namibia

NASA Astrophysics Data System (ADS)

Hamutoko, J. T.; Wanke, H.

2017-12-01

Integrated isotopic and hydrological tracers along with standard hydrological data are used to understand complex dry land hydrological processes on different spatial and temporal scales. The objective of this study is to analyse the relationship between the perched aquifers and the regional aquifer using hydrochemical data and isotopic composition in the Cuvelai-Etosha Basin in Namibia. This relation between the aquifers will aid in understanding groundwater recharge processes and flow dynamics. Perched aquifers are discontinuous shallow aquifers with water level ranging from 0 to 30 meters below ground level. The regional aquifer occurs in semi-consolidated sandstone at depths between about 60 and 160 meters below ground level. Water samples were collected from both aquifers in 10 villages and were analysed for major ions and stable isotopes. The results show overlapping hydrochemistry and isotopic compositions of both aquifers in 8 villages which suggest the possibility of perched aquifer water infiltrating into the regional aquifer. In two villages the hydrochemistry and isotopic composition of the aquifers are totally different and this suggests that there is no interaction between this aquifers. Areas where perched aquifers are connected to regional aquifers maybe recharge zones. These finding have important implications for groundwater resource management.

Characterization of calcium isotopes in natural and synthetic barite

USGS Publications Warehouse

Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

2008-01-01

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

STABLE ISOTOPES AS INDICATORS OF SOIL WATER DYNAMICS IN WATERSHEDS

EPA Science Inventory

Stream water quality and quantity depend on discharge rates of water and nutrients from soils. However, soil-water storage is very dynamic and strongly influenced by plants. We analyzed stable isotopes of oxygen and hydrogen to quantify spatial and temporal changes in evaporati...

Carbon and hydrogen isotopic systematics of dissolved methane in small seasonally ice-covered lakes near the margin of the Greenland ice sheet

NASA Astrophysics Data System (ADS)

Cadieux, S. B.; White, J. R.; Pratt, L. M.; Peng, Y.; Young, S. A.

2013-12-01

Northern lakes contribute from 6-16% of annual methane inputs to Earth's atmosphere, yet little is known about the seasonal biogeochemistry of CH4 cycling, particularly for lakes in the Arctic. Studies during ice-free conditions have been conducted in Alaskan, Swedish and Siberian lakes. However, there is little information on CH4 cycling under ice-covered conditions, and few stable isotopic measurements, which can help elucidate production and consumption pathways. In order to better understand methane dynamics of ice-covered Arctic lakes, 4 small lakes (surface area <1 km2) within a narrow valley extending from the Russells Glacier to Søndre Strømfjord in Southwestern Greenland were examined during summer stratification and winter ice-cover. Lakes in the study area are ice-covered from mid-September to mid-June. In both seasons, variations in the concentrations and isotopic composition of methane with depth were related to redox fluctuations. During late winter under~2 m of ice, the entire water column was anoxic with wide variation in methane concentrationsand isotopic composition from lake to lake. In three of the lakes, CH4 concentrations and δ13C were relatively stable over the depth of the water column, averaging from 120 to 480μM, with δ13CH4 values from -56‰ to -66‰, respectively. Methane concentrations in the other lake increased with depth from <1 μM below the ice to 800 μM at the sediment/water interface, while δ13C decreased by 30‰ from -30‰ to -70‰ over this depth. In all the lakes, δ13C of sediment porewater was lighter than the overlying water by at least 10‰. The δD-CH4 in the water column ranged from -370‰ to -50‰, exhibiting covariance with δ13C consistent with significant methanotrophic activity. In the sediment, δD-CH4 values ranged from -330‰ to -275‰, and were inversely correlated with δ13C. We will present detailed information on redox dynamics as a controlling factor in methane cycling, and explore the effects of differing microbial communities and carbon supply. Our study suggests that shallow lakes in continuous permafrost landscapes of the Arctic develop distinct methane cycling dynamics despite their close proximity.

Gas geochemistry of the Mount Elbert Gas Hydrate Stratigraphic Test Well, Alaska North Slope: implications for gas hydrate exploration in the Arctic

USGS Publications Warehouse

Lorenson, T.D.; Collett, T.S.; Hunter, R.B.

2011-01-01

Gases were analyzed from well cuttings, core, gas hydrate, and formation tests at the BPXA-DOE-USGS Mount Elbert Gas Hydrate Stratigraphic Test Well, drilled within the Milne Point Unit, Alaska North Slope. The well penetrated a portion of the Eileen gas hydrate deposit, which overlies the more deeply buried Prudhoe Bay, Milne Point, West Sak, and Kuparuk River oil fields. Gas sources in the upper 200 m are predominantly from microbial sources (C1 isotopic compositions ranging from −86.4 to −80.6‰). The C1 isotopic composition becomes progressively enriched from 200 m to the top of the gas hydrate-bearing sands at 600 m. The tested gas hydrates occur in two primary intervals, units D and C, between 614.0 m and 664.7 m, containing a total of 29.3 m of gas hydrate-bearing sands. The hydrocarbon gases in cuttings and core samples from 604 to 914 m are composed of methane with very little ethane. The isotopic composition of the methane carbon ranges from −50.1 to −43.9‰ with several outliers, generally decreasing with depth. Gas samples collected by the Modular Formation Dynamics Testing (MDT) tool in the hydrate-bearing units were similarly composed mainly of methane, with up to 284 ppm ethane. The methane isotopic composition ranged from −48.2 to −48.0‰ in the C sand and from −48.4 to −46.6‰ in the D sand. Methane hydrogen isotopic composition ranged from −238 to −230‰, with slightly more depleted values in the deeper C sand. These results are consistent with the concept that the Eileen gas hydrates contain a mixture of deep-sourced, microbially biodegraded thermogenic gas, with lesser amounts of thermogenic oil-associated gas, and coal gas. Thermal gases are likely sourced from existing oil and gas accumulations that have migrated up-dip and/or up-fault and formed gas hydrate in response to climate cooling with permafrost formation.

Practical strategies when using a stable isotope labeled microtracer for absolute bioavailability assessment: A case study of a high oral dose clinical candidate GDC-0810.

PubMed

Chen, Buyun; Lu, Pingping; Freeman, Dugan; Gao, Yang; Choo, Edna; DeMent, Kevin; Savage, Scott; Zhang, Kelly; Milanwoski, Dennis; Liu, Lichuan; Dean, Brian; Deng, Yuzhong

2018-05-30

The pH labile metabolite, hydrophobicity, high oral dose and systematic exposure of GDC-0810 posed tremendous challenges to develop a LC-MS method for a stable isotope labeled aBA study. In this study, we explored practical solutions to balance stability and sensitivity and to cope with the impact of high C p.o. to C i.v. ratio on the labeling selection and assay dynamic range. A [ 13 C 9 ] GDC-0810 was synthesized to minimize the isotopic interference between PO dose, internal standard and I.V. microtracer. A highly sensitive LC-MS assay was validated for quantitation of [ 13 C 9 ] GDC-0810 from 5 to 1250 pg/mL. The optimized method was applied to a proof of concept cynomolgus monkey aBA study and the bioavailability calculated using microtracer dosing and regular dosing were similar to each other. Copyright © 2018 Elsevier B.V. All rights reserved.

Time-dependent view of an isotope effect in electron-nuclear nonequilibrium dynamics with applications to N2.

PubMed

Ajay, Jayanth S; Komarova, Ksenia G; Remacle, Francoise; Levine, R D

2018-06-05

Isotopic fractionation in the photodissociation of N 2 could explain the considerable variation in the 14 N/ 15 N ratio in different regions of our galaxy. We previously proposed that such an isotope effect is due to coupling of photoexcited bound valence and Rydberg electronic states in the frequency range where there is strong state mixing. We here identify features of the role of the mass in the dynamics through a time-dependent quantum-mechanical simulation. The photoexcitation of N 2 is by an ultrashort pulse so that the process has a sharply defined origin in time and so that we can monitor the isolated molecule dynamics in time. An ultrafast pulse is necessarily broad in frequency and spans several excited electronic states. Each excited molecule is therefore not in a given electronic state but in a superposition state. A short time after excitation, there is a fairly sharp onset of a mass-dependent large population transfer when wave packets on two different electronic states in the same molecule overlap. This coherent overlap of the wave packets on different electronic states in the region of strong coupling allows an effective transfer of population that is very mass dependent. The extent of the transfer depends on the product of the populations on the two different electronic states and on their relative phase. It is as if two molecules collide but the process occurs within one molecule, a molecule that is simultaneously in both states. An analytical toy model recovers the (strong) mass and energy dependence.

Detection of boron nitride radicals by emission spectroscopy in a laser-induced plasma

NASA Astrophysics Data System (ADS)

Dutouquet, C.; Acquaviva, S.; Hermann, J.

2001-06-01

Several vibrational bands of boron nitride radicals have been observed in a plasma produced by pulsed-laser ablation of a boron nitride target in low-pressure nitrogen or argon atmospheres. Using time- and space-resolved emission spectroscopic measurements with a high dynamic range, the most abundant isotopic species B 11N have been detected. The emission bands in the spectral range from 340 to 380 nm belong to the Δυ =-1, 0, +1 sequences of the triplet system (transition A 3Π-X 3Π). For positive identification, the molecular emission bands have been compared with synthetic spectra obtained by computer simulations. Furthermore, B 10N emission bands have been reproduced by computer simulation using molecular constants which have been deduced from the B 11N constants. Nevertheless, the presence of the lower abundant isotopic radical B 10N was not proved due the noise level which masked the low emission intensity of the B 10N band heads.

Deep sulfur cycle

NASA Astrophysics Data System (ADS)

Shimizu, N.; Mandeville, C. W.

2009-12-01

Geochemical cycle of sulfur in near-surface reservoirs has been a subject of intense studies for decades. It has been shown that sulfur isotopic compositions of sedimentary sulfides and sulfates record interactions of the atmosphere, hydrosphere, biosphere and lithosphere, with δ34S of sedimentary sulfides continuously decreasing from 0‰ toward present-day values of ~-30 to -40‰ over the Phanerozoic (e.g., Canfield, 2004). It has also been shown that microbial reduction of the present-day seawater sulfate (δ34S=+21‰) results in large shifts in isotopic compositions of secondary pyrites in altered oceanic crust (to δ34S=-70‰: Rouxel et al., 2009). How much of these near surface isotopic variations survive during deep geochemical cycle of sulfur interacting with the mantle infinite reservoir with δ34S=0‰? Could extent of their survival be used as a tracer of processes and dynamics involved in deep geochemical cycle? As a first step toward answering these questions, δ34S was determined in-situ using a Cameca IMS 1280 ion microprobe at Woods Hole Oceanographic Institution in materials representing various domains of deep geochemical cycle. They include pyrites in altered MORB as potential subducting materials and pyrites in UHP eclogites as samples that have experienced subduction zone processes, and mantle-derived melts are represented by olivine-hosted melt inclusions in MORB and those in IAB, and undegassed submarine OIB glasses. Salient features of the results include: (1) pyrites in altered MORB (with O. Rouxel; from ODP site 801 and ODP Hole 1301B) range from -70 to +19‰, (2) pyrites in UHP eclogites from the Western Gneiss Region, Norway (with B. Hacker and A. Kylander-Clark) show a limited overall range from -3.4 to + 2.8‰ among five samples, with one of them covering almost the entire range, indicating limited scale lengths of isotopic equilibration during subduction, (3) olivine-hosted melt inclusions in arc basalts from Galunggung (-2.8 - +5.2‰ with majority between +3 and +5), Krakatau (+1.5 - +8.6‰ with a cluster around +3 - +5), and Augustine (+8 - +12‰) show larger variations among arc magmas than previously known, (4) olivine-hosted melt inclusions from a FAMOUS lava (519-4-1) range from -9.5 to +10.5‰, and (5) undegassed submarine glasses from Samoa (with M. Jackson) appear to show separate ranges for individual islands, including Vailulu clustering around -1.9 to +2.1‰ and Malumalu ranging from -0.9 to -12.1‰. Overall, the results clearly show that low temperature signatures are not completely erased during recycling and isotopic exchange with the mantle infinite reservoir, and that mantle-derived melts still display large isotopic variations for small sampling scales, similar to observations on other isotope systems. Canfield, D. E. (2004) Amer. Jour. Sci., 304, 839-861. Rouxel, O. et al., (2009) Goldschmidt Conf. Abstract.

Water isotope variability across single rainfall events in the tropical Pacific

NASA Astrophysics Data System (ADS)

Cobb, K. M.; Moerman, J. W.; Ellis, S. A.; Bennett, L.; Bosma, C.; Hitt, N. T.

2017-12-01

Water isotopologues provide a powerful diagnostic tool for probing the dynamical processes involved in the initiation and evolution of tropical convective events, yet water isotope observations rarely meet the temporal resolution required to resolve such processes. Here we present timeseries of rainfall oxygen and hydrogen isotopologues across over 30 individual convective events sampled at 1- to 5-minute intervals at both terrestrial (Gunung Mulu National Park, 4N, 115W) and maritime (Kiritimati Island, 2N, 157W) sites located in the equatorial Pacific. The sites are the loci of significant paleoclimate research that employ water isotopologues to reconstruct a variety of climatic parameters of interest over the last century, in the case of coral d18O, to hundreds of thousands of years before present, in the case of stalagmite d18O. As such, there is significant scientific value in refining our understanding of water isotope controls at these particular sites. Our results illustrate large, short-term excursions in water isotope values that far exceed the signals recovered in daily timeseries of rainfall isotopologues from the sites, illustrating the fundamental contribution of mesoscale processes in driving rainfall isotope variability. That said, the cross-event profiles exhibit a broad range of trajectories, even for events collected at the same time of day on adjoining days. Profiles collected at different phases of the 2015-2017 strong El Nino-Southern Oscillation cycle also exhibit appreciable variability. We compare our observations to hypothetical profiles from a 1-dimensional model of each rainfall event, as well as to output from 4-dimensional isotope-equipped, ocean-atmosphere coupled models of rainfall isotope variability in the tropical Pacific. We discuss the implications of our findings for the interpretation of water isotope-based reconstructions of hydroclimate in the tropics.

A new feature in the internal heavy isotope distribution in ozone.

PubMed

Bhattacharya, S K; Savarino, Joel; Michalski, G; Liang, Mao-Chang

2014-10-07

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ((18)O/(16)O and (17)O/(16)O ratio) which does not follow normal mass fractionation rule: δ(17)O ∼ 0.52(*)δ(18)O, expressed as an anomaly Δ(17)O = δ(17)O - 0.52(*)δ(18)O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ(18)O (s) or δ(18)O (as) (and similarly for δ(17)O) as well as position dependent isotope anomaly Δ(17)O (s) and Δ(17)O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ(17)O (s) is zero. Consequently, Δ(17)O (as) = 1.5 (*) Δ(17)O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

A new feature in the internal heavy isotope distribution in ozone

NASA Astrophysics Data System (ADS)

Bhattacharya, S. K.; Savarino, Joel; Michalski, G.; Liang, Mao-Chang

2014-10-01

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition (18O/16O and 17O/16O ratio) which does not follow normal mass fractionation rule: δ17O ˜ 0.52*δ18O, expressed as an anomaly Δ17O = δ17O - 0.52*δ18O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ18O (s) or δ18O (as) (and similarly for δ17O) as well as position dependent isotope anomaly Δ17O (s) and Δ17O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ17O (s) is zero. Consequently, Δ17O (as) = 1.5 * Δ17O (bulk) (named here simply as the "1.5 rule") which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.

Measurement of Enzyme Isotope Effects.

PubMed

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

2017-01-01

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

A non-zircon Hf isotope record in Archean black shales from the Pilbara craton confirms changing crustal dynamics ca. 3 Ga ago.

PubMed

Nebel-Jacobsen, Yona; Nebel, Oliver; Wille, Martin; Cawood, Peter A

2018-01-17

Plate tectonics and associated subduction are unique to the Earth. Studies of Archean rocks show significant changes in composition and structural style around 3.0 to 2.5 Ga that are related to changing tectonic regime, possibly associated with the onset of subduction. Whole rock Hf isotope systematics of black shales from the Australian Pilbara craton, selected to exclude detrital zircon components, are employed to evaluate the evolution of the Archean crust. This approach avoids limitations of Hf-in-zircon analyses, which only provide input from rocks of sufficient Zr-concentration, and therefore usually represent domains that already underwent a degree of differentiation. In this study, we demonstrate the applicability of this method through analysis of shales that range in age from 3.5 to 2.8 Ga, and serve as representatives of their crustal sources through time. Their Hf isotopic compositions show a trend from strongly positive εHf initial values for the oldest samples, to strongly negative values for the younger samples, indicating a shift from juvenile to differentiated material. These results confirm a significant change in the character of the source region of the black shales by 3 Ga, consistent with models invoking a change in global dynamics from crustal growth towards crustal reworking around this time.

Nitrate denitrification with nitrite or nitrous oxide as intermediate products: Stoichiometry, kinetics and dynamics of stable isotope signatures.

PubMed

Vavilin, V A; Rytov, S V

2015-09-01

A kinetic analysis of nitrate denitrification by a single or two species of denitrifying bacteria with glucose or ethanol as a carbon source and nitrite or nitrous oxide as intermediate products was performed using experimental data published earlier (Menyailo and Hungate, 2006; Vidal-Gavilan et al., 2013). Modified Monod kinetics was used in the dynamic biological model. The special equations were added to the common dynamic biological model to describe how isotopic fractionation between N species changes. In contrast to the generally assumed first-order kinetics, in this paper, the traditional Rayleigh equation describing stable nitrogen and oxygen isotope fractionation in nitrate was derived from the dynamic isotopic equations for any type of kinetics. In accordance with the model, in Vidal-Gavilan's experiments, the maximum specific rate of nitrate reduction was proved to be less for ethanol compared to glucose. Conversely, the maximum specific rate of nitrite reduction was proved to be much less for glucose compared to ethanol. Thus, the intermediate nitrite concentration was negligible for the ethanol experiment, while it was significant for the glucose experiment. In Menyailo's and Hungate's experiments, the low value of maximum specific rate of nitrous oxide reduction gives high intermediate value of nitrous oxide concentration. The model showed that the dynamics of nitrogen and oxygen isotope signatures are responding to the biological dynamics. Two microbial species instead of single denitrifying bacteria are proved to be more adequate to describe the total process of nitrate denitrification to dinitrogen. Copyright © 2015 Elsevier Ltd. All rights reserved.

Diffusion coefficients of Mg isotopes in enstatite and forsterite melts calculated by first-principles molecular dynamic simulations

NASA Astrophysics Data System (ADS)

Huang, F.; Qi, Y.; Liu, X.; He, L.

2016-12-01

Stable isotopes can be fractionated by kinetic chemical diffusion because diffusion coefficients (D) of isotopes are mass-dependent. Diffusive isotopic fractionation recorded in rocks and minerals provide unique temporal constrains on geological processes. The mass dependence of D can be described in the form of Di/Dj= (mj/mi)β, where m denotes masses of isotope i and j, and β is an emperical parameter used to quantify the diffusive transport of isotopes [1]. β values can be estimated by experimental calibration and observation of natural samples, which are still rarely reported because it is challenging to precisely quantify the boundary conditions of diffusion processes [2,3,4]. Recent advances in computation technique provide a new way to theoretically calculate β values. For instance, classical molecular dynamics with empirical potential have been used to simulate interactions between atoms and estimate β of Mg isotopes in MgSiO3 melt [3]. Here, to further consider the effect of bonding and electron properties on β values, we apply first-principles Born-Oppenheimer Molecular Dynamics and pseudo-isotope methods (assuming mj/mi = 1/24, 1/4, 2, and 5) to estimate β for MgSiO3 and Mg2SiO4 melts. Our calculation shows that β of Mg isotopes with pseudo-mass ratios are consistent, indicating the reliability of the pseudo-isotope method. For MgSiO3 melt, β is 0.18 at 4000K and 0 GPa, higher than the value calculatedusing molecular dynamics simulations (0.135) [3]. For Mg2SiO4 melt at 0 GPa, β values are: 0.23 ± 0.04 at 2300K, 0.24 ± 0.07 at 3000K, and 0.24 ± 0.01 at 4000K. Notably, β of MgSiO3 and Mg2SiO4 melts are significantly higher than the value determined by diffusion experiments (0.05) [2]. These results indicate that β values are not sensitive to temperature, but dependent on melt composition.

A ring polymer molecular dynamics study of the isotopologues of the H + H2 reaction.

PubMed

Suleimanov, Yury V; de Tudela, Ricardo Pérez; Jambrina, Pablo G; Castillo, Jesús F; Sáez-Rábanos, Vicente; Manolopoulos, David E; Aoiz, F Javier

2013-03-14

The inclusion of Quantum Mechanical (QM) effects such as zero point energy (ZPE) and tunneling in simulations of chemical reactions, especially in the case of light atom transfer, is an important problem in computational chemistry. In this respect, the hydrogen exchange reaction and its isotopic variants constitute an excellent benchmark for the assessment of approximate QM methods. In particular, the recently developed ring polymer molecular dynamics (RPMD) technique has been demonstrated to give very good results for bimolecular chemical reactions in the gas phase. In this work, we have performed a detailed RPMD study of the H + H(2) reaction and its isotopologues Mu + H(2), D + H(2) and Heμ + H(2), at temperatures ranging from 200 to 1000 K. Thermal rate coefficients and kinetic isotope effects have been computed and compared with exact QM calculations as well as with quasiclassical trajectories and experiment. The agreement with the QM results is good for the heaviest isotopologues, with errors ranging from 15% to 45%, and excellent for Mu + H(2), with errors below 15%. We have seen that RPMD is able to capture the ZPE effect very accurately, a desirable feature of any method based on molecular dynamics. We have also verified Richardson and Althorpe's prediction [J. O. Richardson and S. C. Althorpe, J. Chem. Phys., 2009, 131, 214106] that RPMD will overestimate thermal rates for asymmetric reactions and underestimate them for symmetric reactions in the deep tunneling regime. The ZPE effect along the reaction coordinate must be taken into account when assigning the reaction symmetry in the multidimensional case.

A qualitative quantum rate model for hydrogen transfer in soybean lipoxygenase

NASA Astrophysics Data System (ADS)

Jevtic, S.; Anders, J.

2017-09-01

The hydrogen transfer reaction catalysed by soybean lipoxygenase (SLO) has been the focus of intense study following observations of a high kinetic isotope effect (KIE). Today high KIEs are generally thought to indicate departure from classical rate theory and are seen as a strong signature of tunnelling of the transferring particle, hydrogen or one of its isotopes, through the reaction energy barrier. In this paper, we build a qualitative quantum rate model with few free parameters that describes the dynamics of the transferring particle when it is exposed to energetic potentials exerted by the donor and the acceptor. The enzyme's impact on the dynamics is modelled by an additional energetic term, an oscillatory contribution known as "gating." By varying two key parameters, the gating frequency and the mean donor-acceptor separation, the model is able to reproduce well the KIE data for SLO wild-type and a variety of SLO mutants over the experimentally accessible temperature range. While SLO-specific constants have been considered here, it is possible to adapt these for other enzymes.

Quantum dynamics of the Mu+H2(HD,D2) and H+MuH(MuD) reactions

NASA Astrophysics Data System (ADS)

Tsuda, Ken-ichiro; Moribayashi, Kengo; Nakamura, Hiroki

1995-10-01

Quantum mechanically accurate calculations are carried out for the following reactions involving muonium atom (Mu) using the hyperspherical coordinate approach: Mu+H2→MuH+H, Mu+D2→MuD+D, Mu+HD→MuH(MuD)+D(H), H+MuH→MuH+H, and H+MuD ↔MuH+D. The initial vibrational state is restricted to the ground state (vi=0) and the collision energies considered are up to ˜1.2 eV. The various aspects of the dynamics, such as the isotope effects, the initial rotational state (ji) dependence, and the final rotational state (jf) distribution are analyzed for a wide range of ji and jf. Some of the isotope effects can be interpreted in terms of the variations in reaction barrier and endothermicity. The following two intriguing features are also found: (1) strong enhancement of reaction by initial rotational excitation, and (2) oscillation of integral cross section as a function of collision energy in the case of the Mu-transfer reactions.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Stable Isotope Mapping of Alaskan Grasses and Marijuana

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Using cumulative diet data and stable isotope analysis to determine trophic position of walleye Sander vitreus in a large, complex system

USGS Publications Warehouse

Fincel, Mark J.; James, Daniel A.; Chipps, Steven R.; Davis, Blake A.

2014-01-01

Diet studies have traditionally been used to determine prey use and food web dynamics, while stable isotope analysis provides for a time-integrated approach to evaluate food web dynamics and characterize energy flow in aquatic systems. Direct comparison of the two techniques is rare and difficult to conduct in large, species rich systems. We compared changes in walleye Sander vitreus trophic position (TP) derived from paired diet content and stable isotope analysis. Individual diet-derived TP estimates were dissimilar to stable isotope-derived TP estimates. However, cumulative diet-derived TP estimates integrated from May 2001 to May 2002 corresponded to May 2002 isotope-derived estimates of TP. Average walleye TP estimates from the spring season appear representative of feeding throughout the entire previous year.

The potential for retreating alpine glaciers to alter alpine ecosystems in the Colorado Front Range

NASA Astrophysics Data System (ADS)

Hall, E.; Baron, J.

2013-12-01

Glaciers are retreating at an unprecedented rate. In mid-latitude alpine ecosystems the presence of glaciers and rock glaciers govern rates and ecology of alpine and sub-alpine ecosystems. Changes in the thermal environment due to the loss of isothermal habitat and inputs from glacier melt chemistry are altering alpine ecosystems in unpredictable ways. In particular, glacier may be a source of nitrogen that is altering alpine ecosystem dynamics. Loch Vale Watershed (LVWS) located within Rocky Mountain National Park. LVWS contains a surface glacier (Andrew's glacier) and a rock glacier (Taylor's glacier) at the headwater of each of the two drainages within the watershed. We collected precipitation from a National Atmospheric Deposition Site and surface water from multiple alpine lakes and streams during a particularly high and low snow year in the Colorado Front Range. We also sampled stream and lake sediments at each site to analyze the associated microbial community. Concentrations of nitrate and ammonium, relative abundance of amoA (the gene responsible for a key step in the microbial nitrification pathway), and the dual isotope signal to nitrate all point to snow melt as a key deliverer of nitrogen to ecosystems along the Colorado Front Range. However, late summer surface water chemistry is isotopically similar to the chemistry of glacial ice. This suggests that retreating glacier may be an additional source of N to alpine ecosystems and have the potential to alter microbial community composition, biogeochemical rate processes, and ecosystem function. These dynamics are most likely not unique to the Colorado Front Range and should be globally distributed as glaciers continue to retreat in high altitude ecosystems around the world.

Comparing spatial and temporal patterns of river water isotopes across networks

EPA Science Inventory

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

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Needle trap extraction for GC analysis of formic and acetic acids in aqueous solution.

PubMed

Lee, Xinqing; Huang, Daikuan; Lou, Dawei; Pawliszyn, Janusz

2012-07-01

Formic and acetic acids are ubiquitous in the environment, food, and most of the natural products. Extraction of the acids from aqueous solution is required for their isotope analysis by the gas chromatography-isotope ratio mass spectrometry. To this objective, we have previously developed a purge-and-trap technique using the dynamic solid-phase microextraction technology, the NeedlEX. The extraction efficiency, however, remains unexamined. Here, we address this question using the flame ionization detector and isotope ratio mass spectrometer while comparing it with that of the CAR/PDMS fiber. The results show that the NeedlEX is applicable at a wide range of concentration through coordination of purge volume given the minimum amount 3.7 ng and 1.8 ng of formic and acetic, respectively, is extracted. The efficiency of NeedlEX was 6-7 times lower than the fiber at 1000 μg/mL depending on the analyte. It is, however, superior to the latter at 10 μg/mL or less owing to its lower detection limit. The extraction efficiency of both acids is equivalent in molar amount. This is, however, disguised by the different response of the flame ionization detector. The isotope ratio mass spectrometor overcomes this problem but is compromised by relatively large errors. These results are particularly useful for isotopic analysis of carboxylic acids. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

PubMed

Flakus, Henryk T; Michta, Anna

2010-02-04

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

Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

PubMed

Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

2016-06-01

The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental data presented in the two-dimensional plot of hydrogen versus carbon stable isotope signatures.

Exploring water cycle dynamics by sampling multiple stable water isotope pools in a developed landscape in Germany

NASA Astrophysics Data System (ADS)

Orlowski, Natalie; Kraft, Philipp; Pferdmenges, Jakob; Breuer, Lutz

2016-09-01

A dual stable water isotope (δ2H and δ18O) study was conducted in the developed (managed) landscape of the Schwingbach catchment (Germany). The 2-year weekly to biweekly measurements of precipitation, stream, and groundwater isotopes revealed that surface and groundwater are isotopically disconnected from the annual precipitation cycle but showed bidirectional interactions between each other. Apparently, snowmelt played a fundamental role for groundwater recharge explaining the observed differences to precipitation δ values. A spatially distributed snapshot sampling of soil water isotopes at two soil depths at 52 sampling points across different land uses (arable land, forest, and grassland) revealed that topsoil isotopic signatures were similar to the precipitation input signal. Preferential water flow paths occurred under forested soils, explaining the isotopic similarities between top- and subsoil isotopic signatures. Due to human-impacted agricultural land use (tilling and compression) of arable and grassland soils, water delivery to the deeper soil layers was reduced, resulting in significant different isotopic signatures. However, the land use influence became less pronounced with depth and soil water approached groundwater δ values. Seasonally tracing stable water isotopes through soil profiles showed that the influence of new percolating soil water decreased with depth as no remarkable seasonality in soil isotopic signatures was obvious at depths > 0.9 m and constant values were observed through space and time. Since classic isotope evaluation methods such as transfer-function-based mean transit time calculations did not provide a good fit between the observed and calculated data, we established a hydrological model to estimate spatially distributed groundwater ages and flow directions within the Vollnkirchener Bach subcatchment. Our model revealed that complex age dynamics exist within the subcatchment and that much of the runoff must has been stored for much longer than event water (average water age is 16 years). Tracing stable water isotopes through the water cycle in combination with our hydrological model was valuable for determining interactions between different water cycle components and unravelling age dynamics within the study area. This knowledge can further improve catchment-specific process understanding of developed, human-impacted landscapes.

Extending the Dynamic Range of a Time Projection Chamber

NASA Astrophysics Data System (ADS)

Estee, Justin; S πRIT Collaboration

2017-09-01

The use of Time Projection Chambers (TPCs) in intermediate heavy ion reactions faces some challenges in addressing the energy losses that range from the small energy loss of relativistic pions to the large energy loss of slow moving heavy ions. A typical trade-off can be to set the smallest desired signals to be well within the lower limits of the dynamic range of the electronics while allowing for some larger signals to saturate the electronics. With wire plane anodes, signals from readout pads further away from the track remain unsaturated and allow signals from tracks with saturated pads to be accurately recovered. We illustrate this technique using data from the SAMURAI Pion-Reconstruction and Ion-Tracker (S πRIT) TPC , which recently measured pions and light charged particles in collisions of Sn+Sn isotopes. Our method exploits knowledge of how the induced charge distribution depends on the distance from the track to smoothly extend dynamic range even when some of the pads in the track are saturated. To accommodate the analysis of slow moving heavy ions, we have extended the Bichsel energy loss distributions to handle slower moving ions as well. In this talk, I will discuss a combined approach which successfully extends the dynamic range of the TPC electronics. This work is supported by the U.S. DOE under Grant Nos. DE-SC0014530, DE-NA0002923, US NSF Grant No. PHY-1565546 and the Japan MEXT KAKENHI Grant No. 24105004.

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

NASA Astrophysics Data System (ADS)

Wright, Z.

2015-12-01

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

Carbon isotope constraints on degassing of carbon dioxide from Kilauea Volcano

USGS Publications Warehouse

Gerlach, T.M.; Taylor, B.E.

1990-01-01

We examine models for batch-equilibrium and fractional-equilibrium degassing of CO2 from magma at Kilauea Volcano. The models are based on 1. (1) the concept of two-stage degassing of CO2 from magma supplied to the summit chamber, 2. (2) C isotope data for CO2 in eruptive and noneruptive (quiescent) gases from Kilauea and 3. (3) data for the isotopic fractionation of C between CO2 and C dissolved in tholeiitic basalt melt. The results of our study indicate that 1. (1) both eruptive and noneruptive degassing of CO2 most closely approach a batch equilibrium process, 2. (2) the ??13C of parental magma supplied to the summit chamber is in the range -4.1 to-3.4??? and 3. (3) the ??13C of melt after summit chamber degassing is in the range -7 to -8???, depending upon the depth of equilibration. We also present ??13C data for CO2 in eruptive gases from the current East Rift Zone eruption. These are the first C isotope data for CO2 in high-temperature (>900??C) eruptive gases from Kilauea; they have a mean ??13C value of -7.82 ?? 0.24??? and are similar to those predicted for the melt after summit chamber degassing. The minor role played by fractional degassing of ascending magma at Kilauea means that exsolved CO2 tends to remain entrained in and coherent with its host melt during ascent from both mantle source regions and crustal magma reservoirs. This has important implications for magma dynamics at Kilauea. ?? 1990.

NMR studies of double proton transfer in hydrogen bonded cyclic N,N'-diarylformamidine dimers: conformational control, kinetic HH/HD/DD isotope effects and tunneling.

PubMed

Lopez, Juan Miguel; Männle, Ferdinand; Wawer, Iwona; Buntkowsky, Gerd; Limbach, Hans-Heinrich

2007-08-28

Using dynamic NMR spectroscopy, the kinetics of the degenerate double proton transfer in cyclic dimers of polycrystalline (15)N,(15)N'-di-(4-bromophenyl)-formamidine (DBrFA) have been studied including the kinetic HH/HD/DD isotope effects in a wide temperature range. This transfer is controlled by intermolecular interactions, which in turn are controlled by the molecular conformation and hence the molecular structure. At low temperatures, rate constants were determined by line shape analysis of (15)N NMR spectra obtained using cross-polarization (CP) and magic angle spinning (MAS). At higher temperatures, in the microsecond time scale, rate constants and kinetic isotope effects were obtained by a combination of longitudinal (15)N and (2)H relaxation measurements. (15)N CPMAS line shape analysis was also employed to study the non-degenerate double proton transfer of polycrystalline (15)N,(15)N'-diphenyl-formamidine (DPFA). The kinetic results are in excellent agreement with the kinetics of DPFA and (15)N,(15)N'-di-(4-fluorophenyl)-formamidine (DFFA) studied previously for solutions in tetrahydrofuran. Two large HH/HD and HD/DD isotope effects are observed in the whole temperature range which indicates a concerted double proton transfer mechanism in the domain of the reaction energy surface. The Arrhenius curves are non-linear indicating a tunneling mechanism. Arrhenius curve simulations were performed using the Bell-Limbach tunneling model. The role of the phenyl group conformation and hydrogen bond compression on the barrier of the proton transfer is discussed.

Use of stable isotope analysis in determining aquatic food webs

EPA Science Inventory

Stable isotope analysis is a useful tool for describing resource-consumer dynamics in ecosystems. In general, organisms of a given trophic level or functional feeding group will have a stable isotope ratio identifiable different than their prey because of preferential use of one ...

A toolkit for determining historical eco-hydrological interactions

NASA Astrophysics Data System (ADS)

Singer, M. B.; Sargeant, C. I.; Evans, C. M.; Vallet-Coulomb, C.

2016-12-01

Contemporary climate change is predicted to result in perturbations to hydroclimatic regimes across the globe, with some regions forecast to become warmer and drier. Given that water is a primary determinant of vegetative health and productivity, we can expect shifts in the availability of this critical resource to have significant impacts on forested ecosystems. The subject is particularly complex in environments where multiple sources of water are potentially available to vegetation and which may also exhibit spatial and temporal variability. To anticipate how subsurface hydrological partitioning may evolve in the future and impact overlying vegetation, we require well constrained, historical data and a modelling framework for assessing the dynamics of subsurface hydrology. We outline a toolkit to retrospectively investigate dynamic water use by trees. We describe a synergistic approach, which combines isotope dendrochronology of tree ring cellulose with a biomechanical model, detailed climatic and isotopic data in endmember waters to assess the mean isotopic composition of source water used in annual tree rings. We identify the data requirements and suggest three versions of the toolkit based on data availability. We present sensitivity analyses in order to identify the key variables required to constrain model predictions and then develop empirical relationships for constraining these parameters based on climate records. We demonstrate our methodology within a Mediterranean riparian forest site and show how it can be used along with subsurface hydrological modelling to validate source water determinations, which are fundamental to understanding climatic fluctuations and trends in subsurface hydrology. We suggest that the utility of our toolkit is applicable in riparian zones and in a range of forest environments where distinct isotopic endmembers are present.

Magnesium isotope systematics in Martian meteorites

NASA Astrophysics Data System (ADS)

Magna, Tomáš; Hu, Yan; Teng, Fang-Zhen; Mezger, Klaus

2017-09-01

Magnesium isotope compositions are reported for a suite of Martian meteorites that span the range of petrological and geochemical types recognized to date for Mars, including crustal breccia Northwest Africa (NWA) 7034. The δ26Mg values (per mil units relative to DSM-3 reference material) range from -0.32 to -0.11‰; basaltic shergottites and nakhlites lie to the heavier end of the Mg isotope range whereas olivine-phyric, olivine-orthopyroxene-phyric and lherzolitic shergottites, and chassignites have slightly lighter Mg isotope compositions, attesting to modest correlation of Mg isotopes and petrology of the samples. Slightly heavier Mg isotope compositions found for surface-related materials (NWA 7034, black glass fraction of the Tissint shergottite fall; δ26Mg > -0.17‰) indicate measurable Mg isotope difference between the Martian mantle and crust but the true extent of Mg isotope fractionation for Martian surface materials remains unconstrained. The range of δ26Mg values from -0.19 to -0.11‰ in nakhlites is most likely due to accumulation of clinopyroxene during petrogenesis rather than garnet fractionation in the source or assimilation of surface material modified at low temperatures. The rather restricted range in Mg isotope compositions between spatially and temporally distinct mantle-derived samples supports the idea of inefficient/absent major tectonic cycles on Mars, which would include plate tectonics and large-scale recycling of isotopically fractionated surface materials back into the Martian mantle. The cumulative δ26Mg value of Martian samples, which are not influenced by late-stage alteration processes and/or crust-mantle interactions, is - 0.271 ± 0.040 ‰ (2SD) and is considered to reflect δ26Mg value of the Bulk Silicate Mars. This value is robust taking into account the range of lithologies involved in this estimate. It also attests to the lack of the Mg isotope variability reported for the inner Solar System bodies at current analytical precision, also noted for several other major elements.

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.

High dynamic range spectroscopic studies of shocked nitromethane

NASA Astrophysics Data System (ADS)

Bhowmick, Mithun; Nissen, Erin J.; Dlott, Dana D.

In this talk we describe a tabletop apparatus that can reproducibly drive shocks through tiny cells containing liquid arranged in an array for high-throughput shock compression studies. This talk will focus on nitromethane, a liquid reactive to shocks and capable of detonation. In our studies, a laser-driven flyer plate was used to shock nitromethane, and a spectrometer with high dynamic range was employed to measure emission spectra from nanosecond to millisecond time scales. Typically, 50 single-shock experiments were performed per day with precisely controllable shock speeds below, above, or equal to the detonation shock speed. The emission spectra provide temperature histories using the graybody approximation. The ability to conveniently shock nitromethane on a benchtop will be used with isotopically substituted and amine-sensitized nitromethane and in future will be combined with other spectroscopies such as infrared absorption. Multidisciplinary University Research Initiative (MURI), Office of Naval Research.

Studies in shocked nitromethane through High dynamic range spectroscopy

NASA Astrophysics Data System (ADS)

Bhowmick, Mithun; Nissen, Erin; Matveev, Sergey; Dlott, Dana

2017-06-01

In this talk we describe a tabletop apparatus that can reproducibly drive shocks through tiny cells containing liquid arranged in an array for high-throughput shock compression studies. This talk will focus on nitromethane, a liquid reactive to shocks and capable of detonation. In our studies, a laser-driven ?yer plate was used to shock nitromethane, and a spectrometer with high dynamic range was employed to measure emission spectra from nanosecond to millisecond time scales. Typically, 50 single-shock experiments were performed per day with precisely controllable shock speeds below, above, or equal to the detonation shock speed. The emission spectra provide temperature histories using the grey body approximation. The ability to conveniently shock nitromethane on a benchtop was used with isotopically substituted and amine-sensitized nitromethane and in future will be combined with other spectroscopies such as infrared absorption. Multidisciplinary University Research Initiative (MURI), Office of Naval Research.

On structural identifiability analysis of the cascaded linear dynamic systems in isotopically non-stationary 13C labelling experiments.

PubMed

Lin, Weilu; Wang, Zejian; Huang, Mingzhi; Zhuang, Yingping; Zhang, Siliang

2018-06-01

The isotopically non-stationary 13C labelling experiments, as an emerging experimental technique, can estimate the intracellular fluxes of the cell culture under an isotopic transient period. However, to the best of our knowledge, the issue of the structural identifiability analysis of non-stationary isotope experiments is not well addressed in the literature. In this work, the local structural identifiability analysis for non-stationary cumomer balance equations is conducted based on the Taylor series approach. The numerical rank of the Jacobian matrices of the finite extended time derivatives of the measured fractions with respect to the free parameters is taken as the criterion. It turns out that only one single time point is necessary to achieve the structural identifiability analysis of the cascaded linear dynamic system of non-stationary isotope experiments. The equivalence between the local structural identifiability of the cascaded linear dynamic systems and the local optimum condition of the nonlinear least squares problem is elucidated in the work. Optimal measurements sets can then be determined for the metabolic network. Two simulated metabolic networks are adopted to demonstrate the utility of the proposed method. Copyright © 2018 Elsevier Inc. All rights reserved.

Spatio-temporal variation in the tap water isotope ratios of Salt Lake City: a novel indicator of urban water system structure and dynamics.

NASA Astrophysics Data System (ADS)

Jameel, M. Y.; Bowen, G. J.

2015-12-01

Public water supply systems are the life-blood of urban areas. How we use urban water systems affects more than human health and well-being. Our water use can alter a city's energy balance, including how much solar energy is absorbed as heat or reflected back into space. The severity of these effects, and the need to better understand connections between climate, water extraction, water use, and water use impacts, is strongest in areas of climatic aridity and substantial land-use change, such as the rapidly urbanizing areas of Utah. We have gathered and analyzed stable water isotope data from a series of semi-annual hydrological surveys (spring and fall, 2013 and 2014) in urban tap water sampled across the Salt Lake Valley. Our study has led to four major findings thus far: 1) Clear and substantial variation in tap water isotopic composition in space and time that can be linked to different water sources and management practices within the urban area, 2) There is a strong correlation between the range of observed isotope values and the population of water districts, reflecting use of water from multiple local and non-local sources in districts with high water demand, 3) Water isotopes reflect significant and variable loss of water due to evaporation of surface water resources and 4) Overall, tap water contains lower concentrations of the heavy H and O isotopes than does precipitation within the basin, reflecting the connection between city water supplies and mountain water sources. Our results highlight the utility of isotopic data as an indicator of heterogeneities within urban water systems, management practices and their variation across a major metropolitan area, and effects of climate variability on urban water supplies

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

NASA Technical Reports Server (NTRS)

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

How much of stream and groundwater comes from snow? A stable isotope perspective in the Swiss Alps

NASA Astrophysics Data System (ADS)

Beria, H.; Schaefli, B.; Ceperley, N. C.; Michelon, A.; Larsen, J.

2017-12-01

Precipitation which once fell as snow is predicted to fall more often as liquid rain now that climate is, and continues, warming. Within snow dominated areas, preferential winter groundwater recharge has been observed, however a shorter winter season and smaller snow fraction results in earlier snowmelt and thinner snowpacks. This has the potential to change the supply of snow water sources to both streams and groundwater, which has important implications for flow regimes and water resources. Stable isotopes of water (2H and 18O) allow us to discriminate rain vs snow signatures within water flowing in the stream or the subsurface. Using one year of isotope data collected in a Swiss Alpine catchment (Vallon de Nant, Vaud), we developed novel forward Bayesian mixing models, based on statistical and empirical likelihoods, to quantify source contributions and uncertainty estimates. To account for the spatial heterogeneity in precipitation isotopes, we parameterized the model accounting for elevation effects on isotopes, calculated using the network of GNIP stations in Switzerland. Instead of sampling meltwater, we sampled snowpack throughout the season and across a steep elevation gradient (1241m to 2455m) to infer the snowmelt transformation factor. Due to continuous mixing within the snowpack, the snowmelt water shows much lower variability in its isotopic range which is reflected in the snow transformation factor. Snowmelt yield to groundwater recharge per unit amount of precipitation was found to be greater than rainfall in Vallon de Nant, suggesting strongly preferential winter recharge. Seasonal dynamics of stream responses to rain-on-snow events, fog deposition, snowmelt and summer rain were also explored. Innovative monitoring and sampling with tools such as stable isotopes and forward Bayesian mixing models are key to improved comprehension of global recharge mechanisms.

A novel membrane inlet mass spectrometer method to measure ¹⁵NH4₄⁺ for isotope-enrichment experiments in aquatic ecosystems.

PubMed

Yin, Guoyu; Hou, Lijun; Liu, Min; Liu, Zhanfei; Gardner, Wayne S

2014-08-19

Nitrogen (N) pollution in aquatic ecosystems has attracted much attention over the past decades, but the dynamics of this bioreactive element are difficult to measure in aquatic oxygen-transition environments. Nitrogen-transformation experiments often require measurement of (15)N-ammonium ((15)NH4(+)) ratios in small-volume (15)N-enriched samples. Published methods to determine N isotope ratios of dissolved ammonium require large samples and/or costly equipment and effort. We present a novel ("OX/MIMS") method to determine N isotope ratios for (15)NH4(+) in experimental waters previously enriched with (15)N compounds. Dissolved reduced (15)N (dominated by (15)NH4(+)) is oxidized with hypobromite iodine to nitrogen gas ((29)N2 and/or (30)N2) and analyzed by membrane inlet mass spectrometry (MIMS) to quantify (15)NH4(+) concentrations. The N isotope ratios, obtained by comparing the (15)NH4(+) to total ammonium (via autoanalyzer) concentrations, are compared to the ratios of prepared standards. The OX/MIMS method requires only small sample volumes of water (ca. 12 mL) or sediment slurries and is rapid, convenient, accurate, and precise (R(2) = 0.9994, p < 0.0001) over a range of salinities and (15)N/(14)N ratios. It can provide data needed to quantify rates of ammonium regeneration, potential ammonium uptake, and dissimilatory nitrate reduction to ammonium (DNRA). Isotope ratio results agreed closely (R = 0.998, P = 0.001) with those determined independently by isotope ratio mass spectrometry for DNRA measurements or by ammonium isotope retention time shift liquid chromatography for water-column N-cycling experiments. Application of OX/MIMS should simplify experimental approaches and improve understanding of N-cycling rates and fate in a variety of freshwater and marine environments.

An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

NASA Astrophysics Data System (ADS)

Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

2016-09-01

Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

Wobbling mode inf {sup 167}Ta.

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

Hartley, D. J.; Janssens, R. V. F.; Riedinger, L. L.

2009-01-01

The collective wobbling mode, the strongest signature for the rotation of a triaxial nucleus, has previously been seen only in a few Lu isotopes in spite of extensive searches in nearby isotopes. A sequence of transitions in the N = 94 {sup 167}Ta nucleus exhibiting features similar to those attributed to the wobbling bands in the Lu nuclei has now been found. This band feeds into the {pi}/{sub 13/2} band at a relative energy similar to that seen in the established wobbling bands and its dynamic moment of inertia and alignment properties are nearly identical to the /{sub 13/2} structuremore » over a significant frequency range. Given these characteristics, it is likely that the wobbling mode has been observed for the first time in a nucleus other than Lu, making this collective motion a more general phenomenon.« less

Soil drying effects on the carbon isotope composition of soil respiration

EPA Science Inventory

Stable isotopes are used widely as a tool for determining sources of carbon (C) fluxes in ecosystem C studies. Environmental factors that change over time, such as moisture, can create dynamic changes in the isotopic composition of C assimilated by plants, and offers a unique opp...

‘Leaves and Eats Shoots’: Direct Terrestrial Feeding Can Supplement Invasive Red Swamp Crayfish in Times of Need

PubMed Central

Grey, Jonathan; Jackson, Michelle C.

2012-01-01

We used stable isotope analyses to characterise the feeding dynamics of a population of red swamp crayfish in Lake Naivasha, Kenya, after the crash of submerged macrophytes and associated macroinvertebrates, and during a natural draw-down of the lake water level. We expected a heavy reliance upon a diet of detrital matter to sustain the population as a consequence, and indeed, for the majority of the crayfish population caught from the lake, we saw a concomitant shift in isotopic values reflecting a dietary change. However, we also caught individual crayfish that had occupied the footprints of hippopotamus and effectively extended their range beyond the lake up to 40 m into the riparian zone. Isotopic analysis confirmed limited nocturnal observations that these individuals were consuming living terrestrial plants in the vicinity of the footprints. These are the first empirical data to demonstrate direct use of terrestrial resources by an aquatic crayfish species and further highlight the traits that make red swamp crayfish such opportunistic and successful invaders. PMID:22880039

The Lamont--Doherty Geological Observatory Isolab 54 isotope ratio mass spectrometer

NASA Astrophysics Data System (ADS)

England, J. G.; Zindler, A.; Reisberg, L. C.; Rubenstone, J. L.; Salters, V.; Marcantonio, F.; Bourdon, B.; Brueckner, H.; Turner, P. J.; Weaver, S.; Read, P.

1992-12-01

The Lamont--Doherty Geological Observatory (LDGO) Isolab 54 is a double focussing isotope ratio mass spectrometer that allows the measurement of thermal ions produced on a hot filament, (thermal-ionization mass spectrometry (TIMS)), secondary ions produced by sputtering a sample using a primary ion beam, (secondary ion mass spectrometry (SIMS)), and sputtered neutrals resonantly ionized using laser radiation, (sputter-induced resonance ionization mass spectrometry (SIRIMS)). Sputtering is carried out using an Ar primary beam generated in a duoplasmatron and focussed onto the sample using a two-lens column. Resonance ionization is accomplished using a frequency-doubled dye laser pumped by an excimer laser. The Isolab's forward geometry analyzer, consisting of an electrostatic followed by a magnetic sector, allows the simultaneous collection of different isotopes of the same element. This instrument is the first to have a multicollector that contains an ion-counting system based on a microchannel plate as well as traditional Faraday cups. A second electrostatic sector after the multicollector is equipped with an ion-counting Daly detector to allow high abundance sensitivity for measurements of large dynamics range. Selectable source, collector, [alpha] and energy slits on the instrument allow analyses to be made over a range of mass resolving powers and analyzer acceptances. Recent applications of the instrument have included the analyses of U by TIMS, Hf, Th and Re by SIMS and Re and Os by SIRIMS.

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

USGS Publications Warehouse

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

2013-01-01

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

Estimating pothole wetland connectivity to Pipestem Creek ...

EPA Pesticide Factsheets

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding how reliant stream flow is on wetlands within their watershed. We used the isotopic evaporation signal in water to examine hydrologic connectivity within Pipestem Creek, North Dakota, with a watershed dominated by prairie potholes. During a decadal period of wet conditions, Pipestem Creek contained evaporated water that had approximately half the isotopic evaporative enrichment signal found in most evaporated permanent wetlands. If evaporation was mainly occurring within the stream, we expected the evaporation signal to increase from the headwaters with distance downstream. However, the signal either remained similar or decreased downstream over the two years of sampling. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporation. Using isotopic theory and discharge data, we estimated the surface area of open water necessary to generate the evaporation signal found within Pipestem Creek over time. The range of evaporating surface-area estimates was highly dynamic, spanning from 43 to 2653 ha and varying primarily with discharge. The average value (just over 600 ha) was well above the surface area of Pipestem Creek network (245 ha). This estimate of contributing area indicated that Prairie Pothole wetlands were important sources of stream fl

Estimating pothole wetland connectivity to Pipestem Creek ...

EPA Pesticide Factsheets

Understanding hydrologic connectivity between wetlands and perennial streams is critical to understanding how reliant stream flow is on wetlands within their watershed. We used the isotopic evaporation signal in water to examine wetland-stream hydrologic connectivity within the Pipestem Creek watershed, North Dakota, a watershed dominated by prairie-pothole wetlands. During a wetter-than-normal decade, Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched pothole wetlands. If evaporation was mainly occurring within the stream, we expected the evaporation signal to increase from upstream towards downstream. However, the signal either remained similar or decreased downstream over the two years of sampling. Groundwater measured at the water table adjacent to Pipestem Creek had isotopic values that indicated recharge from winter precipitation and had no significant evaporative enrichment. Using isotopic theory and discharge data, we estimated the surface area of open water necessary to generate the evaporation signal found within Pipestem Creek over time. The range of evaporating surface-area estimates was highly dynamic, spanning from 35 to 2380 ha of open water contributing to streamflow over time, and varied primarily with the amount of discharge. The median value (417 ha) was well above the surface area of the Pipestem Creek network (245 ha), and only two periods

High-Precision In Situ 87Sr/86Sr Analyses through Microsampling on Solid Samples: Applications to Earth and Life Sciences

PubMed Central

Di Salvo, Sara; Casalini, Martina; Marchionni, Sara; Adani, Teresa; Ulivi, Maurizio; Tommasini, Simone; Avanzinelli, Riccardo; Mazza, Paul P. A.; Francalanci, Lorella

2018-01-01

An analytical protocol for high-precision, in situ microscale isotopic investigations is presented here, which combines the use of a high-performing mechanical microsampling device and high-precision TIMS measurements on micro-Sr samples, allowing for excellent results both in accuracy and precision. The present paper is a detailed methodological description of the whole analytical procedure from sampling to elemental purification and Sr-isotope measurements. The method offers the potential to attain isotope data at the microscale on a wide range of solid materials with the use of minimally invasive sampling. In addition, we present three significant case studies for geological and life sciences, as examples of the various applications of microscale 87Sr/86Sr isotope ratios, concerning (i) the pre-eruptive mechanisms triggering recent eruptions at Nisyros volcano (Greece), (ii) the dynamics involved with the initial magma ascent during Eyjafjallajökull volcano's (Iceland) 2010 eruption, which are usually related to the precursory signals of the eruption, and (iii) the environmental context of a MIS 3 cave bear, Ursus spelaeus. The studied cases show the robustness of the methods, which can be also be applied in other areas, such as cultural heritage, archaeology, petrology, and forensic sciences. PMID:29850369

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada

PubMed Central

Longstaffe, Fred J.; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0–1 ‰) in δ13C of modern Yukon grasses. A major change (~2–10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time. PMID:29447202

Catalytic-site design for inverse heavy-enzyme isotope effects in human purine nucleoside phosphorylase

PubMed Central

Harijan, Rajesh K.; Zoi, Ioanna; Antoniou, Dimitri; Schwartz, Steven D.; Schramm, Vern L.

2017-01-01

Heavy-enzyme isotope effects (15N-, 13C-, and 2H-labeled protein) explore mass-dependent vibrational modes linked to catalysis. Transition path-sampling (TPS) calculations have predicted femtosecond dynamic coupling at the catalytic site of human purine nucleoside phosphorylase (PNP). Coupling is observed in heavy PNPs, where slowed barrier crossing caused a normal heavy-enzyme isotope effect (kchem light/kchem heavy > 1.0). We used TPS to design mutant F159Y PNP, predicted to improve barrier crossing for heavy F159Y PNP, an attempt to generate a rare inverse heavy-enzyme isotope effect (kchem light/kchem heavy < 1.0). Steady-state kinetic comparison of light and heavy native PNPs to light and heavy F159Y PNPs revealed similar kinetic properties. Pre–steady-state chemistry was slowed 32-fold in F159Y PNP. Pre–steady-state chemistry compared heavy and light native and F159Y PNPs and found a normal heavy-enzyme isotope effect of 1.31 for native PNP and an inverse effect of 0.75 for F159Y PNP. Increased isotopic mass in F159Y PNP causes more efficient transition state formation. Independent validation of the inverse isotope effect for heavy F159Y PNP came from commitment to catalysis experiments. Most heavy enzymes demonstrate normal heavy-enzyme isotope effects, and F159Y PNP is a rare example of an inverse effect. Crystal structures and TPS dynamics of native and F159Y PNPs explore the catalytic-site geometry associated with these catalytic changes. Experimental validation of TPS predictions for barrier crossing establishes the connection of rapid protein dynamics and vibrational coupling to enzymatic transition state passage. PMID:28584087

Nitrogen isotopes suggest a change in nitrogen dynamics between the Late Pleistocene and modern time in Yukon, Canada.

PubMed

Tahmasebi, Farnoush; Longstaffe, Fred J; Zazula, Grant

2018-01-01

A magnificent repository of Late Pleistocene terrestrial megafauna fossils is contained in ice-rich loess deposits of Alaska and Yukon, collectively eastern Beringia. The stable carbon (δ13C) and nitrogen (δ15N) isotope compositions of bone collagen from these fossils are routinely used to determine paleodiet and reconstruct the paleoecosystem. This approach requires consideration of changes in C- and N-isotope dynamics over time and their effects on the terrestrial vegetation isotopic baseline. To test for such changes between the Late Pleistocene and modern time, we compared δ13C and δ15N for vegetation and bone collagen and structural carbonate of some modern, Yukon, arctic ground squirrels with vegetation and bones from Late Pleistocene fossil arctic ground squirrel nests preserved in Yukon loess deposits. The isotopic discrimination between arctic ground squirrel bone collagen and their diet was measured using modern samples, as were isotopic changes during plant decomposition; Over-wintering decomposition of typical vegetation following senescence resulted in a minor change (~0-1 ‰) in δ13C of modern Yukon grasses. A major change (~2-10 ‰) in δ15N was measured for decomposing Yukon grasses thinly covered by loess. As expected, the collagen-diet C-isotope discrimination measured for modern samples confirms that modern vegetation δ13C is a suitable proxy for the Late Pleistocene vegetation in Yukon Territory, after correction for the Suess effect. The N-isotope composition of vegetation from the fossil arctic ground squirrel nests, however, is determined to be ~2.8 ‰ higher than modern grasslands in the region, after correction for decomposition effects. This result suggests a change in N dynamics in this region between the Late Pleistocene and modern time.

Elucidating the nutritional dynamics of fungi using stable isotopes.

PubMed

Mayor, Jordan R; Schuur, Edward A G; Henkel, Terry W

2009-02-01

Mycorrhizal and saprotrophic (SAP) fungi are essential to terrestrial element cycling due to their uptake of mineral nutrients and decomposition of detritus. Linking these ecological roles to specific fungi is necessary to improve our understanding of global nutrient cycling, fungal ecophysiology, and forest ecology. Using discriminant analyses of nitrogen (delta(15)N) and carbon (delta(13)C) isotope values from 813 fungi across 23 sites, we verified collector-based categorizations as either ectomycorrhizal (ECM) or SAP in > 91% of the fungi, and provided probabilistic assignments for an additional 27 fungi of unknown ecological role. As sites ranged from boreal tundra to tropical rainforest, we were able to show that fungal delta(13)C (26 sites) and delta(15)N (32 sites) values could be predicted by climate or latitude as previously shown in plant and soil analyses. Fungal delta(13)C values are likely reflecting differences in C-source between ECM and SAP fungi, whereas (15)N enrichment of ECM fungi relative to SAP fungi suggests that ECM fungi are consistently delivering (15)N depleted N to host trees across a range of ecosystem types.

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

PubMed

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

2017-04-01

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

Development and Deployment of a Portable Water Isotope Analyzer for Accurate, Continuous and High-Frequency Oxygen and Hydrogen Isotope Measurements in Water Vapor and Liquid Water

NASA Astrophysics Data System (ADS)

Dong, Feng; Baer, Douglas

2010-05-01

Stable isotopes of water in liquid and vapor samples are powerful tracers to investigate the hydrological cycle and ecological processes. Therefore, continuous, in-situ and accurate measurements of del_18O and del_2H are critical to advance the understanding of water cycle dynamics around the globe. Furthermore, the combination of meteorological techniques and high-frequency isotopic water measurements can provide detailed time-resolved information on the eco-physiological performance of plants and enable improved understanding of water fluxes at ecosystem scales. In this work, we present recent laboratory development and field deployment of a novel Water Vapor Isotope Analyzer (WVIA), based on cavity enhanced laser absorption spectroscopy, capable of simultaneous in-situ measurements of del_18O and del_2H and water mixing ratio with high precision and high frequency (up to 10 Hz measurement rate). In addition, to ensure the accuracy of the water vapor isotope measurements, a novel Water Vapor Isotope Standard Source (WVISS), based on the instantaneous evaporation of micro-droplets of liquid water (with known isotope composition), has been developed to provide the reference water vapor with widely adjustable mixing ratio (500-30,000 ppmv) for real-time calibration of the WVIA. The comprehensive system that includes the WVIA and WVISS has been validated in extensive laboratory and field studies to be insensitive to ambient temperature changes (5-40 C) and to changes in water mixing ratio over a wide range of mixing ratios. In addition, by operating in the dual inlet mode, measurement drift has essentially been eliminated. The system (WVIA+WVISS) has also been deployed for long-term unattended continuous measurements in the field. In addition to water vapor isotope measurements, the new Water Vapor Isotopic Standard Source (WVISS) may be combined with the WVIA to provide continuous isotopic measurements of liquid water samples at rapid data rate. The availability of these new field instruments provides new opportunities for detailed continuous measurements of the hydrological cycle and ecological systems.

A free-air system for long-term stable carbon isotope labeling of adult forest trees

EPA Science Inventory

Stable carbon (C) isotopes, in particular employed in labeling experiments, are an ideal tool to broaden our understanding of C dynamics in trees and forest ecosystems. Here, we present a free-air exposure system, named isoFACE, designed for long-term stable C isotope labeling in...

Selective IR multiphoton dissociation of molecules in a pulsed gas-dynamically cooled molecular flow interacting with a solid surface as an alternative to low-energy methods of molecular laser isotope separation

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

Makarov, G N; Petin, A N

2016-03-31

We report the results of studies on the isotope-selective infrared multiphoton dissociation (IR MFD) of SF{sub 6} and CF{sub 3}I molecules in a pulsed, gas-dynamically cooled molecular flow interacting with a solid surface. The productivity of this method in the conditions of a specific experiment (by the example of SF{sub 6} molecules) is evaluated. A number of low-energy methods of molecular laser isotope separation based on the use of infrared lasers for selective excitation of molecules are analysed and their productivity is estimated. The methods are compared with those of selective dissociation of molecules in the flow interacting with amore » surface. The advantages of this method compared to the low-energy methods of molecular laser isotope separation and the IR MPD method in the unperturbed jets and flows are shown. It is concluded that this method could be a promising alternative to the low-energy methods of molecular laser isotope separation. (laser separation of isotopes)« less

Interrogating trees for isotopic archives of atmospheric sulphur deposition and comparison to speleothem records.

PubMed

Wynn, P M; Loader, N J; Fairchild, I J

2014-04-01

Palaeorecords which depict changes in sulphur dynamics form an invaluable resource for recording atmospheric pollution. Tree rings constitute an archive that are ubiquitously available and can be absolutely dated, providing the potential to explore local- to regional-scale trends in sulphur availability. Rapid isotopic analysis by a novel "on-line" method using elemental analyser isotope ratio mass spectrometry (EA-IRMS) is developed, achieving sample precision of <0.4‰ using sample sizes of 40 mg wood powder. Tree cores from NE Italy show trends in pollution, evidenced through increasing concentrations of sulphur towards the youngest growth, and inverse trends in sulphur isotopes differentiating modern growth with light sulphur isotopes (+0.7‰) from pre-industrial growth (+7.5‰) influenced by bedrock composition. Comparison with speleothem records from the same location demonstrate replication, albeit offset in isotopic value due to groundwater storage. Using EA-IRMS, tree ring archives form a valuable resource for understanding local- to regional-scale sulphur pollution dynamics. Copyright © 2013 Elsevier Ltd. All rights reserved.

Using Isotopic Age of Water as a Constraint on Model Identification at a Critical Zone Observatory

NASA Astrophysics Data System (ADS)

Duffy, C.; Thomas, E.; Bhatt, G.; George, H.; Boyer, E. W.; Sullivan, P. L.

2016-12-01

This paper presents an ecohydrologic model constrained by comprehensive space and time observations of water and stable isotopes of oxygen and hydrogen for an upland catchment, the Susquehanna/Shale Hills Critical Zone Observatory (SSH_CZO). The paper first develops the theoretical basis for simulation of flow, isotope ratios and "age" as water moves through the canopy, to the unsaturated and saturated zones and finally to an intermittent stream. The model formulation demonstrates that the residence time and age of environmental tracers can be directly simulated without knowledge of the form of the underlying residence time distribution function and without the addition of any new physical parameters. The model is used to explore the observed rapid attenuation of event and seasonal isotopic ratios in precipitation over the depth of the soil zone and the impact of decreasing hydraulic conductivity with depth on the dynamics of streamflow and stream isotope ratios. The results suggest the importance of mobile macropore flow on recharge to groundwater during the non-growing cold-wet season. The soil matrix is also recharged during this season with a cold-season isotope signature. During the growing-dry season, root uptake and evaporation from the soil matrix along with a declining water table provides the main source of water for plants and determines the growing season signature. Flow path changes during storm events and transient overland flow is inferred by comparing the frequency distribution of groundwater and stream isotope histories with model results. Model uncertainty is evaluated for conditions of matrix-macropore partitioning and heterogeneous variations in conductivity with depth. The paper concludes by comparing the fully dynamical model with the simplified mixing model form in dynamic equilibrium. The comparison illustrates the importance of system memory on the time scales for flow and mixing processes and the limitations of the dynamic equilibrium assumption on estimated age and residence time.

Improvements in Calibration and Analysis of the CTBT-relevant Radioxenon Isotopes with High Resolution SiPIN-based Electron Detectors

NASA Astrophysics Data System (ADS)

Khrustalev, K.

2016-12-01

Current process for the calibration of the beta-gamma detectors used for radioxenon isotope measurements for CTBT purposes is laborious and time consuming. It uses a combination of point sources and gaseous sources resulting in differences between energy and resolution calibrations. The emergence of high resolution SiPIN based electron detectors allows improvements in the calibration and analysis process to be made. Thanks to high electron resolution of SiPIN detectors ( 8-9 keV@129 keV) compared to plastic scintillators ( 35 keV@129keV) there are a lot more CE peaks (from radioxenon and radon progenies) can be resolved and used for energy and resolution calibration in the energy range of the CTBT-relevant radioxenon isotopes. The long term stability of the SiPIN energy calibration allows one to significantly reduce the time of the QC measurements needed for checking the stability of the E/R calibration. The currently used second order polynomials for the E/R calibration fitting are unphysical and shall be replaced by a linear energy calibration for NaI and SiPIN, owing to high linearity and dynamic range of the modern digital DAQ systems, and resolution calibration functions shall be modified to reflect the underlying physical processes. Alternatively, one can completely abandon the use of fitting functions and use only point-values of E/R (similar to the efficiency calibration currently used) at the energies relevant for the isotopes of interest (ROI - Regions Of Interest ). Current analysis considers the detector as a set of single channel analysers, with an established set of coefficients relating the positions of ROIs with the positions of the QC peaks. The analysis of the spectra can be made more robust using peak and background fitting in the ROIs with a single free parameter (peak area) of the potential peaks from the known isotopes and a fixed E/R calibration values set.

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

USGS Publications Warehouse

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

2006-01-01

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

Using stable isotopes to resolve eco-hydrological dynamics of soil-plant-atmosphere feedbacks

NASA Astrophysics Data System (ADS)

Dubbert, M.; Piayda, A.; Kübert, A.; Cuntz, M.; Werner, C.

2016-12-01

Water is the main driver of ecosystem productivity in most terrestrial ecosystems worldwide. Extreme events are predicted to increase in frequency in many regions and dynamic responses in soil-vegetation-atmosphere feedbacks play a privotal role in understanding the ecosystem water balance and functioning. In this regard, more interdisciplinary approaches, bridging hydrology, ecophysiology and atmospheric sciences are needed and particularly water stable isotopes are a powerful tracer of water transfer in soils and at the soil-plant interface (Werner and Dubbert 2016). Here, we present observations 2 different ecosystems. Water fluxes, atmospheric concentrations and their isotopic compositions were measured using laser spectroscopy. Soil moisture and its isotopic composition in several depths as well as further water sources in the ecosystem were monitored throughout the year. Using these isotopic approaches we disentangled soil-plant-atmosphere feedback processes controlling the ecosystem water cycle including vegetation effects on soil water infiltration and distribution, event water use of vegetation and soil fluxes, vegetational soil water uptake depths plasticity and partitioning of ecosystem water fluxes. In this regard, we review current strategies of ET partitioning and highlight pitfalls in the presented strategies (Dubbert et al. 2013, Dubbert et al.2014a). We demonstrate that vegetation strongly influenced water cycling, altering infiltration and distribution of precipitation. In conclusion, application of stable water isotope tracers delivers a process based understanding of interactions between soil, understorey and trees governing ecosystem water cycling necessary for prediction of climate change impact on ecosystem productivity and vulnerability. ReferencesDubbert, M. et al. (2013): Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. Journal of Hydrology Dubbert, M. et al. (2014a): Oxygen isotope signatures of transpired water vapor: the role of isotopic non-steady-state transpiration under natural conditions. New Phytologist. Werner, C. and Dubbert, M. (2016): Resolving rapid dynamics of soil-plant-atmosphere interactions. New Phytologist.

A new feature in the internal heavy isotope distribution in ozone

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

Bhattacharya, S. K., E-mail: skbhatta1@gmail.com; Liang, Mao-Chang; Savarino, Joel

Ozone produced by discharge or photolysis of oxygen has unusually heavy isotopic composition ({sup 18}O/{sup 16}O and {sup 17}O/{sup 16}O ratio) which does not follow normal mass fractionation rule: δ{sup 17}O ∼ 0.52{sup *}δ{sup 18}O, expressed as an anomaly Δ{sup 17}O = δ{sup 17}O − 0.52{sup *}δ{sup 18}O. Ozone molecule being an open isosceles triangle can have the heavy isotope located either in its apex or symmetric (s) position or the base or asymmetric (as) position. Correspondingly, one can define positional isotopic enrichment, written as δ{sup 18}O (s) or δ{sup 18}O (as) (and similarly for δ{sup 17}O) as well asmore » position dependent isotope anomaly Δ{sup 17}O (s) and Δ{sup 17}O (as). Marcus and co-workers have proposed a semi-empirical model based in principle on the RRKM model of uni-molecular dissociation but with slight modification (departure from statistical randomness assumption for symmetrical molecules) which explains many features of ozone isotopic enrichment. This model predicts that the bulk isotope anomaly is contained wholly in the asymmetric position and the Δ{sup 17}O (s) is zero. Consequently, Δ{sup 17}O (as) = 1.5 {sup *} Δ{sup 17}O (bulk) (named here simply as the “1.5 rule”) which has been experimentally confirmed over a range of isotopic enrichment. We now show that a critical re-analysis of the earlier experimental data demonstrates a small but significant departure from this 1.5 rule at the highest and lowest levels of enrichments. This departure provides the first experimental proof that the dynamics of ozone formation differs from a statistical model constrained only by restriction of symmetry. We speculate over some possible causes for the departure.« 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.

Isoscalar giant monopole resonance in Sn isotopes using a quantum molecular dynamics model

NASA Astrophysics Data System (ADS)

Tao, C.; Ma, Y. G.; Zhang, G. Q.; Cao, X. G.; Fang, D. Q.; Wang, H. W.; Xu, J.

2013-12-01

The isoscalar giant monopole resonance (GMR) in Sn isotopes and other nuclei is investigated in the framework of the isospin-dependent quantum molecular dynamics (IQMD) model. The spectrum of GMR is calculated by taking the rms radius of a nucleus as its monopole moment. The peak energy, the FWHM, and the strength of the GMR extracted by a Gaussian fit to the spectrum have been studied. The GMR peak energies for Sn isotopes from the calculations using a mass-number-dependent Gaussian wave-packet width σr for nucleons are found to be overestimated and show a weak dependence on the mass number compared with the experimental data. However, it is found that experimental data of the GMR peak energies for 56Ni, 90Zr, and 208Pb as well as Sn isotopes can be nicely reproduced after taking into account the isospin dependence in isotope chains in addition to the mass-number dependence of σr for nucleons in the IQMD model calculation.

C Diffusion in Fe: Isotope Effects and Other Complexities

NASA Astrophysics Data System (ADS)

Watson, E. B.; Muller, T.; Trail, D.; Van Orman, J. A.; Papineau, D.

2011-12-01

Carbon is a minor but significant component of iron meteorites, and probably also of planetary cores, including that of Earth. Given the dynamical nature of core-forming processes, C diffusion in the metal phase may play a role in C equilibration between Fe-Ni metal and silicate, carbide or oxide at some stage. Despite its relevance to steel-making, C diffusion in Fe is not well characterized over the range of conditions of interest in planetary bodies, and the likelihood of an isotope mass effect on C diffusion has not been explored. The prospect of incomplete diffusive equilibration of carbon in Fe-Ni raises the possibility that carbon isotopes might be fractionated by diffusion during core formation and evolution-perhaps to an extent that could affect the C isotope ratio of the bulk silicate Earth. Here we report results of preliminary experiments addressing the isotopic mass effect on C diffusion in Fe. Initial low-pressure experiments were conducted by placing a layer of ^{13}C-enriched graphite ( 20% ^{13}C) at the end of a high-purity, polycrystalline Fe cylinder in a silica glass container. These diffusion couples were run in a piston-cylinder apparatus at 1.5 GPa and 1000-1100^{o}C for several hours, and the resulting C-uptake profiles in the Fe cylinders were measured by EPMA and SIMS. In traverses moving away from the original C-Fe interface, total carbon decreases monotonically and becomes significantly lighter, indicating that ^{12}C diffuses faster than ^{13}C. Preliminary estimates of β in the relative isotope diffusivity relation D_{1}/D_{2} = [M_{2}/M_{1}]^{β} (where D is diffusivity and M is mass of isotopes 1 and 2) suggest values as high as 0.5, corresponding to predictions for gaseous diffusion. Isotope mass effects approaching this magnitude have been observed previously for diffusion in metals, and are expected to be highest for interstitial diffusion. Such a high β value will lead to major C isotope fractionation in some partial equilibration scenarios in planets and meteorite parent bodies. Caution is warranted at this point, however, because D_{carbon} is sensitive to carbon concentration, complicating quantification of the isotope effect.

Stable water isotopes suggest sub-canopy water recycling in a northern forested catchment

Treesearch

Mark B. Green; Bethany K. Laursen; John L. Campbell; Kevin J. McGuire; Eric P. Kelsey

2015-01-01

Stable water isotopes provide a means of tracing many hydrologic processes, including poorly understood dynamics like soil water interactions with the atmosphere. We present a four-year dataset of biweekly water isotope samples from eight fluxes and stores in a headwater catchment at the Hubbard Brook Experimental Forest, New Hampshire, USA. We use Dansgaard's...

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

TS34 is a Type B1 Ca-Al-rich inclusion (CAI) from the Allende CV3 chondrite, consisting of spinel, melilite, Ti-Al-rich clinopyroxene (fassaite) and minor anorthite in an igneous texture. Oxygen and magnesium isotopic compositions were measured by secondary ion mass spectrometry in spots of known chemical composition in all major minerals in TS34. Using the sequence of formation from dynamic crystallization experiments and from chemical compositions of melilite and fassaite, the oxygen isotopic evolution of the CAI melt was established. Oxygen isotopic compositions of the constituent minerals plot along the carbonaceous chondrite anhydrous mineral line. The spinel grains are uniformly 16O-rich (Δ17O = -22.7 ± 1.7‰, 2SD), while the melilite grains are uniformly 16O-poor (Δ17O = -2.8 ± 1.8‰) irrespective of their åkermanite content and thus their relative time of crystallization. The fassaite crystals exhibit growth zoning overprinting poorly-developed sector zoning; they generally grow from Ti-rich to Ti-poor compositions. The fassaite crystals also show continuous variations in Δ17O along the inferred directions of crystal growth, from 16O-poor (Δ17O ∼ -3‰) to 16O-rich (Δ17O ∼ -23‰), covering the full range of oxygen isotopic compositions observed in TS34. The early-crystallized 16O-poor fassaite and the melilite are in oxygen isotope equilibrium and formed simultaneously. The correlation of oxygen isotopic compositions with Ti content in the fassaite imply that the oxygen isotopic composition of the CAI melt evolved from 16O-poor to 16O-rich during fassaite crystallization, presumably due to oxygen isotope exchange with a surrounding 16O-rich nebular gas. Formation of spinel, the liquidus phase in melts of this composition, predates crystallization of all other phases, so its 16O-rich composition is a relic of an earlier stage. Anorthite exhibits oxygen isotopic compositions between Δ17O ∼ -2‰ and -9‰, within the range of those of fassaite, indicating co-crystallization of these two minerals during the earliest to intermediate stage of fassaite growth. The melilite and fassaite yield an 26Al-26Mg mineral isochron with an initial value of (26Al/27Al)0 = (5.003 ± 0.075) × 10-5, corresponding to a relative age of 0.05 ± 0.02 Myr from the canonical Al-Mg age of CAIs. These data demonstrate that both 16O-rich and 16O-poor reservoirs existed in the solar nebula at least ∼0.05 Myr after the birth of the Solar System.

Constraining the dynamic response of subcontinental lithospheric mantle to rifting using Re-Os model ages in the Western Ross Sea, Antarctica

NASA Astrophysics Data System (ADS)

Doherty, C.; Class, C.; Goldstein, S. L.; Shirey, S. B.; Martin, A. P.; Cooper, A. F.; Berg, J. H.; Gamble, J. A.

2012-12-01

In order to understand the dynamic response of the subcontinental lithospheric mantle (SCLM) to rifting, it is important to be able to distinguish the geochemical signatures of SCLM vs. asthenosphere. Recent work demonstrates that unradiogenic Os isotope ratios can indicate old depletion events in the convecting upper mantle (e.g. Rudnick & Walker, 2009), and allow us to make these distinctions. Thus, if SCLM can be traced across a rifted margin, its fate during rifting can be established. The Western Ross Sea provides favorable conditions to test the dynamic response of SCLM to rifting. Re-Os measurements from 8 locations extending from the rift shoulder to 200 km into the rift basin reveal 187Os/188Os ranging from 0.1056 at Foster Crater on the shoulder, to 0.1265 on Ross Island within the rift. While individual sample model ages vary widely throughout the margin, 'aluminochron' ages (Reisberg & Lorand, 1995) reveal a narrower range of lithospheric stabilization ages. Franklin Island and Sulfur Cones show a range of Re-depletion ages (603-1522 Ma and 436-1497 Ma) but aluminochrons yield Paleoproterozoic stabilization ages of 1680 Ma and 1789 Ma, respectively. These ages coincide with U-Pb zircon ages from Transantarctic Mountain (TAM) crustal rocks, in support of SCLM stabilization at the time of crust formation along the central TAM. The Paleoproterozoic stabilization age recorded at Franklin Island is especially significant, since it lies 200km off of the rift shoulder. The similar ages beneath the rift shoulder and within the rift suggests stretched SCLM reaches into the rift and thus precludes replacement by asthenospheric mantle. The persistence of thinned Paleoproterozoic SCLM into the rifted zone in WARS suggests that it represents a 'type I' margin of Huismans and Beaumont (2011), which is characterized by crustal breakup before loss of lithospheric mantle. The Archean Re-depletion age of 3.2 Ga observed on the rift shoulder suggests that cratonic lithosphere extends beneath the TAM. With further analyses we hope to determine if there is lateral flow of cratonic lithosphere into the rift. Huismans, R., Beaumount, C., 2011. Depth-dependent extension, two stage breakup and cratonic underplating at rifted margins. Nature 473, 74-78. Reisberg, L.C., Lorand, J.P., 1995. Longevity of sub-continental mantle lithosphere from osmium isotope systematics in orogenic peridotite massifs. Nature 376, 159-162. Rudnick, R.L., Walker, R.J., 2009. Interpreting ages from Re-Os isotopes in peridotites. Lithos 1125, 1083-1095.

Systematic study of the isotopic dependence of fusion dynamics for neutron- and proton-rich nuclei using a proximity formalism

NASA Astrophysics Data System (ADS)

Ghodsi, O. N.; Gharaei, R.; Lari, F.

2012-08-01

The behaviors of barrier characteristics and fusion cross sections are analyzed by changing neutrons over a wide range of colliding systems. For this purpose, we have extended our previous study [Ghodsi and Gharaei, Eur. Phys. J. AEPJAFV1434-600110.1140/epja/i2012-12021-x 48, 21 (2012), it is devoted to the colliding systems with neutron-rich nuclei] to 125 isotopic systems with the condition of 0.5⩽N/Z⩽1.6 for their compound nuclei. The AW 95, Bass 80, Denisov DP, and Prox. 2010 potentials are used to calculate the nuclear part of the interacting potential. The obtained results show that the trend of barrier heights VB and positions RB as well as nuclear VN and Coulomb VC potentials (at R=RB) as a function of (N/Z-1) quantity are nonlinear (second order) whereas the fusion cross sections follow a linear dependence.

Isotopic niches support the resource breadth hypothesis

USGS Publications Warehouse

Rader, Jonathan A.; Newsome, Seth D.; Sabat, Pablo; Chesser, R. Terry; Dillon, Michael E.; Martinez del Rio, Carlos

2017-01-01

Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges.We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology.We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology.Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies.

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

NASA Astrophysics Data System (ADS)

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

2016-05-01

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

Using stable isotopes of dissolved oxygen for the determination of gas exchange in the Grand River, Ontario, Canada.

PubMed

Jamieson, Terra S; Schiff, Sherry L; Taylor, William D

2013-02-01

Gas exchange can be a key component of the dissolved oxygen (DO) mass balance in aquatic ecosystems. Quantification of gas transfer rates is essential for the estimation of DO production and consumption rates, and determination of assimilation capacities of systems receiving organic inputs. Currently, the accurate determination of gas transfer rate is a topic of debate in DO modeling, and there are a wide variety of approaches that have been proposed in the literature. The current study investigates the use of repeated measures of stable isotopes of O₂ and DO and a dynamic dual mass-balance model to quantify gas transfer coefficients (k) in the Grand River, Ontario, Canada. Measurements were conducted over a longitudinal gradient that reflected watershed changes from agricultural to urban. Values of k in the Grand River ranged from 3.6 to 8.6 day⁻¹, over discharges ranging from 5.6 to 22.4 m³ s⁻¹, with one high-flow event of 73.1 m³ s⁻¹. The k values were relatively constant over the range of discharge conditions studied. The range in discharge observed in this study is generally representative of non-storm and summer low-flow events; a greater range in k might be observed under a wider range of hydrologic conditions. Overall, k values obtained with the dual model for the Grand River were found to be lower than predicted by the traditional approaches evaluated, highlighting the importance of determining site-specific values of k. The dual mass balance approach provides a more constrained estimate of k than using DO only, and is applicable to large rivers where other approaches would be difficult to use. The addition of an isotopic mass balance provides for a corroboration of the input parameter estimates between the two balances. Constraining the range of potential input values allows for a direct estimate of k in large, productive systems where other k-estimation approaches may be uncertain or logistically infeasible. Copyright © 2012 Elsevier Ltd. All rights reserved.

Isotopy of the hydrosphere

NASA Astrophysics Data System (ADS)

Ferronskii, V. I.; Poliakov, V. A.

This book is concerned with the natural relations regarding the distribution of the stable isotopes of hydrogen and oxygen in the hydrosphere, taking into account the most important problems with respect to the dynamics and the origin of waters. The solution of these problems on an isotopic basis is considered. The physicochemical principles of isotope separation are discussed along with the isotopic composition of atmospheric moisture, the isotopic composition of surface continental waters, the hydrogen and oxygen isotopic composition of minerals of magmatic and metamorphic rocks and fluid inclusions, the isotopic composition of groundwaters of modern volcanic regions, and the origin of the earth's hydrosphere in the light of isotopic, cosmochemical, and theoretical studies. Attention is also given to the separation of hydrogen and oxygen isotopes of waters in the underground cycle, the isotopic composition of the deep-formation waters of sedimentary basins, the relationship between surface and ground waters, and the groundwater residence time in an aquifer.

Palaeoclimate signal recorded by stable isotopes in cave ice: a modeling approach

NASA Astrophysics Data System (ADS)

Perşoiu, A.; Bojar, A.-V.

2012-04-01

Ice accumulations in caves preserve a large variety of geochemical information as candidate proxies for both past climate and environmental changes, one of the most significant being the stable isotopic composition of the ice. A series of recent studies have targeted oxygen and hydrogen stable isotopes in cave ice as proxies for past air temperatures, but the results are far from being as straightforward as they are in high latitude and altitude glaciers and ice caps. The main problems emerging from these studies are related to the mechanisms of cave ice formation (i.e., freezing of water) and post-formation processes (melting and refreezing), which both alter the original isotopic signal in water. Different methods have been put forward to solve these issues and a fair understanding of the present-day link between stable isotopes in precipitation and cave ice exists now. However, the main issues still lays unsolved: 1) is it possible to extend this link to older ice and thus reconstruct past changes in air temperature?; 2) to what extent are ice dynamics processes modifying the original climatic signal and 3) what is the best method to be used in extracting a climatic signal from stable isotopes in cave ice? To respond to these questions, we have conducted a modeling experiment, in which a theoretical cave ice stable isotope record was constructed using present-day observations on stable isotope behavior in cave ice and ice dynamics, and different methods (presently used for both polar and cave glaciers), were used to reconstruct the original, known, isotopic values. Our results show that it is possible to remove the effects of ice melting and refreezing on stable isotope composition of cave ice, and thus reconstruct the original isotopic signal, and further the climatic one.

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.

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.

Novel stable isotope laser spectrometry elucidates changing mechanisms of CH4 production and consumption across a climate change sequence in an arctic wetland

NASA Astrophysics Data System (ADS)

McCalley, C. K.; Wehr, R.; Crill, P. M.; Chanton, J.; Hodgkins, S. B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Rich, V.; Tyson, G.; Mondav, R.; Frolking, S.; Li, C.; Saleska, S. R.

2011-12-01

Methane flux from high latitude wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change, with expected increases in emissions as permafrost thaws. Gaps in our understanding of the mechanisms driving changing CH4 production and consumption dynamics under permafrost thaw, however, limit our ability to predict the magnitude of this response under future climate conditions. To address these gaps, we quantified the isotopic composition of carbon gas fluxes (δ13C of CH4 and CO2) from a high latitude (68° N) wetland in Sweden (Stordalen Mire) to partition net CH4 emissions into its component parts, methanogenesis (including both acetoclastic, and CO2-reductive pathways) and methanotrophy (which consumes CH4 primarily via aerobic metabolism). We used newly developed quantum cascade laser technology, linked to automated chambers, to quantify isotopes at high frequency. Our measurements across a permafrost thaw gradient, going from permafrost-dominated, well-drained palsas to intermediate permafrost sites dominated by Sphagnum spp. to wet sites with no underlying permafrost, dominated by Eriophorum angustifolium, show both large increases in productivity and CH4 emissions as well as shifts in the CH4 production pathway. Across this permafrost thaw gradient the isotopic composition of CH4 becomes 13C enriched, due to increased acetoclastic CH4 production. While the palsa sites have no detectable CH4 emissions, fluxes in the Sphagnum site have an average isotopic composition of -79%, a value indicative of CH4 production dominated by CO2 reduction, in contrast the isotopic composition of CH4 produced in the Eriophorum sites ranged from -71 to -57%, showing increased CH4 production via the acetate pathway. We also observed an increase in acetoclastic methanogenesis as the growing season progressed. Together, these initial results suggest that thaw induced changes in hydrology and plant community composition increase peat lability, stimulating acetate fermentation and yielding increased methane emissions. We conclude that the biological controls on metabolic pathways of methanogenesis, though poorly represented in most ecosystem models, may nonetheless be important, in interaction with permafrost thaw dynamics, in determining future CH4 emissions under changing climate.

Manned space flight nuclear system safety. Volume 5: Nuclear System safety guidelines. Part 1: Space base nuclear safety

NASA Technical Reports Server (NTRS)

1972-01-01

The design and operations guidelines and requirements developed in the study of space base nuclear system safety are presented. Guidelines and requirements are presented for the space base subsystems, nuclear hardware (reactor, isotope sources, dynamic generator equipment), experiments, interfacing vehicles, ground support systems, range safety and facilities. Cross indices and references are provided which relate guidelines to each other, and to substantiating data in other volumes. The guidelines are intended for the implementation of nuclear safety related design and operational considerations in future space programs.

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.

Intraspecific carbon and nitrogen isotopic variability in foxtail millet (Setaria italica).

PubMed

Lightfoot, Emma; Przelomska, Natalia; Craven, Martha; O Connell, Tamsin C; He, Lu; Hunt, Harriet V; Jones, Martin K

2016-07-15

Isotopic palaeodietary studies generally focus on bone collagen from human and/or animal remains. While plant remains are rarely analysed, it is known that plant isotope values can vary as a result of numerous factors, including soil conditions, the environment and type of plant. The millets were important food crops in prehistoric Eurasia, yet little is known about the isotopic differences within millet species. Here we compare the stable isotope ratios within and between Setaria italica plants grown in a controlled environment chamber. Using homogenised samples, we compare carbon isotope ratios of leaves and grains, and nitrogen isotope ratios of grains, from 29 accessions of Setaria italica. We find significant isotopic variability within single leaves and panicles, and between leaves and panicles within the same plant, which must be considered when undertaking plant isotope studies. We find that the leaves and grains from the different accessions have a ca 2‰ range in δ(13) C values, while the nitrogen isotope values in the grains have a ca 6‰ range. We also find an average offset of 0.9‰ between leaves and grains in their δ(13) C values. The variation found is large enough to have archaeological implications and within- and between-plant isotope variability should be considered in isotope studies. The range in δ(15) N values is particularly significant as it is larger than the typical values quoted for a trophic level enrichment, and as such may lead to erroneous interpretations of the amount of animal protein in human or animal diets. It is therefore necessary to account for the variability in plant stable isotope values during palaeodietary reconstructions. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

High-resolution passive sampling of dissolved methane in the water column of lakes in Greenland

NASA Astrophysics Data System (ADS)

Goldman, A. E.; Cadieux, S. B.; White, J. R.; Pratt, L. M.

2013-12-01

Arctic lakes are important participants in the global carbon cycle, releasing methane in a warming climate and contributing to a positive feedback to climate change. In order to yield detailed methane budgets and understand the implications of warming on methane dynamics, high-resolution profiles revealing methane behavior within the water column need to be obtained. Single day sampling using disruptive techniques has the potential to result in biases. In order to obtain high-resolution, undisturbed profiles of methane concentration and isotopic composition, this study evaluates a passive sampling method over a multi-day equilibration period. Selected for this study were two small lakes (<1km2) within a narrow valley stretching between Russells Glacier and Søndre Strømfjord in southwestern Greenland, which are part of an ongoing study of a series of seven lakes. Commercially available, 150 mL, polyethylene Passive Diffusion Bags (PDB's) were deployed in July 2013 for five days at 0.5-meter depth intervals. PDB samples were compared to samples collected with a submersible, electric pump taken immediately before PBD deployment. Preliminary CH4 concentrations and carbon isotopes for one lake were obtained in the field using a Los Gatos Research Methane Carbon Isotope Analyzer. PDB sampling and pump sampling resulted in statistically similar concentrations (R2=0.89), ranging from 0.85 to 135 uM from PDB and 0.74 to 143 uM from pump sampling. In anoxic waters of the lake, where concentrations were high enough to yield robust isotopic results on the LGR MCIA, δ13C were also similar between the two methods, yielding -73‰ from PDB and -74‰ from pump sampling. Further investigation will produce results for a second lake and methane carbon and hydrogen isotopic composition for both lakes. Preliminary results for this passive sampling method are promising. We envision the use of this technique in future studies of dissolved methane and expect that it will provide a more finely resolved vertical profile, allowing for a more complete understanding of lacustrine methane dynamics.

Optimizing isotope substitution in graphene for thermal conductivity minimization by genetic algorithm driven molecular simulations

NASA Astrophysics Data System (ADS)

Davies, Michael; Ganapathysubramanian, Baskar; Balasubramanian, Ganesh

2017-03-01

We present results from a computational framework integrating genetic algorithm and molecular dynamics simulations to systematically design isotope engineered graphene structures for reduced thermal conductivity. In addition to the effect of mass disorder, our results reveal the importance of atomic distribution on thermal conductivity for the same isotopic concentration. Distinct groups of isotope-substituted graphene sheets are identified based on the atomic composition and distribution. Our results show that in structures with equiatomic compositions, the enhanced scattering by lattice vibrations results in lower thermal conductivities due to the absence of isotopic clusters.

Analysis of dissolved organic carbon concentration and 13C isotopic signature by TOC-IRMS - assessment of analytical performance

NASA Astrophysics Data System (ADS)

Kirkels, Frédérique; Cerli, Chiara; Federherr, Eugen; Kalbitz, Karsten

2013-04-01

Stable carbon isotopes provide a powerful tool to assess carbon pools and their dynamics. Dissolved organic carbon (DOC) has been recognized to play an important role in ecosystem functioning and carbon cycling and has therefore gained increased research interest. However, direct measurement of 13C isotopic signature of carbon in the dissolved phase is technically challenging particularly using high temperature combustion. Until recently, mainly custom-made systems existed which were modified for coupling of TOC instruments with IRMS for simultaneous assessment of C content and isotopic signature. The variety of coupled systems showed differences in their analytical performances. For analysis of DOC high temperature combustion is recognized as best performing method, owing to its high efficiency of conversion to CO2 also for highly refractory components (e.g. humic, fulvic acids) present in DOC and soil extracts. Therefore, we tested high temperature combustion TOC coupled to IRMS (developed by Elementar Group) for bulk measurements of DOC concentration and 13C signature. The instruments are coupled via an Interface to exchange the carrier gas from O2 to He and to concentrate the derived CO2 for the isotope measurement. Analytical performance of the system was assessed for a variety of organic compounds characterized by different stability and complexity, including humic acid and DOM. We tested injection volumes between 0.2-3 ml, thereby enabling measurement of broad concentration ranges. With an injection volume of 0.5 ml (n=3, preceded by 1 discarded injection), DOC and 13C signatures for concentrations between 5-150 mg C/L were analyzed with high precision (standard deviation (SD) predominantly <0.1‰), good accuracy and linearity (overall SD <0.9‰). For the same settings, slightly higher variation in precision was observed among the lower concentration range and depending upon specific system conditions. Differences in 13C signatures of about 50‰ among samples did not affect the precision of the analysis of natural abundance and labeled samples. Natural DOM, derived from different soils and assessed at various concentrations, was measured with similar good analytical performance, and also tested for the effect of freezing and re-dissolving. We found good performance of TOC-IRMS in comparison with other systems capable of determining C concentration and isotopic signatures. We recognize the advantages of this system providing: - High sample throughput, short measurement time (15 minutes), flexible sample volume - Easy maintenance, handling, rapid sample preparation (no pretreatment) This preliminary assessment highlights wide-ranging opportunities for further research on concentrations and isotopic signatures by TOC-IRMS to elucidate the role of dissolved carbon in terrestrial and aquatic systems.

Speleothem records of acid sulphate deposition and organic carbon mobilisation

NASA Astrophysics Data System (ADS)

Wynn, Peter; Fairchild, Ian; Bourdin, Clement; Baldini, James; Muller, Wolfgang; Hartland, Adam; Bartlett, Rebecca

2017-04-01

Dramatic increases in measured surface water DOC in recent decades have been variously attributed to either temperature rise, or destabilisation of long-term soil carbon pools following sulphur peak emissions status. However, whilst both drivers of DOC dynamics are plausible, they remain difficult to test due to the restricted nature of the available records of riverine DOC flux (1978 to present), and the limited availability of SO2 emissions inventory data at the regional scale. Speleothems offer long term records of both sulphur and carbon. New techniques to extract sulphur concentrations and isotopes from speleothem calcite have enabled archives of pollution history and environmental acidification to be reconstructed. Due to the large dynamic range in sulphur isotopic values from end member sources (marine aerosol +21 ‰ to continental biogenic emissions -30 ‰) and limited environmental fractionation under oxidising conditions, sulphur isotopes form an ideal tracer of industrial pollution and environmental acidification in the palaeo-record. We couple this acidification history to the carbon record, using organic matter fluorescence and trace metals. Trace metal ratios and abundance can be used to infer the type and size of organic ligand and are therefore sensitive to changes in temperature as a driver of organic carbon processing and biodegradation. This allows fluorescent properties and ratios of trace metals in speleothem carbonate to be used to represent both the flux of organic carbon into the cave as well as the degradation pathway. Here we present some of the first results of this work, exploring sulphur acidification as a mechanistic control on carbon solubility and export throughout the twentieth century.

Environmental controls on sulfur isotopic composition of sulfide minerals in seep carbonates from the South China Sea

NASA Astrophysics Data System (ADS)

Gong, S.; Li, N.; Liang, Q.; Chen, D.; Feng, D.

2017-12-01

Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34Spy value of authigenic sulfide has been used to trace the AOM-related processes. However, the detail mechanism for this is unknown. We proposed the δ34Spy characteristics result from high sulfate reduction rate and its competition with sulfate supply rate. To test this hypothesis, we investigated Mo content, Sr/Ca and Mg/Ca ratios, pyrite content, and its sulfur isotopic compositions in methane-derived carbonates from Site F and Haima in northern South China Sea. Calcite and aragonite were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34Spy values compared to calcites. The Mo content and pyrite have good linear correlations in both aragonites and calcites, and aragonites have more positive slope than calcites. This indicates that there is more Mo available from seawater during the aragonite precipitation. The data suggest that the low δ34Spy values are formed at higher supply rate of sulfate under relatively open system, and high δ34Spy values result from a deep sulfate methane transition zone where dissolve sulfate near to complete exhausted via AOM. The combination of a detailed elemental study of authigenic carbonate with sulfur isotopes of sulfide minerals in carbonates are promising tools for reconstructing the dynamics of seep intensities in modern and, potentially, geological record.

Li diffusion and the effect of local structure on Li mobility in Li2O-SiO2 glasses.

PubMed

Bauer, Ute; Welsch, Anna-Maria; Behrens, Harald; Rahn, Johanna; Schmidt, Harald; Horn, Ingo

2013-12-05

Aimed to improve the understanding of lithium migration mechanisms in ion conductors, this study focuses on Li dynamics in binary Li silicate glasses. Isotope exchange experiments and conductivity measurements were carried out to determine self-diffusion coefficients and activation energies for Li migration in Li2Si3O7 and Li2Si6O13 glasses. Samples of identical composition but different isotope content were combined for diffusion experiments in couples or triples. Diffusion profiles developed between 511 and 664 K were analyzed by femtosecond laser ablation combined with multiple collector inductively coupled plasma mass spectrometry (fs LA-MC-ICP-MS) and secondary ion mass spectrometry (SIMS). Analyses of diffusion profiles and comparison of diffusion data reveal that the isotope effect of lithium diffusion in silicate glasses is rather small, consistent with classical diffusion behavior. Ionic conductivity of glasses was measured between 312 and 675 K. The experimentally obtained self-diffusion coefficient, D(IE), and ionic diffusion coefficient, D(σ), derived from specific DC conductivity provided information about correlation effects during Li diffusion. The D(IE)/D(σ) is higher for the trisilicate (0.27 ± 0.05) than that for the hexasilicate (0.17 ± 0.02), implying that increasing silica content reduces the efficiency of Li jumps in terms of long-range movement. This trend can be rationalized by structural concepts based on nuclear magnetic resonance (NMR) and Raman spectroscopy as well as molecular dynamic simulations, that is, lithium is percolating in low-dimensional, alkali-rich regions separated by a silica-rich matrix.

Fingerprints of carbon, nitrogen, and silicon isotopes in small interstellar SiC grains from the Murchison meteorite

NASA Technical Reports Server (NTRS)

Hoppe, Peter; Geiss, Johannes; Buehler, Fritz; Neuenschwander, Juerg; Amari, Sachiko; Lewis, Roy S.

1993-01-01

We report ion microprobe determinations of the carbon, nitrogen, and silicon isotopic compositions of small SiC grains from the Murchison CM2 chondrite. Analyses were made on samples containing variable numbers of grains and on 14 individual grains. In some cases the multiple-grain sample compositions were probably dominated by only one or two grains. Total ranges observed are given. Only a few grains show values near the range limits. Both the total ranges of carbon and nitrogen isotopic compositions, and even the narrower ranges typical for the majority of the grains, are similar to those observed for larger SiC grains. Two rare components appear to be present in the smaller-size fraction, one characterized by C-12/C-13 about 12-16 and the other by very heavy nitrogen. The carbon and nitrogen isotopic compositions qualitatively may reflect hydrostatic H-burning via the CNO cycle and He-burning in red giants, as well as explosive H-burning in novae. The silicon isotopic compositions of most grains qualitatively show what is the signature of He-burning. The silicon isotopic composition of one grain, however, suggests a different process.

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.

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.

Temporal geochemical variations in lavas from Kīlauea's Pu`u `Ō`ō eruption (1983-2010): Cyclic variations from melting of source heterogeneities

NASA Astrophysics Data System (ADS)

Greene, Andrew R.; Garcia, Michael O.; Pietruszka, Aaron J.; Weis, Dominique; Marske, Jared P.; Vollinger, Michael J.; Eiler, John

2013-11-01

Geochemical time series analysis of lavas from Kīlauea's ongoing Pu`u `Ō`ō eruption chronicle mantle and crustal processes during a single, prolonged (1983 to present) magmatic event, which has shown nearly two-fold variation in lava effusion rates. Here we present an update of our ongoing monitoring of the geochemical variations of Pu`u `Ō`ō lavas for the entire eruption through 2010. Oxygen isotope measurements on Pu`u `Ō`ō lavas show a remarkable range (δ18O values of 4.6-5.6‰), which are interpreted to reflect moderate levels of oxygen isotope exchange with or crustal contamination by hydrothermally altered Kīlauea lavas, probably in the shallow reservoir under the Pu`u `Ō`ō vent. This process has not measurably affected ratios of radiogenic isotope or incompatible trace elements, which are thought to vary due to mantle-derived changes in the composition of the parental magma delivered to the volcano. High-precision Pb and Sr isotopic measurements were performed on lavas erupted at ˜6 month intervals since 1983 to provide insights about melting dynamics and the compositional structure of the Hawaiian plume. The new results show systematic variations of Pb and Sr isotope ratios that continued the long-term compositional trend for Kīlauea until ˜1990. Afterward, Pb isotope ratios show two cycles with ˜10 year periods, whereas the Sr isotope ratios continued to increase until ˜2003 and then shifted toward slightly less radiogenic values. The short-term periodicity of Pb isotope ratios may reflect melt extraction from mantle with a fine-scale pattern of repeating source heterogeneities or strands, which are about 1-3 km in diameter. Over the last 30 years, Pu`u `Ō`ō lavas show 15% and 25% of the known isotopic variation for Kīlauea and Mauna Kea, respectively. This observation illustrates that the dominant time scale of mantle-derived compositional variation for Hawaiian lavas is years to decades.

Comparative feeding ecology of bull sharks (Carcharhinus leucas) in the coastal waters of the southwest Indian Ocean inferred from stable isotope analysis.

PubMed

Daly, Ryan; Froneman, Pierre W; Smale, Malcolm J

2013-01-01

As apex predators, sharks play an important role shaping their respective marine communities through predation and associated risk effects. Understanding the predatory dynamics of sharks within communities is, therefore, necessary to establish effective ecologically based conservation strategies. We employed non-lethal sampling methods to investigate the feeding ecology of bull sharks (Carcharhinus leucas) using stable isotope analysis within a subtropical marine community in the southwest Indian Ocean. The main objectives of this study were to investigate and compare the predatory role that sub-adult and adult bull sharks play within a top predatory teleost fish community. Bull sharks had significantly broader niche widths compared to top predatory teleost assemblages with a wide and relatively enriched range of δ(13)C values relative to the local marine community. This suggests that bull sharks forage from a more diverse range of δ(13)C sources over a wider geographical range than the predatory teleost community. Adult bull sharks appeared to exhibit a shift towards consistently higher trophic level prey from an expanded foraging range compared to sub-adults, possibly due to increased mobility linked with size. Although predatory teleost fish are also capable of substantial migrations, bull sharks may have the ability to exploit a more diverse range of habitats and appeared to prey on a wider diversity of larger prey. This suggests that bull sharks play an important predatory role within their respective marine communities and adult sharks in particular may shape and link ecological processes of a variety of marine communities over a broad range.

Comparative Feeding Ecology of Bull Sharks (Carcharhinus leucas) in the Coastal Waters of the Southwest Indian Ocean Inferred from Stable Isotope Analysis

PubMed Central

Daly, Ryan; Froneman, Pierre W.; Smale, Malcolm J.

2013-01-01

As apex predators, sharks play an important role shaping their respective marine communities through predation and associated risk effects. Understanding the predatory dynamics of sharks within communities is, therefore, necessary to establish effective ecologically based conservation strategies. We employed non-lethal sampling methods to investigate the feeding ecology of bull sharks (Carcharhinus leucas) using stable isotope analysis within a subtropical marine community in the southwest Indian Ocean. The main objectives of this study were to investigate and compare the predatory role that sub-adult and adult bull sharks play within a top predatory teleost fish community. Bull sharks had significantly broader niche widths compared to top predatory teleost assemblages with a wide and relatively enriched range of δ13C values relative to the local marine community. This suggests that bull sharks forage from a more diverse range of δ13C sources over a wider geographical range than the predatory teleost community. Adult bull sharks appeared to exhibit a shift towards consistently higher trophic level prey from an expanded foraging range compared to sub-adults, possibly due to increased mobility linked with size. Although predatory teleost fish are also capable of substantial migrations, bull sharks may have the ability to exploit a more diverse range of habitats and appeared to prey on a wider diversity of larger prey. This suggests that bull sharks play an important predatory role within their respective marine communities and adult sharks in particular may shape and link ecological processes of a variety of marine communities over a broad range. PMID:24205168

Scaling Effects of Riparian Peatlands on Stable Isotopes in Runoff and DOC Mobilization

NASA Astrophysics Data System (ADS)

Tetzlaff, D.; Tunaley, C.; Soulsby, C.

2016-12-01

We combined 13 months of daily isotope measurements in stream water with daily DOC and 15 minute FDOM (fluorescent component of dissolved organic matter) data at three nested scales to identify how riparian peatlands generate runoff and influence DOC dynamics in streams. We investigated how runoff generation processes in a small, riparian peatland dominated headwater catchment (0.65 km2) propagate to larger scales (3.2 km2 and 31 km2) with decreasing percentage of riparian peatland coverage. Isotope damping was most pronounced in the 0.65 km2 headwater catchment due to high water storage in the organic soils which encourage tracer mixing. At the largest scale, stream flow and water isotope dynamics showed a more flashy response. The isotopic difference between the sites was most pronounced in the summer months when stream water signatures were enriched. During the winter months, the inter-site difference reduced. The isotopes also revealed evaporative fractionation in the peatland dominated catchment, in particular during summer low flows, which implied high hydrological connectivity in form of constant seepage from the peatlands sustaining high baseflows at the headwater scale. This connectivity resulted in high DOC concentrations at the peatland site during baseflow ( 5 mg l-1). In contrast, at the larger scales, DOC was minimal during low flows ( 2 mg l-1) due to increased groundwater influence and the disconnection between DOC sources and the stream. High frequency data also revealed diel variability during low flows. Insights into event dynamics through the analysis of hysteresis loops showed slight dilution on the rising limb, the strong influence of dry antecedent conditions and a quick recovery between events at the riparian peatland site. Again, these dynamics are driven by the tight coupling and high connectivity of the landscape to the stream. At larger scales, the disconnection between the landscape units increase and the variable connectivity controls runoff generation and DOC dynamics. The results presented here suggest that the processes occurring in riparian peatlands in headwater catchments are less evident at larger scales which may have implications for the larger scale impact of peatland restoration projects.

Simulating dynamics of δ13C of CO2 in the planetary boundary layer over a boreal forest region: covariation between surface fluxes and atmospheric mixing

NASA Astrophysics Data System (ADS)

Chen, Baozhang; Chen, Jing M.; Tans, Pieter P.; Huang, Lin

2006-11-01

Stable isotopes of CO2 contain unique information on the biological and physical processes that exchange CO2 between terrestrial ecosystems and the atmosphere. Ecosystem exchange of carbon isotopes with the atmosphere is correlated diurnally and seasonally with the planetary boundary layer (PBL) dynamics. The strength of this kind of covariation affects the vertical gradient of δ13C and thus the global δ13C distribution pattern. We need to understand the various processes involved in transport/diffusion of carbon isotope ratio in the PBL and between the PBL and the biosphere and the troposphere. In this study, we employ a one-dimensional vertical diffusion/transport atmospheric model (VDS), coupled to an ecosystem isotope model (BEPS-EASS) to simulate dynamics of 13CO2 in the PBL over a boreal forest region in the vicinity of the Fraserdale (FRD) tower (49°52'29.9''N, 81°34'12.3''W) in northern Ontario, Canada. The data from intensive campaigns during the growing season in 1999 at this site are used for model validation in the surface layer. The model performance, overall, is satisfactory in simulating the measured data over the whole course of the growing season. We examine the interaction of the biosphere and the atmosphere through the PBL with respect to δ13C on diurnal and seasonal scales. The simulated annual mean vertical gradient of δ13C in the PBL in the vicinity of the FRD tower was about 0.25‰ in 1999. The δ13C vertical gradient exhibited strong diurnal (29%) and seasonal (71%) variations that do not exactly mimic those of CO2. Most of the vertical gradient (96.5% +/-) resulted from covariation between ecosystem exchange of carbon isotopes and the PBL dynamics, while the rest (3.5%+/-) was contributed by isotopic disequilibrium between respiration and photosynthesis. This disequilibrium effect on δ13C of CO2 dynamics in PBL, moreover, was confined to the near surface layers (less than 350 m).

Scaling effects of riparian peatlands on stable isotopes in runoff and DOC mobilisation

NASA Astrophysics Data System (ADS)

Tunaley, C.; Tetzlaff, D.; Soulsby, C.

2017-06-01

We combined 13 months of daily isotope measurements in stream water with daily DOC and 15 min FDOM (fluorescent component of dissolved organic matter) data at three nested scales to identify how riparian peatlands generate runoff and influence DOC dynamics in streams. We investigated how runoff generation processes in a small, riparian peatland-dominated headwater catchment (0.65 km2) propagate to larger scales (3.2 km2 and 31 km2) with decreasing percentage of riparian peatland coverage. Isotope damping was most pronounced in the 0.65 km2 headwater catchment due to high water storage in the organic soils encouraging tracer mixing. At the largest scale, stream flow and water isotope dynamics showed a more flashy response. The isotopic difference between the sites was most pronounced in the summer months when stream water signatures were enriched. During the winter months, the inter-site difference reduced. The isotopes also revealed evaporative fractionation in the peatland dominated catchment, in particular during summer low flows, which implied high hydrological connectivity in the form of constant seepage from the peatlands sustaining high baseflows at the headwater scale. This connectivity resulted in high DOC concentrations at the peatland site during baseflow (∼5 mg l-1). In contrast, at the larger scales, DOC was minimal during low flows (∼2 mg l-1) due to increased groundwater influence and the disconnection between DOC sources and the stream. High frequency data also revealed diel variability during low flows. Insights into event dynamics through the analysis of hysteresis loops showed slight dilution on the rising limb, the strong influence of dry antecedent conditions and a quick recovery between events at the riparian peatland site. Again, these dynamics are driven by the tight coupling and high connectivity of the landscape to the stream. At larger scales, the disconnection between the landscape units increases and the variable connectivity controls runoff generation and DOC dynamics. The results presented here suggest that the processes occurring in riparian peatlands in headwater catchments are less evident at larger scales which may have implications for the larger scale impact of peatland restoration projects.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Evaluation of the plasma hydrogen isotope content by residual gas analysis at JET and AUG

NASA Astrophysics Data System (ADS)

Drenik, A.; Alegre, D.; Brezinsek, S.; De Castro, A.; Kruezi, U.; Oberkofler, M.; Panjan, M.; Primc, G.; Reichbauer, T.; Resnik, M.; Rohde, V.; Seibt, M.; Schneider, P. A.; Wauters, T.; Zaplotnik, R.; ASDEX-Upgrade, the; EUROfusion MST1 Teams; contributors, JET

2017-12-01

The isotope content of the plasma reflects on the dynamics of isotope changeover experiments, efficiency of wall conditioning and the performance of a fusion device in the active phase of operation. The assessment of the isotope ratio of hydrogen and methane molecules is used as a novel method of assessing the plasma isotope ratios at JET and ASDEX-Upgrade (AUG). The isotope ratios of both molecules in general shows similar trends as the isotope ratio detected by other diagnostics. At JET, the absolute values of RGA signals are in relatively good agreement with each other and with spectroscopy data, while at AUG the deviation from neutral particle analyser data are larger, and the results show a consistent spatial distribution of the isotope ratio. It is further shown that the isotope ratio of the hydrogen molecule can be used to study the degree of dissociation of the injected gas during changeover experiments.

Isotopic niches support the resource breadth hypothesis.

PubMed

Rader, Jonathan A; Newsome, Seth D; Sabat, Pablo; Chesser, R Terry; Dillon, Michael E; Martínez Del Rio, Carlos

2017-03-01

Because a broad spectrum of resource use allows species to persist in a wide range of habitat types, and thus permits them to occupy large geographical areas, and because broadly distributed species have access to more diverse resource bases, the resource breadth hypothesis posits that the diversity of resources used by organisms should be positively related with the extent of their geographic ranges. We investigated isotopic niche width in a small radiation of South American birds in the genus Cinclodes. We analysed feathers of 12 species of Cinclodes to test the isotopic version of the resource breadth hypothesis and to examine the correlation between isotopic niche breadth and morphology. We found a positive correlation between the widths of hydrogen and oxygen isotopic niches (which estimate breadth of elevational range) and widths of the carbon and nitrogen isotopic niches (which estimates the diversity of resources consumed, and hence of habitats used). We also found a positive correlation between broad isotopic niches and wing morphology. Our study not only supports the resource breadth hypothesis but it also highlights the usefulness of stable isotope analyses as tools in the exploration of ecological niches. It is an example of a macroecological application of stable isotopes. It also illustrates the importance of scientific collections in ecological studies. © 2016 The Authors. Journal of Animal Ecology © 2016 British Ecological Society.

Tap water isotope ratios reflect urban water system structure and dynamics across a semiarid metropolitan area

NASA Astrophysics Data System (ADS)

Jameel, Yusuf; Brewer, Simon; Good, Stephen P.; Tipple, Brett J.; Ehleringer, James R.; Bowen, Gabriel J.

2016-08-01

Water extraction for anthropogenic use has become a major flux in the hydrological cycle. With increasing demand for water and challenges supplying it in the face of climate change, there is a pressing need to better understand connections between human populations, climate, water extraction, water use, and its impacts. To understand these connections, we collected and analyzed stable isotopic ratios of more than 800 urban tap water samples in a series of semiannual water surveys (spring and fall, 2013-2015) across the Salt Lake Valley (SLV) of northern Utah. Consistent with previous work, we found that mean tap water had a lower 2H and 18O concentration than local precipitation, highlighting the importance of nearby montane winter precipitation as source water for the region. However, we observed strong and structured spatiotemporal variation in tap water isotopic compositions across the region which we attribute to complex distribution systems, varying water management practices and multiple sources used across the valley. Water from different sources was not used uniformly throughout the area and we identified significant correlation between water source and demographic parameters including population and income. Isotopic mass balance indicated significant interannual and intra-annual variability in water losses within the distribution network due to evaporation from surface water resources supplying the SLV. Our results demonstrate the effectiveness of isotopes as an indicator of water management strategies and climate impacts within regional urban water systems, with potential utility for monitoring, regulation, forensic, and a range of water resource research.

A Pleistocene palaeovegetation record from plant wax biomarkers from the Nachukui Formation, West Turkana, Kenya

PubMed Central

Uno, Kevin T.; Polissar, Pratigya J.; Kahle, Emma; Feibel, Craig; Harmand, Sonia; Roche, Hélène; deMenocal, Peter B.

2016-01-01

Reconstructing vegetation at hominin fossil sites provides us critical information about hominin palaeoenvironments and the potential role of climate in their evolution. Here we reconstruct vegetation from carbon isotopes of plant wax biomarkers in sediments of the Nachukui Formation in the Turkana Basin. Plant wax biomarkers were extracted from samples from a wide range of lithologies that include fluvial–lacustrine sediments and palaeosols, and therefore provide a record of vegetation from diverse depositional environments. Carbon isotope ratios from biomarkers indicate a highly dynamic vegetation structure (ca 5–100% C4 vegetation) from 2.3 to 1.7 Ma, with an overall shift towards more C4 vegetation on the landscape after about 2.1 Ma. The biomarker isotope data indicate ca 25–30% more C4 vegetation on the landscape than carbon isotope data of pedogenic carbonates from the same sequence. Our data show that the environments of early Paranthropus and Homo in this part of the Turkana Basin were primarily mixed C3–C4 to C4-dominated ecosystems. The proportion of C4-based foods in the diet of Paranthropus increases through time, broadly paralleling the increase in C4 vegetation on the landscape, whereas the diet of Homo remains unchanged. Biomarker isotope data associated with the Kokiselei archaeological site complex, which includes the site where the oldest Acheulean stone tools to date were recovered, indicate 61–97% C4 vegetation on the landscape. This article is part of the themed issue ‘Major transitions in human evolution’. PMID:27298466

Coupled extremely light Ca and Fe isotopes in peridotites

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

You are not always what we think you eat: selective assimilation across multiple whole-stream isotopic tracer studies

Treesearch

W. K. Dodds; S. M. Collins; S. K. Hamilton; J. L. Tank; S. Johnson; J. R. Webster; K. S. Simon; M. R. Whiles; H. M. Rantala; W. H. McDowell; S. D. Peterson; T. Riis; C. L. Crenshaw; S. A. Thomas; P. B. Kristensen; B. M. Cheever; A. S. Flecker; N. A. Griffiths; T. Crowl; E. J. Rosi-Marshall; R. El-Sabaawi; E. Martí

2014-01-01

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N...

Food-web dynamics and isotopic niches in deep-sea communities residing in a submarine canyon and on the adjacent open slopes

USGS Publications Warehouse

Demopoulos, Amanda W.J.; McClain-Counts, Jennifer; Ross, Steve W.; Brooke, Sandra; Mienis, Furu

2017-01-01

Examination of food webs and trophic niches provide insights into organisms' functional ecology, yet few studies have examined trophodynamics within submarine canyons, where the interaction of canyon morphology and oceanography influences habitat provision and food deposition. Using stable isotope analysis and Bayesian ellipses, we documented deep-sea food-web structure and trophic niches in Baltimore Canyon and the adjacent open slopes in the US Mid-Atlantic Region. Results revealed isotopically diverse feeding groups, comprising approximately 5 trophic levels. Regression analysis indicated that consumer isotope data are structured by habitat (canyon vs. slope), feeding group, and depth. Benthic feeders were enriched in 13C and 15N relative to suspension feeders, consistent with consuming older, more refractory organic matter. In contrast, canyon suspension feeders had the largest and more distinct isotopic niche, indicating they consume an isotopically discrete food source, possibly fresher organic material. The wider isotopic niche observed for canyon consumers indicated the presence of feeding specialists and generalists. High dispersion in δ13C values for canyon consumers suggests that the isotopic composition of particulate organic matter changes, which is linked to depositional dynamics, resulting in discrete zones of organic matter accumulation or resuspension. Heterogeneity in habitat and food availability likely enhances trophic diversity in canyons. Given their abundance in the world's oceans, our results from Baltimore Canyon suggest that submarine canyons may represent important havens for trophic diversity.

Combinatorial modification of human histone H4 quantitated by two-dimensional liquid chromatography coupled with top down mass spectrometry.

PubMed

Pesavento, James J; Bullock, Courtney R; LeDuc, Richard D; Mizzen, Craig A; Kelleher, Neil L

2008-05-30

Quantitative proteomics has focused heavily on correlating protein abundances, ratios, and dynamics by developing methods that are protein expression-centric (e.g. isotope coded affinity tag, isobaric tag for relative and absolute quantification, etc.). These methods effectively detect changes in protein abundance but fail to provide a comprehensive perspective of the diversity of proteins such as histones, which are regulated by post-translational modifications. Here, we report the characterization of modified forms of HeLa cell histone H4 with a dynamic range >10(4) using a strictly Top Down mass spectrometric approach coupled with two dimensions of liquid chromatography. This enhanced dynamic range enabled the precise characterization and quantitation of 42 forms uniquely modified by combinations of methylation and acetylation, including those with trimethylated Lys-20, monomethylated Arg-3, and the novel dimethylated Arg-3 (each <1% of all H4 forms). Quantitative analyses revealed distinct trends in acetylation site occupancy depending on Lys-20 methylation state. Because both modifications are dynamically regulated through the cell cycle, we simultaneously investigated acetylation and methylation kinetics through three cell cycle phases and used these data to statistically assess the robustness of our quantitative analysis. This work represents the most comprehensive analysis of histone H4 forms present in human cells reported to date.

Novel Apparatus for the Real-Time Quantification of Dissolved Gas Concentrations and Isotope Ratios

NASA Astrophysics Data System (ADS)

Gupta, M.; Leen, J.; Baer, D. S.; Owano, T. G.; Liem, J.

2013-12-01

Measurements of dissolved gases and their isotopic composition are critical in studying a variety of phenomena, including underwater greenhouse gas generation, air-surface exchange, and pollution migration. These studies typically involve obtaining water samples from streams, lakes, or ocean water and transporting them to a laboratory, where they are degased. The gases obtained are then generally measured using gas chromatography and isotope ratio mass spectrometry for concentrations and isotope ratios, respectively. This conventional, off-line methodology is time consuming, significantly limits the number of the samples that can be measured and thus severely inhibits detailed spatial and temporal mapping of gas concentrations and isotope ratios. In this work, we describe the development of a new membrane-based degassing device that interfaces directly to Los Gatos Research (cavity enhanced laser absorption or Off-Axis ICOS) gas analyzers (cavity enhanced laser absorption or Off-Axis ICOS analyzers) to create an autonomous system that can continuously and quickly measure concentrations and isotope ratios of dissolved gases in real time in the field. By accurately controlling the water flow rate through the membrane degasser, gas pressure on the outside of the membrane, and water pressure on the inside of the membrane, the system is able to generate precise and highly reproducible results. Moreover, by accurately measuring the gas flow rates in and out of the degasser, the gas-phase concentrations (ppm) could be converted into dissolved gas concentrations (nM). We will present detailed laboratory test data that quantifies the linearity, precision, and dynamic range of the system for the concentrations and isotope ratios of dissolved methane, carbon dioxide, and nitrous oxide. By interfacing the degassing device to a novel cavity-enhanced spectrometer (developed by LGR), preliminary data will also be presented for dissolved volatile organics (VOC) and other pollutants. Finally, the system was deployed shipboard, and field deployment data will also be presented.

Proteomic Stable Isotope Probing Reveals Biosynthesis Dynamics of Slow Growing Methane Based Microbial Communities

DOE PAGES

Marlow, Jeffery; Skennerton, Connor T.; Li, Zhou; ...

2016-04-29

Marine methane seep habitats represent an important control on the global flux of methane between the subsurface and water column reservoirs. Meta-omics studies have begun to outline community-wide metabolic potential, but expression patterns of proteins that enact sulfate-mediated anaerobic methane oxidation in seeps are poorly characterized. Proteomic stable isotope probing (proteomic SIP) offers an additional layer of information for characterizing phylogenetically specific, functionally relevant activity in mixed microbial communities. Here we applied proteomic SIP to 15NH4+ and CH4 amended seep sediment microcosms in an attempt to track the protein synthesis of slow-growing, low-energy microbial systems. Across all samples, 3495 proteinsmore » were identified, 21% of which were 15N-labeled. We observed active synthesis (15N enrichment) of all proteins believed to be involved in sulfate reduction and reverse methanogenesis including methylenetetrahydromethanopterin reductase (Mer). The abundance and phylogenetic range of methyl-coenzyme M reductase (Mcr) orthologs produced during incubation experiments suggests that seeps provide sufficient niches for multiple organisms performing analogous metabolisms. Twenty-eight previously unreported post-translational modifications of McrA were measured, indicating dynamic enzymatic machinery and offering a dimension of functional diversity beyond gene-dictated sequence. RNA polymerase associated with putative sulfur-oxidizing Epsilonproteobacteria and aerobic Gammaproteobacteria were more abundant among pre-incubation proteins, suggesting diminished metabolic activity in long-term anoxic, sulfidic experimental incubations. Twenty-six proteins of unknown function were detected in all proteomic experiments and actively expressed in labeled experiments, suggesting that they play important roles in methane seep ecosystems. The addition of stable isotope probing to environmental proteomics experiments provides a mechanism to begin to assess the degree to which diagnostic meatbolic proteins are long-lived or acively synthesized in complex, slow-growing microbial communities. Our work here demonstrates that sediment-hosted microbial assemblages in marine methane seeps are dynamic, heterogeneous systems with broad functional diversity.« less

Proteomic Stable Isotope Probing Reveals Biosynthesis Dynamics of Slow Growing Methane Based Microbial Communities

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

Marlow, Jeffery; Skennerton, Connor T.; Li, Zhou

Marine methane seep habitats represent an important control on the global flux of methane between the subsurface and water column reservoirs. Meta-omics studies have begun to outline community-wide metabolic potential, but expression patterns of proteins that enact sulfate-mediated anaerobic methane oxidation in seeps are poorly characterized. Proteomic stable isotope probing (proteomic SIP) offers an additional layer of information for characterizing phylogenetically specific, functionally relevant activity in mixed microbial communities. Here we applied proteomic SIP to 15NH4+ and CH4 amended seep sediment microcosms in an attempt to track the protein synthesis of slow-growing, low-energy microbial systems. Across all samples, 3495 proteinsmore » were identified, 21% of which were 15N-labeled. We observed active synthesis (15N enrichment) of all proteins believed to be involved in sulfate reduction and reverse methanogenesis including methylenetetrahydromethanopterin reductase (Mer). The abundance and phylogenetic range of methyl-coenzyme M reductase (Mcr) orthologs produced during incubation experiments suggests that seeps provide sufficient niches for multiple organisms performing analogous metabolisms. Twenty-eight previously unreported post-translational modifications of McrA were measured, indicating dynamic enzymatic machinery and offering a dimension of functional diversity beyond gene-dictated sequence. RNA polymerase associated with putative sulfur-oxidizing Epsilonproteobacteria and aerobic Gammaproteobacteria were more abundant among pre-incubation proteins, suggesting diminished metabolic activity in long-term anoxic, sulfidic experimental incubations. Twenty-six proteins of unknown function were detected in all proteomic experiments and actively expressed in labeled experiments, suggesting that they play important roles in methane seep ecosystems. The addition of stable isotope probing to environmental proteomics experiments provides a mechanism to begin to assess the degree to which diagnostic meatbolic proteins are long-lived or acively synthesized in complex, slow-growing microbial communities. Our work here demonstrates that sediment-hosted microbial assemblages in marine methane seeps are dynamic, heterogeneous systems with broad functional diversity.« less

Stable isotopes of C and S as indicators of habitat use by fish in small oregon Coast range streams

EPA Science Inventory

We are using stable isotopes of C, N, O and S (H planned) to study the ecology of coho salmon in streams of the Oregon Coast Range. We have found isotopes of C and, surprisingly, S to be very useful in discriminating rearing habitats in our small streams. We found 13C values ...

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

PubMed

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

2008-05-21

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

Decay of Plutonium isotopes via spontaneous and heavy-ion induced fission paths

NASA Astrophysics Data System (ADS)

Sharma, Kanishka; Sawhney, Gudveen; Sharma, Manoj K.; Gupta, Raj K.

2018-04-01

Based on the collective clusterization approach, we have extended our earlier study on α-decay, exotic cluster-decay, and heavy particle radioactivity, to the phenomenon of spontaneous fission (SF) in the ground-state (g.s.) decays of even mass 234-246Pu parents. The calculations for the SF half-lives of these Pu-isotopes have been made within the framework of preformed cluster model (PCM), both for spherical as well as β2-deformed choices of shapes, and a comparison is made with the relevant available experimental data, which prefer spherical shapes. The importance of the orientation degree of freedom (hot compact or cold elongated configurations) is also explored. Next, in order to look for the exclusive role of heavy-ion induced fission, the dynamics of 6He + 238U reaction forming 244Pu* is studied over the center of mass energy range of E c . m . = 15.0- 28.8MeV, using the dynamical cluster-decay model (DCM), an extension of the PCM with temperature T- and angular momentum ℓ-effects included. The β2-deformed fragments of 244Pu* in the mass range A2 = 106- 113 (plus their complementary heavy fragments), corresponding to asymmetric fission peaks, are found contributing towards the fission cross-section. Finally, the potential energy surfaces and barrier modification effects are presented for the relative comparison of spontaneous and the heavy-ion induced fission processes. Both are found to behave similar with respect to the probable emission of fragments and hence point out to the shell closure property of the decay fragments.

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

Chang, Shih-Jung

Dynamic strength of the High Flux Isotope Reactor (HFIR) vessel to resist hypothetical accidents is analyzed by using the method of fracture mechanics. Vessel critical stresses are estimated by applying dynamic pressure pulses of a range of magnitudes and pulse-durations. The pulses versus time functions are assumed to be step functions. The probability of vessel fracture is then calculated by assuming a distribution of possible surface cracks of different crack depths. The probability distribution function for the crack depths is based on the form that is recommended by the Marshall report. The toughness of the vessel steel used in themore » analysis is based on the projected and embrittled value after 10 effective full power years from 1986. From the study made by Cheverton, Merkle and Nanstad, the weakest point on the vessel for fracture evaluation is known to be located within the region surrounding the tangential beam tube HB3. The increase in the probability of fracture is obtained as an extension of the result from that report for the regular operating condition to include conditions of higher dynamic pressures due to accident loadings. The increase in the probability of vessel fracture is plotted for a range of hoop stresses to indicate the vessel strength against hypothetical accident conditions.« less

An optical method for carbon dioxide isotopes and mole fractions in small gas samples: tracing microbial respiration from soil, litter, and lignin.

Treesearch

Steven J. Hall; Wenjuan Huang; Kenneth Hammel

2017-01-01

RATIONALE: Carbon dioxide isotope (Δ13C value) measurements enable quantification of the sources of soil microbial respiration, thus informing ecosystem C dynamics. Tunable diode lasers (TDLs) can precisely measure CO2 isotopes at low cost and high throughput, but are seldom used for small samples (≤5 mL). We developed a...

Modeling whole-tree carbon assimilation rate using observed transpiration rates and needle sugar carbon isotope ratios.

PubMed

Hu, Jia; Moore, David J P; Riveros-Iregui, Diego A; Burns, Sean P; Monson, Russell K

2010-03-01

*Understanding controls over plant-atmosphere CO(2) exchange is important for quantifying carbon budgets across a range of spatial and temporal scales. In this study, we used a simple approach to estimate whole-tree CO(2) assimilation rate (A(Tree)) in a subalpine forest ecosystem. *We analysed the carbon isotope ratio (delta(13)C) of extracted needle sugars and combined it with the daytime leaf-to-air vapor pressure deficit to estimate tree water-use efficiency (WUE). The estimated WUE was then combined with observations of tree transpiration rate (E) using sap flow techniques to estimate A(Tree). Estimates of A(Tree) for the three dominant tree species in the forest were combined with species distribution and tree size to estimate and gross primary productivity (GPP) using an ecosystem process model. *A sensitivity analysis showed that estimates of A(Tree) were more sensitive to dynamics in E than delta(13)C. At the ecosystem scale, the abundance of lodgepole pine trees influenced seasonal dynamics in GPP considerably more than Engelmann spruce and subalpine fir because of its greater sensitivity of E to seasonal climate variation. *The results provide the framework for a nondestructive method for estimating whole-tree carbon assimilation rate and ecosystem GPP over daily-to weekly time scales.

Examining the response of larch needle carbohydrates to climate using compound-specific δ13C and concentration analyses

NASA Astrophysics Data System (ADS)

Rinne, Katja T.; Saurer, Matthias; Kirdyanov, Alexander V.; Bryukhanova, Marina V.; Prokushkin, Anatoly S.; Churakova Sidorova, Olga V.; Siegwolf, Rolf T. W.

2016-04-01

Little is known about the dynamics of concentrations and carbon isotope ratios of individual carbohydrates in leaves in response to climatic and physiological factors. Improved knowledge of the isotopic ratio in sugars will enhance our understanding of the tree ring isotope ratio and will help to decipher environmental conditions in retrospect more reliably. Carbohydrate samples from larch (Larix gmelinii) needles of two sites in the continuous permafrost zone of Siberia with differing growth conditions were analysed with the Compound-Specific Isotope Analysis (CSIA). We compared concentrations and carbon isotope values (δ13C) of sucrose, fructose, glucose and pinitol combined with phenological data. The results for the variability of the needle carbohydrates show high dynamics with distinct seasonal characteristics between and within the studied years with a clear link to the climatic conditions, particularly vapour pressure deficit. Compound-specific differences in δ13C values as a response to climate were detected. The δ13C of pinitol, which contributes up to 50% of total soluble carbohydrates, was almost invariant during the whole growing season. Our study provides the first in-depth characterization of compound-specific needle carbohydrate isotope variability, identifies involved mechanisms and shows the potential of such results for linking tree physiological responses to different climatic conditions.

Comparing sulfur and oxygen isotope variability of sulfate in the Mississippi River during high and low discharge from 2009-2011

NASA Astrophysics Data System (ADS)

Killingsworth, B.; Kohl, I. E.; Bao, H.

2011-12-01

S and O isotope compositions of ocean and river sulfate, SO42-, reflect Earth surface processes and can thus be used to understand the Earth's dynamic past. It has been estimated that riverine SO42- is 22% evaporite (SO42-riv-evap), 11% oxidative weathering (SO42-riv-ow), and 54% atmospheric and agricultural pollution [1]. Two parameters are poorly constrained: 1) the ratio of SO42-riv-evap to SO42-riv-ow, and 2) the extent of human influence on SO42- flux. Furthermore, for isotopic modeling, natural riverine SO42- O and S isotope compositions, δ18OSO4-riv and δ34SSO4-riv, have large measured ranges (e.g. δ18OSO4-riv from -2% to +7% [2]) that are based on limited empirical data with variable and unconstrained influence from human activities. In the lower Mississippi River Basin (MRB) we have sampled river water SO42- biweekly since 2009. Our isotope dataset is used in conjunction with US Geological Survey and US Army Corps of Engineers SO42- concentration and river discharge data. In comparison to MRB low discharge periods, the periods of annual high water discharge are characterized by 1) a doubling in water discharge 2) a concomitant high MRB SO42- flux (>1100 kg/s) 3) an average SO42- concentration at 85% of the low discharge concentrations and 4) a more constrained variability of SO42- isotope composition. The δ18OSO4-riv ranges from +3.2% to +5.5% at high discharge and from +2.6% to +8.8% at low discharge. The δ34SSO4-riv ranges from -4.3% to -0.4 at high discharge and from -6.3% to -0.2% at low discharge. Atmospheric SO42- is estimated from 2009 National Atmospheric Deposition Program maps to contribute only ~10% of total MRB SO42-. We conclude that during annual high discharge a large river basin such as the MRB is less sensitive to variable sub-basin input and that average MRB SO42- isotope composition is best represented by a δ18OSO4-riv value of ~+4.0% and δ34SSO4-riv value of ~-3.0%. MRB SO42- concentration during high discharge is diluted less than expected, given the low concentration of SO42- in precipitation, and this result reveals the existence of a spatially dispersed and significant SO42- sink, such as soil, within the MRB. The all-negative range for MRB δ34SSO4-riv indicates that oxidative weathering of both (1) reduced sulfur (e.g. biologically cycled sulfur in soil) and (2) sulfides (e.g. pyrite in coal), is the dominant source of SO42- in the MRB because all other sources of riverine SO42- have positive δ34SSO4-riv values [3]. Moreover, the Upper Ohio (UORB) and Upper Missouri (UMRB) MRB sub-basins both contain significant coalfields which are likely sources of much of the isotopically lighter SO42- in the MRB. The UORB and UMRB contributed ~1/3 of all MRB SO42- during high discharge and low discharge, respectively, and a combined 1/2 of all MRB SO42- each year in the 10-year period 1999-2009. [1]Berner, E. K., and R. A. Berner (1996), Global environment; [2]Turchyn, A. V., and D. P. Schrag (2004), Science, 303(5666), 2004-2007; [3]Rock, L., and B. Mayer (2009), Chem. Geol., 262(3-4), 121-130.

Analysis of stable isotopes in fish to identify habitat use and switching

EPA Science Inventory

In our isotopic studies of fish in Oregon Coast Range streams we have found stable isotopes of carbon, oxygen and sulfur to be surprisingly useful in identifying and discriminating specific habitat or tributary use by a variety of fish species. Stable isotopes of carbon can be u...

Stable isotopes in fish as indicators of habitat use

EPA Science Inventory

In our isotopic studies of fish in Oregon Coast Range streams we have found stable isotopes of carbon, oxygen and sulfur to be surprisingly useful in identifying and discriminating specific habitat or tributary use by a variety of fish species. Stable isotopes of carbon can be u...

Stable Oxygen isotopes in otoliths to reconstruct salmon and striped bass habitat use within the San Francisco Bay estuary

NASA Astrophysics Data System (ADS)

Malamud-Roam, F.; Phillis, C.; Ingram, B. L.; Schmitt, A. K.; Weber, P. K.

2008-12-01

Understanding the habitat use of anadromous fish species within major riverine and estuarine settings can provide useful information for protecting these fish populations. The inner ear bone, or otolith, of these fish is an accretionary carbonate structure that contains a high-resolution record of the life history of the fish, including certain chemical properties of the ambient waters occupied by the fish. Stable isotopes measured in the daily-accreting otolith layers can provide highly-resolved histories of habitat occupation. For the salmon, the juvenile phase is a critical life history period and researchers, as well as agencies charged with protecting these fish, seek detailed information about habitat use during this phase. We have measured isotopic ratios of 18O/16O (δ18O permil) in the otoliths of Chinook Salmon and striped bass, sampling along the growth axis, to produce a history of habitat use by these fish. The 18O/16O ratios of the carbonate otolith samples are primarily influenced by the 18O/16O ratio of the surrounding waters (which range from ~0 permil near the Golden Gate to -11 permil for river water), modified by temperature (- 0.326 permil/°C, so a range of approximately 1.6 permil over the course of a year. We have modeled the expected values for carbonate samples for locations throughout the estuary based upon seasonally averaged salinity and temperature values for these locations; for example, we expect delta 18O values of about -7.5 permil in otoliths for fish at the entrance to the estuary and about 2.7 permil in the ocean. We find good agreement between the δ18O data and 87/86Sr data collected earlier on the same fish samples (which also varies as a function of salinity). The value of the oxygen isotope data is that they provide great dynamic range in the brackish to saline portion of the estuary. The combined data provide a record of where the fish spent significant portions of their lives.

Controls of Isotopic Patterns in Saprotrophic and Ectomycorrhizal Fungi

EPA Science Inventory

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

Variation in nitrate isotopic signatures in sewage for source apportionment with urbanization: a case study in Beijing, China.

PubMed

Xian, Chaofan; Ouyang, Zhiyun; Li, Yanmin; Xiao, Yang; Ren, Yufen

2016-11-01

Nitrate (NO 3 - ) pollution is a severe problem in urban aquatic systems especially within megacity undergoing rapid urbanization, and mostly, sewage is supposed as the prevailing NO 3 - source. A dual isotope approach (δ 15 N-NO 3 - and δ 18 O-NO 3 - ) was applied to explore the variation in NO 3 - isotopic signatures in sewage processed by wastewater treatment plants (WWTPs) in Beijing from 2014 to 2015. We found that the raw and treated sewage owned the different NO 3 - isotopic signatures, including δ 15 N from 1.1 to 24.7 ‰ and δ 18 O from 1.6 to 22.8 ‰ in raw sewage, as well as δ 15 N from 6.1 to 22.8 ‰ and δ 18 O from 1.6 to 13.2 ‰ in treated effluents. The WWTP processing would result in the enrichment of NO 3 - isotopic compositions in discharged effluents with NO 3 - concentrations increasing. Besides, advanced sewage treatment technology with more pollutant N reduction may raise the heavier NO 3 - isotopic compositions further. The NO 3 - isotope value ranges of urban sewage and manure should be separated, and the seasonal and tighter NO 3 - isotope value ranges are supposed to improve the accuracy of source apportionment. The NO 3 - isotope value ranges conducted in this study might provide useful information for tracing NO 3 - sources towards the implementation of efficient water pollution control in Beijing.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

The planet Mars is unique in our solar system with a positive O-isotope anomaly observed in its bulk silicate and carbonates minerals ranging from 0.3 to 0.6 ‰. The carbonate isotopic signature can be used to reveal its origin, past history and atmosphere-hydrosphere-geosphere-interactions. Ozone is a powerful natural tracer of photochemical processes in Earth's atmosphere. It possess the highest enrichment in heavy isotopes δ17O ≈ δ18O (70-150‰) and oxygen isotopic anomaly (Δ17O = 30-40‰). The oxygen isotopic anomaly from ozone is transferred to other oxygen carrying molecules in the atmosphere through different mechanisms. Laboratory experiments were conducted with the JSC-Mars Simulant and iron oxide to investigate how this anomaly can be transferred to water and minerals under conditions similar to present day Mars. Three sets of laboratory experiments (O3-H2O-UV-minerals; O2-H2O-UV-minerals; O3-H2O-minerals) were performed. The oxygen triple isotopic analysis of product mineral carbonates formed from adsorbed CO2 reaction showed an oxygen isotopic anomaly (Δ17O = 0.4-3‰). The oxygen triple isotopic composition of water at photochemical equilibrium shifted towards ozone with Δ17O = 9‰ indicating reaction of ozone with water vapor via electronically excited oxygen atoms and transfer of the anomaly via hydroxyl radicals. HOx (HO, HO2) are extremely reactive and have very short life time (< μs), however, our data indicate that its signature is preserved through surficial interactions with adsorbed CO2 on mineral surfaces. Hydroxyl radicals may have played a significant role in heterogeneous photochemical transformations on mineral dust in the atmosphere of Mars and transfer of ozone anomaly to water and other oxygen bearing minerals through surficial reactions. Series of experiments were performed to constrain the amount of H2O required to preserve the oxygen isotope anomaly observed in carbonate minerals in the Martian meteorites. These observation will help refine Mars photochemistry models and also to constrain the past hydrological cycle and its coupling with the regolith. The observed inverse correlation between ozone and water vapor also suggests a dynamic role of hydroxyl radical chemistry in the atmosphere of Mars.

Decadal record of monsoon dynamics across the Himalayas using tree ring data

NASA Astrophysics Data System (ADS)

Brunello, Camilla Francesca; Andermann, Christoff; Helle, Gerhard; Comiti, Francesco; Tonon, Giustino; Ventura, Maurizio; Hovius, Niels

2017-04-01

The temporal variability of the Indian monsoon penetrating through the Himalayan range and into the southern Tibetan Plateau is poorly understood. Intermittent ingress of wet monsoon air masses into the otherwise arid and deserted landscapes beyond the orographic barrier can have consequences for erosion and flooding, as well as for water availability. Furthermore, the latitudinal rainfall distribution across the mountain range is crucial to better understand the hydrological cycles of rivers originating there. Because instrumental measurements are rare in the High Himalayas and on the Plateau, hydro-climatic sensitive proxies, such as oxygen stable isotope ratios in cellulose of tree-rings, are a valuable source of data covering decades to centuries. Here we present new findings on how often and how far the Indian monsoon penetrated into trans-Himalayan region over the last century. To cope with the lack of direct measurements, we strive to reconstruct a record of intense monsoon years based on tree-ring width chronologies along a latitudinal gradient. Thus, we need to answer whether water availability is the main driver of tree growth in the trans-Himalayan region and how dendro-isotopic data relate to seasonal precipitation inputs and sources. In order to study the monsoon dynamics, we selected four sites along the Kali Gandaki River valley in the central Himalayas (Nepal). This valley connects the very wet, monsoon dominated south Himalayan front with the arid trans-Himalayan region and the southern Tibetan Plateau. Our study area covers the sensitive northern end of the precipitation gradient, located in the upper part of the catchment. Water availability, which drastically varies at each site, was explored by using the climate signal- and isotope-transfer within arboreal systems composed of Juniperus sp., Cupressus sp. and Pinus sp. Results from continuous dendrometer measurements for the entire growing season (Mar-Oct) allowed us to assess the link between tree growth and precipitation, confirming the sensitivity of the trees to water availability. A set of cores from at least 20 individual trees was collected at each site. Dating revealed records with lengths from 80 to 500 years. Tree-ring width measurements were detrended to minimize the ecological influence on growth, and analyzed against local climate parameters such as temperature and precipitation. The site chronologies were compared to highlight the propagation of the monsoonal events along the latitudinal transect. Additionally, 80-year tree-ring oxygen isotope records from the lowest site (Lete, 2500 m a.s.l.) of the transect were compared with precipitation patterns derived from historical rain gauge and satellite data. This study provides first insights into the relationship among tree-ring width, cellulose isotopes and monsoon signature, shedding light on decadal variations of precipitation in the high-elevated arid area of the High Himalayas.

Diverging effects of isotopic fractionation upon molecular diffusion of noble gases in water: mechanistic insights through ab initio molecular dynamics simulations.

PubMed

Pinto de Magalhães, Halua; Brennwald, Matthias S; Kipfer, Rolf

2017-03-22

Atmospheric noble gases are routinely used as natural tracers to analyze gas transfer processes in aquatic systems. Their isotopic ratios can be employed to discriminate between different physical transport mechanisms by comparison to the unfractionated atmospheric isotope composition. In many applications of aquatic systems molecular diffusion was thought to cause a mass dependent fractionation of noble gases and their isotopes according to the square root ratio of their masses. However, recent experiments focusing on isotopic fractionation within a single element challenged this broadly accepted assumption. The determined fractionation factors of Ne, Ar, Kr and Xe isotopes revealed that only Ar follows the prediction of the so-called square root relation, whereas within the Ne, Kr and Xe elements no mass-dependence was found. The reason for this unexpected divergence of Ar is not yet understood. The aim of our computational exercise is to establish the molecular-resolved mechanisms behind molecular diffusion of noble gases in water. We make the hypothesis that weak intermolecular interactions are relevant for the dynamical properties of noble gases dissolved in water. Therefore, we used ab initio molecular dynamics to explicitly account for the electronic degrees of freedom. Depending on the size and polarizability of the hydrophobic particles such as noble gases, their motion in dense and polar liquids like water is subject to different diffusive regimes: the inter-cavity hopping mechanism of small particles (He, Ne) breaks down if a critical particle size achieved. For the case of large particles (Kr, Xe), the motion through the water solvent is governed by mass-independent viscous friction leading to hydrodynamical diffusion. Finally, Ar falls in between the two diffusive regimes, where particle dispersion is propagated at the molecular collision time scale of the surrounding water molecules.

Investigating temperature effects on methane production and oxidation in the rice ecosystem using stable carbon and hydrogen isotope ratios

NASA Astrophysics Data System (ADS)

Rice, A. L.; Sithole, A.; Shearer, M. J.; Hanson, E.; Fisher, A.; Khalil, A. K.

2010-12-01

Irrigated rice is a major agricultural source of methane emissions that contributes about 15% of global atmospheric methane (CH4). Our work investigates the relationships between temperature and CH4 production, oxidation, and flux in the rice ecosystem. This is central to understanding the response of the global CH4 emissions from rice under a changing climate. Temperatures were regulated in sixteen rice plots grown in a research greenhouse using four waterbath-temperature control systems held at 20°C, 24°C, 28°C, and 32°C over the course of a growing season. Belowground porewater samples were collected from each treatment weekly and CH4 was extracted into headspace N2 after vigorous shaking. Weekly flux samples were collected using acrylic static flux chambers placed over the rice plots. CH4 concentrations below and aboveground were measured using gas chromatography-flame ionization detection. The carbon (δ13C) and hydrogen (δD) isotopic composition of CH4 was measured using continuous-flow gas chromatography isotope ratio mass spectrometry. Results show that CH4 flux ranged from near zero to 30-60 mg/m2/hr in mid-season corresponding to a rise in porewater CH4 to 8-12 mg/L. Early season CH4 fluxes were larger in elevated temperature treatments but this difference was smaller, or even reversed in some cases, in the late season. Similar trends were observed in CH4 porewater concentration profiles. Results from isotopic measurements show mean belowground δ13C values between -44‰ and -52‰ relative to VPDB and δD values between -290‰ and -320‰ relative to VSMOW. Emitted CH4 had mean δ13C values which ranged from -50‰ to -60‰ VPDB. We integrate these results and interpret them using an empirically-driven concentration and isotope model to understand CH4 dynamics and to examine the effect of temperature on mechanisms that control CH4 emissions.

Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from Small Samples.

NASA Astrophysics Data System (ADS)

Field, P.; Lloyd, N. S.

2016-12-01

V002: Advances in approaches and instruments for isotope studies Session ID#: 12653 Recent Developments in MC-ICP-MS for Uranium Isotopic Determination from small samples.M. Paul Field 1 & Nicholas S. Lloyd. 1 Elemental Scientific Inc., Omaha, Nebraska, USA. field@icpms.com 2 Thermo Fisher Scientific, Hanna-Kunath-Str. 11, 28199 Bremen, Germany. nicholas.lloyd@thermofisher.com Uranium isotope ratio determination for nuclear, nuclear safeguards and for environmental applications can be challenging due to, 1) the large isotopic differences between samples and 2) low abundance of 234U and 236U. For some applications the total uranium quantities can be limited, or it is desirable to run at lower concentrations for radiological protection. Recent developments in inlet systems and detector technologies allow small samples to be analyzed at higher precisions using MC-ICP-MS. Here we evaluate the combination of Elemental Scientific apex omega desolvation system and microFAST-MC dual loop-loading flow-injection system with the Thermo Scientific NEPTUNE Plus MC-ICP-MS. The inlet systems allow for the automated syringe loading and injecting handling of small sample volumes with efficient desolvation to minimize the hydride interference on 236U. The highest ICP ion sampling efficiency is realized using the Thermo Scientific Jet Interface. Thermo Scientific 1013 ohm amplifier technology allows small ion beams to be measured at higher precision, offering the highest signal/noise ratio with a linear and stable response that covers a wide dynamic range (ca. 1 kcps - 30 Mcps). For nanogram quantities of low enriched and depleted uranium standards the 235U was measured with 1013 ohm amplifier technology. The minor isotopes (234U and 236U) were measured by SEM ion counters with RPQ lens filters, which offer the lowest detection limits. For sample amounts ca. 20 ng the minor isotopes can be moved onto 1013 ohm amplifiers and the 235U onto standard 1011 ohm amplifier. To illustrate the application a set of solutions from environmental particles [1] were analyzed, the use of precise three isotope ratio plots allows for source attribution with increased confidence. [1] Lloyd et al. 2009, J. Anal. At. Spectrom., 24(6), 752-758.

Influences of large-scale convection and moisture source on monthly precipitation isotope ratios observed in Thailand, Southeast Asia

NASA Astrophysics Data System (ADS)

Wei, Zhongwang; Lee, Xuhui; Liu, Zhongfang; Seeboonruang, Uma; Koike, Masahiro; Yoshimura, Kei

2018-04-01

Many paleoclimatic records in Southeast Asia rely on rainfall isotope ratios as proxies for past hydroclimatic variability. However, the physical processes controlling modern rainfall isotopic behaviors in the region is poorly constrained. Here, we combined isotopic measurements at six sites across Thailand with an isotope-incorporated atmospheric circulation model (IsoGSM) and the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model to investigate the factors that govern the variability of precipitation isotope ratios in this region. Results show that rainfall isotope ratios are both correlated with local rainfall amount and regional outgoing longwave radiation, suggesting that rainfall isotope ratios in this region are controlled not only by local rain amount (amount effect) but also by large-scale convection. As a transition zone between the Indian monsoon and the western North Pacific monsoon, the spatial difference of observed precipitation isotope among different sites are associated with moisture source. These results highlight the importance of regional processes in determining rainfall isotope ratios in the tropics and provide constraints on the interpretation of paleo-precipitation isotope records in the context of regional climate dynamics.

δ18O and δD of lake waters across the Coast Range and Cascades, central Oregon: Modern insights from hydrologically open lakes into the control of landscape on lake water composition in deep time

NASA Astrophysics Data System (ADS)

Finkelstein, D. B.; Curtin, T.

2016-12-01

Reconstructing the stable isotopic composition of paleolake water normally requires an assumption of paleotemperature. However, hydrologically open paleolakes with short water residence times may have recorded paleoprecipitation along topographic gradients that are independent of lake water temperature. To identify the environmental and geographic controls on the isotopic composition of lake water, we sampled 22 natural lakes and reservoirs along a longitudinal and elevation gradient from the Pacific Ocean up and over the Coast and Cascade Ranges of central Oregon to the High Lava Plains in 2013 and 2015. The transect spans lakes of different origins, 6 geomorphic regions and an elevation range of 2-1942 m absl. The Coast Range lakes are sand hosted whereas the remaining are bedrock (volcanic and sedimentary) hosted. The lakes are hydrologically open and dominated by meteoric recharge. The water residence time ranges from months to decades. Samples were analyzed for temperature, pH, and total dissolved solids (TDS) in the field, and alkalinity and major cations and anions and stable isotopes of D and O in the lab. The pH ranges from 7 to 9.8 and shows no systematic variation based on substrate type or elevation. The lakes are dilute (avg. TDS = 35.8 ppm) and have low alkalinties (18.9 mg/L CaCO3) except for those in the High Lava Plains (avg. TDS = 337 ppm, alk: 291.2 mg/L CaCO3). In the Coast Range, Na is the major cation on an equivalent basis, reflecting proximity to the ocean. The easternmost lakes within the Coast Range are dominated by Ca, reflecting different drainage basins and substrate type. Lakes in the Western and High Cascades are dominated by Ca. The dominant cation and stable isotopic analyses clearly differentiate waters from different geomorphic regions. The δ18O ranges from -5.7 to -9.3 ‰ (VSMOW), and δD ranges from -37.8 to -63.6 ‰ (VSMOW) in the Coast Range whereas the δ18O ranges from -9.7 to -12.1 ‰ (VSMOW) and δD ranges from -71.5 to -86.5‰ (VSMOW) in the Cascades. Stable isotopic differences between mountain ranges reflect distance from the ocean and increasing elevation. Stable isotopes of water show no correlation with air or lake water temperatures. Average annual precipitation and bedrock across this topographic gradient controls the major ions and stable isotopic composition of these lakes.

Early-stage changes in natural (13)C and (15)N abundance and nutrient dynamics during different litter decomposition.

PubMed

Gautam, Mukesh Kumar; Lee, Kwang-Sik; Song, Byeong-Yeol; Lee, Dongho; Bong, Yeon-Sik

2016-05-01

Decomposition, nutrient, and isotopic (δ(13)C and δ(15)N) dynamics during 1 year were studied for leaf and twig litters of Pinus densiflora, Castanea crenata, Erigeron annuus, and Miscanthus sinensis growing on a highly weathered soil with constrained nutrient supply using litterbags in a cool temperate region of South Korea. Decay constant (k/year) ranged from 0.58 to 1.29/year, and mass loss ranged from 22.36 to 58.43 % among litter types. The results demonstrate that mass loss and nutrient dynamics of decomposing litter were influenced by the seasonality of mineralization and immobilization processes. In general, most nutrients exhibited alternate phases of rapid mineralization followed by gradual immobilization, except K, which was released throughout the field incubation. At the end of study, among all the nutrients only N and P showed net immobilization. Mobility of different nutrients from decomposing litter as the percentage of initial litter nutrient concentration was in the order of K > Mg > Ca > N ≈ P. The δ(13)C (0.32-6.70 ‰) and δ(15)N (0.74-3.90 ‰) values of residual litters showed nonlinear increase and decrease, respectively compared to initial isotopic values during decomposition. Litter of different functional types and chemical quality converged toward a conservative nutrient use strategy through mechanisms of slow decomposition and slow nutrient mobilization. Our results indicate that litter quality and season, are the most important regulators of litter decomposition in these forests. The results revealed significant relationships between litter decomposition rates and N, C:N ratio and P, and seasonality (temperature). These results and the convergence of different litters towards conservative nutrient use in these nutrient constrained ecosystems imply optimization of litter management because litter removal can have cascading effects on litter decomposition and nutrient availability in these systems.

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Dynamic Antarctic ice sheet during the early to mid-Miocene

PubMed Central

DeConto, Robert M.; Pollard, David; Levy, Richard H.

2016-01-01

Geological data indicate that there were major variations in Antarctic ice sheet volume and extent during the early to mid-Miocene. Simulating such large-scale changes is problematic because of a strong hysteresis effect, which results in stability once the ice sheets have reached continental size. A relatively narrow range of atmospheric CO2 concentrations indicated by proxy records exacerbates this problem. Here, we are able to simulate large-scale variability of the early to mid-Miocene Antarctic ice sheet because of three developments in our modeling approach. (i) We use a climate–ice sheet coupling method utilizing a high-resolution atmospheric component to account for ice sheet–climate feedbacks. (ii) The ice sheet model includes recently proposed mechanisms for retreat into deep subglacial basins caused by ice-cliff failure and ice-shelf hydrofracture. (iii) We account for changes in the oxygen isotopic composition of the ice sheet by using isotope-enabled climate and ice sheet models. We compare our modeling results with ice-proximal records emerging from a sedimentological drill core from the Ross Sea (Andrill-2A) that is presented in a companion article. The variability in Antarctic ice volume that we simulate is equivalent to a seawater oxygen isotope signal of 0.52–0.66‰, or a sea level equivalent change of 30–36 m, for a range of atmospheric CO2 between 280 and 500 ppm and a changing astronomical configuration. This result represents a substantial advance in resolving the long-standing model data conflict of Miocene Antarctic ice sheet and sea level variability. PMID:26903645

Using vegetation cover type to predict and scale peatland methane dynamics.

NASA Astrophysics Data System (ADS)

McArthur, K. J.; McCalley, C. K.; Palace, M. W.; Varner, R. K.; Herrick, C.; DelGreco, J. L.

2015-12-01

Permafrost ecosystems contain about 50% of the global soil carbon. As these northern ecosystems experience warmer temperature, permafrost thaws and may result in an increase in atmospheric methane. We examined a thawing and discontinuous permafrost boundary at Stordalen Mire, in Northern Sweden, in an effort to better understand methane emissions. Stable isotope analysis of methane in peatland porewater can give insights into the pathway of methane production. By measuring δ13CH4 we can predict whether a system is dominated by either hydrogenotrophic or acetaclastic methane production. Currently, it is a challenge to scale these isotopic patterns, thus, atmospheric inversion models simply assume that acetoclastic production dominates. We analyzed porewater samples collected across a range of vegetation cover types for δ13CH4 using a QCL (Quantum Cascade Laser Spectrometer) in conjunction with highly accurate GPS (3-10cm) measurements and high-resolution UAV imaging. We found δ13CH4 values ranging from -88‰ to -41‰, with averages based on cover type and other vegetation features showing differences of up to -15‰. We then used a computer neural network to predict cover types across Stordalen Mire from UAV imagery based on field-based plot measurements and training samples.. This prediction map was used to scale methane flux and isotope measurements. Our results suggest that the current values used in atmospheric inversion studies may oversimplify the relationship between plant and microbial communities in complex permafrost landscapes. As we gain a deeper understanding of how vegetation relates to methanogenic communities, understanding the spatial component of ecosystem methane metabolism and distribution will be increasingly valuable.

A multi-tracer approach to delineate groundwater dynamics in the Rio Actopan Basin, Veracruz State, Mexico

NASA Astrophysics Data System (ADS)

Pérez Quezadas, Juan; Heilweil, Victor M.; Cortés Silva, Alejandra; Araguas, Luis; Salas Ortega, María del Rocío

2016-12-01

Geochemistry and environmental tracers were used to understand groundwater resources, recharge processes, and potential sources of contamination in the Rio Actopan Basin, Veracruz State, Mexico. Total dissolved solids are lower in wells and springs located in the basin uplands compared with those closer to the coast, likely associated with rock/water interaction. Geochemical results also indicate some saltwater intrusion near the coast and increased nitrate near urban centers. Stable isotopes show that precipitation is the source of recharge to the groundwater system. Interestingly, some high-elevation springs are more isotopically enriched than average annual precipitation at higher elevations, indicating preferential recharge during the drier but cooler winter months when evapotranspiration is reduced. In contrast, groundwater below 1,200 m elevation is more isotopically depleted than average precipitation, indicating recharge occurring at much higher elevation than the sampling site. Relatively cool recharge temperatures, derived from noble gas measurements at four sites (11-20 °C), also suggest higher elevation recharge. Environmental tracers indicate that groundwater residence time in the basin ranges from 12,000 years to modern. While this large range shows varying groundwater flowpaths and travel times, ages using different tracer methods (14C, 3H/3He, CFCs) were generally consistent. Comparing multiple tracers such as CFC-12 with CFC-113 indicates piston-flow to some discharge points, yet binary mixing of young and older groundwater at other points. In summary, groundwater within the Rio Actopan Basin watershed is relatively young (Holocene) and the majority of recharge occurs in the basin uplands and moves towards the coast.

Small-scale studies of roasted ore waste reveal extreme ranges of stable mercury isotope signatures

NASA Astrophysics Data System (ADS)

Smith, Robin S.; Wiederhold, Jan G.; Jew, Adam D.; Brown, Gordon E.; Bourdon, Bernard; Kretzschmar, Ruben

2014-07-01

Active and closed Hg mines are significant sources of Hg contamination to the environment, mainly due to large volumes of mine waste material disposed of on-site. The application of Hg isotopes as source tracer from such contaminated sites requires knowledge of the Hg isotope signatures of different materials potentially released to the environment. Previous work has shown that calcine, the waste residue of the on-site ore roasting process, can exhibit distinct Hg isotope signatures compared with the primary ore. Here, we report results from a detailed small-scale study of Hg isotope variations in calcine collected from the closed New Idria Hg mine, San Benito County, CA, USA. The calcine samples exhibited different internal layering features which were investigated using optical microscopy, micro X-ray fluorescence, micro X-ray absorption spectroscopy (μ-XAS), and stable Hg isotope analysis. Significant Fe, S, and Hg concentration gradients were found across the different internal layers. Isotopic analyses revealed an extreme variation with pronounced isotopic gradients across the internal layered features. Overall, δ202Hg (±0.10‰, 2 SD) describing mass-dependent fractionation (MDF) ranged from -5.96 to 14.49‰, which is by far the largest range of δ202Hg values reported for any environmental sample. In addition, Δ199Hg (±0.06‰, 2 SD) describing mass-independent fractionation (MIF) ranged from -0.17 to 0.21‰. The μ-XAS analyses suggested that cinnabar and metacinnabar are the dominant Hg-bearing phases in the calcine. Our results demonstrate that the incomplete roasting of HgS ores in Hg mines can cause extreme mass-dependent Hg isotope fractionations at the scale of individual calcine pieces with enrichments in both light and heavy Hg isotopes relative to the primary ore signatures. This finding has important implications for the application of Hg isotopes as potential source tracers for Hg released to the environment from closed Hg mines and highlights the need for detailed source signature identification.

Dissolved carbon dynamics in the freshwater-saltwater mixing zone of a coastal river entering the Northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

He, S.; Xu, Y. J.

2017-12-01

Estuaries play an important role in the dynamics of dissolved carbon from freshwater to marine systems. This study aims to determine how dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) concentrations change along an 88-km long estuarine river with salinity ranging from 0.02 to 29.50. The study is expected to elucidate which processes most likely control carbon dynamics in a freshwater-saltwater mixing system, and to evaluate the net metabolism of this estuary using mixing curves and stable isotope analyses. From November 2014 to February 2016, water samples were collected and in-situ measurements on ambient water conditions were performed during eighteen field trips at six sites from upstream to downstream of the Calcasieu River, which enters the Northern Gulf of Mexico in the southern United States. δ13CDIC and δ13CDOC were measured from May 2015 to February 2017 during five of the field trips. The DIC concentration and δ13CDIC increased rapidly with increasing salinity in the mixing zone. The DIC concentrations appeared to be largely influenced by conservative mixing. The δ13CDIC values were close to those suggested by the conservative mixing model for May 2015, June 2015 and November 2015, but lower than those for July 2015 and February 2016, suggesting that an estuarine river can fluctuate from a balanced to a heterotrophic system (i.e., production/respiration < 1) seasonally. Unlike the DIC longitudinal trend, the DOC concentrations in the river estuary decreased from upstream to downstream, but to a much smaller degree. This river estuary consistently showed depleted δ13CDOC values (-30.56‰ to -25.92‰), suggesting that the DOC source in the mixing zone was highly terrestrially derived. However, in this relatively small isotopic range, δ13CDOC alone has limitations in differentiating carbon produced by aquatic photosynthesis from carbon produced by terrestrial photosynthesis in a river-ocean continuum. These findings suggest that riverine dissolved carbon undergoes a rapid change in freshwater-saltwater mixing, and that these dynamics should be taken into account in carbon processing and budgeting in the world's estuarine systems.

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

NASA Astrophysics Data System (ADS)

Price, Gregory; Grimes, Stephen

2015-04-01

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

Magnesium Isotopes as a Tracer of Crustal Materials in Volcanic Arc Magmas in the Northern Cascade Arc

NASA Astrophysics Data System (ADS)

Brewer, Aaron W.; Teng, Fang-Zhen; Mullen, Emily

2018-03-01

Fifteen North Cascade Arc basalts and andesites were analyzed for Mg isotopes to investigate the extent and manner of crustal contributions to this magmatic system. The δ26Mg of these samples vary from within the range of ocean island basalts (the lightest being -0.33 ± 0.07‰) to heavier compositions (as heavy as -0.15 ± 0.06‰). The observed range in chemical and isotopic composition is similar to that of other volcanic arcs that have been assessed to date in the circum-pacific subduction zones and in the Caribbean. The heavy Mg isotope compositions are best explained by assimilation and fractional crystallization within the deep continental crust with a possible minor contribution from the addition of subducting slab-derived fluids to the primitive magma. The bulk mixing of sediment into the primitive magma or mantle source and the partial melting of garnet-rich peridotite are unlikely to have produced the observed range of Mg isotope compositions. The results show that Mg isotopes may be a useful tracer of crustal input into a magma, supplementing traditional methods such as radiogenic isotopic and trace element data, particularly in cases in which a high fraction of crustal material has been added.

Iron isotopic systematics of oceanic basalts

NASA Astrophysics Data System (ADS)

Teng, Fang-Zhen; Dauphas, Nicolas; Huang, Shichun; Marty, Bernard

2013-04-01

The iron isotopic compositions of 93 well-characterized basalts from geochemically and geologically diverse mid-ocean ridge segments, oceanic islands and back arc basins were measured. Forty-three MORBs have homogeneous Fe isotopic composition, with δ56Fe ranging from +0.07‰ to +0.14‰ and an average of +0.105 ± 0.006‰ (2SD/√n, n = 43, MSWD = 1.9). Three back arc basin basalts have similar δ56Fe to MORBs. By contrast, OIBs are slightly heterogeneous with δ56Fe ranging from +0.05‰ to +0.14‰ in samples from Koolau and Loihi, Hawaii, and from +0.09‰ to +0.18‰ in samples from the Society Islands and Cook-Austral chain, French Polynesia. Overall, oceanic basalts are isotopically heavier than mantle peridotite and pyroxenite xenoliths, reflecting Fe isotope fractionation during partial melting of the mantle. Iron isotopic variations in OIBs mainly reflect Fe isotope fractionation during fractional crystallization of olivine and pyroxene, enhanced by source heterogeneity in Koolau samples.

Tracing the origin of pollution in French Alpine snow and aerosols using lead isotopic ratios.

PubMed

Veysseyre, A M; Bollhöfer, A F; Rosman, K J; Ferrari, C P; Boutron, C F

2001-11-15

Fresh snow samples collected at 15 remote locations and aerosols collected at one location in the French Alps between November 1998 and April 1999 have been analyzed for Pb concentration and isotopic composition by thermal ionization mass spectrometry. The snow samples contained 19-1300 pg/g of Pb with isotopic ratios 206Pb/207Pb (208Pb/207Pb) of 1.1279-1.1607 (2.3983-2.4302). Airborne Pb concentrations at one sampling site ranged from 0.42 to 6.0 ng/m3 with isotopic ratios of 1.1321-1.1427 (2.4029-2.4160). Air mass trajectory analysis combined with isotopic compositions of potential source regions did not show discernible evidence of the long-range atmospheric transport of pollutants. Isotopic ratios in the Alpine snow samples and thus the free troposphere were generally higher than airborne Pb isotopic ratios in urban France, which coupled with the relatively high Pb concentrations suggested a regional anthropogenic Pb source, probably Italy but possibly Eastern Europe.

Chlorine isotope geochemistry of Icelandic thermal fluids: Implications for geothermal system behavior at divergent plate boundaries

NASA Astrophysics Data System (ADS)

Stefánsson, Andri; Barnes, Jaime D.

2016-09-01

The chlorine isotope composition of thermal fluids from Iceland were measured in order to evaluate the source of chlorine and possible chlorine isotope fractionation in geothermal systems at divergent plate boundaries. The geothermal systems studied have a wide range of reservoir temperatures from 40 to 437 °C and in-situ pH of 6.15 to 7.15. Chlorine concentrations range from 5.2 to 171 ppm and δ37 Cl values are -0.3 to + 2.1 ‰ (n = 38). The δ37 Cl values of the thermal fluids are interpreted to reflect the source of the chlorine in the fluids. Geothermal processes such as secondary mineral formation, aqueous and vapor speciation and boiling were found to have minimal effects on the δ37 Cl values. However, further work is needed on incorporation of Cl into secondary minerals and its effect on Cl isotope fractionation. Results of isotope geochemical modeling demonstrate that the range of δ37 Cl values documented in the natural thermal fluids can be explained by leaching of the basaltic rocks by meteoric source water under geothermal conditions. Magmatic gas partitioning may also contribute to the source of Cl in some cases. The range of δ37 Cl values of the fluids result mainly from the large range of δ37 Cl values observed for Icelandic basalts, which range from -0.6 to + 1.2 ‰.

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

PubMed

Schweiger, Peter F

2016-10-20

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

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

Gundlach-Graham, Alexander W.; Dennis, Elise; Ray, Steven J.

Here we describe the first combination of a Distance-of-Flight Mass Spectrometry (DOFMS) instrument and an inductively coupled plasma (ICP) ion source. DOFMS is a velocity-based MS technique in which ions of a range of mass-to-charge (m/z) values are detected simultaneously along the length of a spatially selective detector. As a relative of time-of-flight (TOF) MS, DOFMS leverages benefits fromboth TOFMS and spatially dispersive MS. The simultaneous detection of groups of m/z values improves dynamic range by spreading ion signal across many detector elements and reduces correlated noise by signal ratioing. To ascertain the performance characteristics of the ICP-DOFMS instrument, wemore » have employed a microchannel-plate/phosphor detection assembly with a scientific CCD to capture images of the phosphor plate. With this simple (and commercially available) detection scheme, elemental detection limits from 2–30 ng L*1 and a linear dynamic range of 5 orders of magnitude (10–106 ng L1) have been demonstrated. Additionally, a competitive isotope-ratio precision of 0.1% RSD has been achieved with only a 6 s signal integration period. In addition to first figures of merit, this paper outlines technical considerations for the design of the ICP-DOFMS.« less

Tracing Carbon Flow from Primary Production to a Gulf Coast Salt Marsh Consumer, the Seaside Sparrow (Ammodramus maritimus)

NASA Astrophysics Data System (ADS)

Johnson, J. J.; Polito, M. J.; Olin, J.

2016-02-01

Determining the relative contributions of primary producers to salt marsh food webs is fundamental to understanding how these systems are structured. Biomarkers such as bulk carbon isotopes (13C/12C) and fatty acids have become popular tracers of trophic dynamics, based on the principle that the composition of biomarkers in consumer tissues is a reflection of the composition of these same biomarkers in a consumer's diet. However, the use of bulk stable isotope and fatty acid analyses to assess carbon flow in food webs is often hampered by confounding factors such as isotopic fractionation and fatty acid modifications that can occur between trophic levels. In contrast, compound-specific stable isotope analysis of amino acids may offer a more precise tracking of carbon flow through complex food webs. This is because the isotopic values of essential amino acids in consumer tissues are assimilated largely unchanged from their primary sources at the base of the food web. The aim of this study was to test the consistency of three different methods (bulk carbon stable isotope, fatty acid and compound-specific stable isotope analyses) while examining the carbon source pool underlying the diet of a common marsh consumer, the seaside sparrow (A. maritimus). This comparison allows us to gain a better idea of the relative merits of these analytical methods and contribute to a clearer model of overall trophic dynamics in a salt marsh food web.

Stable isotopes and elasmobranchs: tissue types, methods, applications and assumptions.

PubMed

Hussey, N E; MacNeil, M A; Olin, J A; McMeans, B C; Kinney, M J; Chapman, D D; Fisk, A T

2012-04-01

Stable-isotope analysis (SIA) can act as a powerful ecological tracer with which to examine diet, trophic position and movement, as well as more complex questions pertaining to community dynamics and feeding strategies or behaviour among aquatic organisms. With major advances in the understanding of the methodological approaches and assumptions of SIA through dedicated experimental work in the broader literature coupled with the inherent difficulty of studying typically large, highly mobile marine predators, SIA is increasingly being used to investigate the ecology of elasmobranchs (sharks, skates and rays). Here, the current state of SIA in elasmobranchs is reviewed, focusing on available tissues for analysis, methodological issues relating to the effects of lipid extraction and urea, the experimental dynamics of isotopic incorporation, diet-tissue discrimination factors, estimating trophic position, diet and mixing models and individual specialization and niche-width analyses. These areas are discussed in terms of assumptions made when applying SIA to the study of elasmobranch ecology and the requirement that investigators standardize analytical approaches. Recommendations are made for future SIA experimental work that would improve understanding of stable-isotope dynamics and advance their application in the study of sharks, skates and rays. © 2012 The Authors. Journal of Fish Biology © 2012 The Fisheries Society of the British Isles.

A global perspective on the trophic geography of sharks.

PubMed

Bird, Christopher S; Veríssimo, Ana; Magozzi, Sarah; Abrantes, Kátya G; Aguilar, Alex; Al-Reasi, Hassan; Barnett, Adam; Bethea, Dana M; Biais, Gérard; Borrell, Asuncion; Bouchoucha, Marc; Boyle, Mariah; Brooks, Edward J; Brunnschweiler, Juerg; Bustamante, Paco; Carlisle, Aaron; Catarino, Diana; Caut, Stéphane; Cherel, Yves; Chouvelon, Tiphaine; Churchill, Diana; Ciancio, Javier; Claes, Julien; Colaço, Ana; Courtney, Dean L; Cresson, Pierre; Daly, Ryan; de Necker, Leigh; Endo, Tetsuya; Figueiredo, Ivone; Frisch, Ashley J; Hansen, Joan Holst; Heithaus, Michael; Hussey, Nigel E; Iitembu, Johannes; Juanes, Francis; Kinney, Michael J; Kiszka, Jeremy J; Klarian, Sebastian A; Kopp, Dorothée; Leaf, Robert; Li, Yunkai; Lorrain, Anne; Madigan, Daniel J; Maljković, Aleksandra; Malpica-Cruz, Luis; Matich, Philip; Meekan, Mark G; Ménard, Frédéric; Menezes, Gui M; Munroe, Samantha E M; Newman, Michael C; Papastamatiou, Yannis P; Pethybridge, Heidi; Plumlee, Jeffrey D; Polo-Silva, Carlos; Quaeck-Davies, Katie; Raoult, Vincent; Reum, Jonathan; Torres-Rojas, Yassir Eden; Shiffman, David S; Shipley, Oliver N; Speed, Conrad W; Staudinger, Michelle D; Teffer, Amy K; Tilley, Alexander; Valls, Maria; Vaudo, Jeremy J; Wai, Tak-Cheung; Wells, R J David; Wyatt, Alex S J; Yool, Andrew; Trueman, Clive N

2018-02-01

Sharks are a diverse group of mobile predators that forage across varied spatial scales and have the potential to influence food web dynamics. The ecological consequences of recent declines in shark biomass may extend across broader geographic ranges if shark taxa display common behavioural traits. By tracking the original site of photosynthetic fixation of carbon atoms that were ultimately assimilated into muscle tissues of 5,394 sharks from 114 species, we identify globally consistent biogeographic traits in trophic interactions between sharks found in different habitats. We show that populations of shelf-dwelling sharks derive a substantial proportion of their carbon from regional pelagic sources, but contain individuals that forage within additional isotopically diverse local food webs, such as those supported by terrestrial plant sources, benthic production and macrophytes. In contrast, oceanic sharks seem to use carbon derived from between 30° and 50° of latitude. Global-scale compilations of stable isotope data combined with biogeochemical modelling generate hypotheses regarding animal behaviours that can be tested with other methodological approaches.

Strong variations in water vapor in the Asian Monsoon UTLS region observed during the 2017 StratoClim campaign

NASA Astrophysics Data System (ADS)

Moyer, E. J.; Clouser, B.; Sarkozy, L.; Gaeta, D. C.; Singer, C. E.

2017-12-01

The StratoClim campaign in July/August 2017 provided the first in-situ sampling in the UTLS region over the Asian monsoon. Preliminary results from high-precision water vapor measurements from a new instrument, the Chicago Water Isotope Spectrometer, imply substantial variation in water vapor above the local cold-point tropopause and above the 380 K potential temperature surface. Profiles across the cold-point tropopause and attendant variability appear to differ from those both in the Tropical Tropopause Layer in the deep tropics and in the North American Monsoon region. We discuss how these water vapor fluctuations relate to implied convective influence and variations in long-range transport. In at least some cases, enhanced water at high altitudes appears correlated with relative isotopic enhancement, suggesting convective influence. Although results at the time of writing are necessarily very preliminary, measurements suggest that the monsoon anticyclone region is characterized by dynamic transport and convective influence up to and beyond the local cold-point tropopause.

Increase in soil stable carbon isotope ratio relates to loss of organic carbon: results from five long-term bare fallow experiments.

PubMed

Menichetti, Lorenzo; Houot, Sabine; van Oort, Folkert; Kätterer, Thomas; Christensen, Bent T; Chenu, Claire; Barré, Pierre; Vasilyeva, Nadezda A; Ekblad, Alf

2015-03-01

Changes in the (12)C/(13)C ratio (expressed as δ(13)C) of soil organic C (SOC) has been observed over long time scales and with depth in soil profiles. The changes are ascribed to the different reaction kinetics of (12)C and (13)C isotopes and the different isotopic composition of various SOC pool components. However, experimental verification of the subtle isotopic shifts associated with SOC turnover under field conditions is scarce. We determined δ(13)C and SOC in soil sampled during 1929-2009 in the Ap-horizon of five European long-term bare fallow experiments kept without C inputs for 27-80 years and covering a latitudinal range of 11°. The bare fallow soils lost 33-65% of their initial SOC content and showed a mean annual δ(13)C increase of 0.008-0.024‰. The (13)C enrichment could be related empirically to SOC losses by a Rayleigh distillation equation. A more complex mechanistic relationship was also examined. The overall estimate of the fractionation coefficient (ε) was -1.2 ± 0.3‰. This coefficient represents an important input to studies of long-term SOC dynamics in agricultural soils that are based on variations in (13)C natural abundance. The variance of ε may be ascribed to site characteristics not disclosed in our study, but the very similar kinetics measured across our five experimental sites suggest that overall site-specific factors (including climate) had a marginal influence and that it may be possible to isolate a general mechanism causing the enrichment, although pre-fallow land use may have some impact on isotope abundance and fractionation.

Multiple sulfur-isotope signatures in Archean sulfates and their implications for the chemistry and dynamics of the early atmosphere

PubMed Central

Muller, Élodie; Philippot, Pascal; Rollion-Bard, Claire; Cartigny, Pierre

2016-01-01

Sulfur isotopic anomalies (∆33S and ∆36S) have been used to trace the redox evolution of the Precambrian atmosphere and to document the photochemistry and transport properties of the modern atmosphere. Recently, it was shown that modern sulfate aerosols formed in an oxidizing atmosphere can display important isotopic anomalies, thus questioning the significance of Archean sulfate deposits. Here, we performed in situ 4S-isotope measurements of 3.2- and 3.5-billion-year (Ga)-old sulfates. This in situ approach allows us to investigate the diversity of Archean sulfate texture and mineralogy with unprecedented resolution and from then on to deconvolute the ocean and atmosphere Archean sulfur cycle. A striking feature of our data is a bimodal distribution of δ34S values at ∼+5‰ and +9‰, which is matched by modern sulfate aerosols. The peak at +5‰ represents barite of different ages and host-rock lithology showing a wide range of ∆33S between −1.77‰ and +0.24‰. These barites are interpreted as primary volcanic emissions formed by SO2 photochemical processes with variable contribution of carbonyl sulfide (OCS) shielding in an evolving volcanic plume. The δ34S peak at +9‰ is associated with non–33S-anomalous barites displaying negative ∆36S values, which are best interpreted as volcanic sulfate aerosols formed from OCS photolysis. Our findings confirm the occurrence of a volcanic photochemical pathway specific to the early reduced atmosphere but identify variability within the Archean sulfate isotope record that suggests persistence throughout Earth history of photochemical reactions characteristic of the present-day stratosphere. PMID:27330111

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Sedimentary Geochemical and Palynological Evidence of Late-Holocene Paleoenvironmental Change from Baradères Bay, Haiti

NASA Astrophysics Data System (ADS)

Farrington, E. J.; Lane, C.; Hawkes, A.; Donnelly, J. P.; van Hengstum, P. J.; Woodruff, J. D.; Maio, C. V.; Grochocki, K. K.; Taylor, A. K.

2017-12-01

Paleoclimate studies in equatorial regions are essential to decipher the forcing mechanisms controlling tropical precipitation dynamics. Caribbean paleoclimate records are particularly sensitive to changes in tropical convection, as they reside on the edge of the annual migrational range of the Intertropical Convergence Zone and record perturbations to many Pacific and Atlantic climate forcings. Significant sub-regional variability exists in the modern Caribbean climate and responsible forcing mechanisms on centennial to millennial timescales are largely unresolved, as reliable paleohydrological records are geographically sparse. In this study we aim to determine regional paleoenvironmental change with a specific interest in an abrupt dry period between 3200 and 2400 14C yr BP inferred from an oxygen isotope record from the nearby Lake Miragoâne, Haiti. Chronologically synchronous results from a Barbados stalagmite indicate wet conditions, which imply contrasting sub-regional hydrological responses between the northern and southern Caribbean basin. The development of multiple proximal paleoenvironmental records allows for better assessment of sub-regional Caribbean climate dynamics and the verification of existing proxy trends. We are conducting multi-proxy analyses on a 6360 14C yr, 9-meter sediment core extracted from Baradères Bay, Haiti, including loss on ignition (LOI), bulk sediment carbon (δ13C) and nitrogen (δ15N) isotope geochemistry, n-alkane hydrogen (δD) isotope geochemistry, x-ray fluorescence (XRF), and fossil pollen counts. Preliminary LOI data reveal that between 6400 and 3000 14C yr B.P. inorganic carbon ranged from 15 to 30% and organic carbon from 8 to 20%. From 3000 14C yr B.P. to present organic content decreased (9 - 13%) and inorganic carbon content increased (28 - 30%). Preliminary pollen analyses show a decrease in Rhizophora (red mangrove) pollen abundances between 3000 and 4000 14C yr BP, possibly indicating a change in estuary salinity. Additionally, XRF data show low concentrations of titanium and zircon between 5600 and 6200 14C yr BP, which may indicate a reduction in terrestrial material input. Forthcoming δD analyses of terrestrially-derived n-alkanes should help to elucidate potential paleohydrologic mechanisms responsible for the apparent changes.

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

NASA Astrophysics Data System (ADS)

Kavner, Abby; Bonet, François; Shahar, Anat; Simon, Justin; Young, Edward

2005-06-01

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from -0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ 56Fe values (relative to IRMM-14) ranging from -0.18(±0.02) to -2.290(±0.006) ‰, and corresponding δ 57Fe values of -0.247(±0.014) and -3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus's theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.

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

EPA Science Inventory

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Discriminating fluid source regions in orogenic gold deposits using B-isotopes

NASA Astrophysics Data System (ADS)

Lambert-Smith, James S.; Rocholl, Alexander; Treloar, Peter J.; Lawrence, David M.

2016-12-01

The genesis of orogenic gold deposits is commonly linked to hydrothermal ore fluids derived from metamorphic devolatilization reactions. However, there is considerable debate as to the ultimate source of these fluids and the metals they transport. Tourmaline is a common gangue mineral in orogenic gold deposits. It is stable over a very wide P-T range, demonstrates limited volume diffusion of major and trace elements and is the main host of B in most rock types. We have used texturally resolved B-isotope analysis by secondary ion mass spectrometry (SIMS) to identify multiple fluid sources within a single orogenic gold ore district. The Loulo Mining District in Mali, West Africa hosts several large orogenic gold ore bodies with complex fluid chemistry, associated with widespread pre-ore Na- and multi-stage B-metasomatism. The Gara deposit, as well as several smaller satellites, formed through partial mixing between a dilute aqueous-carbonic fluid and a hypersaline brine. Hydrothermal tourmaline occurs as a pre-ore phase in the matrix of tourmalinite units, which host mineralization in several ore bodies. Clasts of these tourmalinites occur in mineralized breccias. Disseminated hydrothermal and vein hosted tourmaline occur in textural sites which suggest growth during and after ore formation. Tourmalines show a large range in δ11B values from -3.5 to 19.8‰, which record a change in fluid source between paragenetic stages of tourmaline growth. Pre-mineralization tourmaline crystals show heavy δ11B values (8-19.8‰) and high X-site occupancy (Na ± Ca; 0.69-1 apfu) suggesting a marine evaporite source for hydrothermal fluids. Syn-mineralization and replacement phases show lighter δ11B values (-3.5 to 15.1‰) and lower X-site occupancy (0.62-0.88 apfu), suggesting a subsequent influx of more dilute fluids derived from devolatilization of marine carbonates and clastic metasediments. The large, overlapping range in isotopic compositions and a skew toward the opposing population in the δ11B data for both tourmaline groups reflects continual tourmaline growth throughout mineralization, which records the process of fluid mixing. A peak in δ11B values at ∼8‰ largely controlled by tourmalines of syn- to post-ore timing represents a mixture of the two isotopically distinct fluids. This paper demonstrates that B-isotopes in tourmaline can be instrumental in interpreting complex and dynamic hydrothermal systems. The importance of B as an integral constituent of orogenic ore forming fluids and as a gangue phase in orogenic gold deposits makes B-isotope analysis a powerful tool for testing the level of source region variability in these fluids, and by extension, that of metal sources.

Biogeochemical Indicators in High- and Low-Arctic Marine and Terrestrial Avian Community Changes: Comparative Isotopic (13C, 15N, and 34S) Studies in Alaska and Greenland

NASA Astrophysics Data System (ADS)

Causey, D.; Bargmann, N. A.; Burnham, K. K.; Burnham, J. L.; Padula, V. M.; Johnson, J. A.; Welker, J. M.

2011-12-01

Understanding the complex dynamics of environmental change in northern latitudes is of paramount importance today, given documented rapid shifts in sea ice, plant phenology, temperatures, deglaciation, and habitat fidelity. This knowledge is particularly critical for Arctic avian communities, which are integral components by which biological teleconnections are maintained between the mid and northern latitudes. Furthermore, Arctic birds are fundamental to Native subsistence lifestyles and a focus for conservation activities. Avian communities of marine and terrestrial Arctic environments represent a broad spectrum of trophic levels, from herbivores (eg., geese Chen spp.), planktivores (eg., auklets Aethia spp.), and insectivores (eg., passerines: Wheatears Oenanthe spp., Longspurs Calcarius spp.), to predators of marine invertebrates (eg., eiders Somateria spp.), nearshore and offshore fish (eg., cormorants Phalacrocorax spp, puffins Fratercula spp.), even other bird species (eg., gulls Larus spp., falcons Peregrinus spp.). This diversity of trophic interconnections is an integral factor in the dynamics of Arctic ecosystem ecology, and they are key indicators for the strength and trajectories of change. We are especially interested in their feeding ecology, using stable isotope-diet relations to examine historical diets and to predict future feeding ecology by this range of species. Since 2009, we have been studying the foodweb ecology using stable isotopes (δ13C, δ15N, δ34S) of contemporaneous coastal and marine bird communities in High Arctic (Northwest Greenland) and Low Arctic (western Aleutian Islands, AK). We are quantifying the isotopic values of blood, organ tissues, and feathers, and have carried out comparisons between native and lipid-extracted samples. Although geographically distant, these communities comprise similar taxonomic and ecological congeners, including several species common to both (eg., Common Eider, Black-legged Kittiwake, Northern Fulmar). Generally, High Arctic species have tissues that are more enriched in δ15N compared to their Low Arctic counterparts, but δ13C values are similar in both regions. These patterns follow observed regional differences in Arctic isoscapes, and are probably related to isotopic variations in food rather than trophic level differentiation. Both Low- and High-Arctic bird communities show decadal-period shifts in stable isotope profiles, based on prior published results and previously collected specimens. For example, Aleutian birds feeding in upper trophic levels have tissues are more enriched in both δ13C and δ15N compared to specimens collected in 2000-2001. We anticipate broadening the time depth of this initial study using museum archival and archeological material, as well as continuing studies in 2013 and 2014.

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.

Quantitative Proteomics by Metabolic Labeling of Model Organisms*

PubMed Central

Gouw, Joost W.; Krijgsveld, Jeroen; Heck, Albert J. R.

2010-01-01

In the biological sciences, model organisms have been used for many decades and have enabled the gathering of a large proportion of our present day knowledge of basic biological processes and their derailments in disease. Although in many of these studies using model organisms, the focus has primarily been on genetics and genomics approaches, it is important that methods become available to extend this to the relevant protein level. Mass spectrometry-based proteomics is increasingly becoming the standard to comprehensively analyze proteomes. An important transition has been made recently by moving from charting static proteomes to monitoring their dynamics by simultaneously quantifying multiple proteins obtained from differently treated samples. Especially the labeling with stable isotopes has proved an effective means to accurately determine differential expression levels of proteins. Among these, metabolic incorporation of stable isotopes in vivo in whole organisms is one of the favored strategies. In this perspective, we will focus on methodologies to stable isotope label a variety of model organisms in vivo, ranging from relatively simple organisms such as bacteria and yeast to Caenorhabditis elegans, Drosophila, and Arabidopsis up to mammals such as rats and mice. We also summarize how this has opened up ways to investigate biological processes at the protein level in health and disease, revealing conservation and variation across the evolutionary tree of life. PMID:19955089

A Teaching Exercise to Introduce Stable Isotope Fractionation of Metals into Geochemistry Courses

ERIC Educational Resources Information Center

Weiss, Dominik J.; Harris, Caroline; Maher, Kate; Bullen, Thomas

2013-01-01

Variations in the isotopic composition of elements have been widely used to study earth's climate, biosphere, and interior, and more recently to track the fate of contaminants. Within the broad range of elements that exhibit measureable isotopic variations, metal stable isotopes are increasingly applied across the biological, geological,…

Specific 13C labeling of leucine, valine and isoleucine methyl groups for unambiguous detection of long-range restraints in protein solid-state NMR studies

NASA Astrophysics Data System (ADS)

Fasshuber, Hannes Klaus; Demers, Jean-Philippe; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

2015-03-01

Here we present an isotopic labeling strategy to easily obtain unambiguous long-range distance restraints in protein solid-state NMR studies. The method is based on the inclusion of two biosynthetic precursors in the bacterial growth medium, α-ketoisovalerate and α-ketobutyrate, leading to the production of leucine, valine and isoleucine residues that are exclusively 13C labeled on methyl groups. The resulting spectral simplification facilitates the collection of distance restraints, the verification of carbon chemical shift assignments and the measurement of methyl group dynamics. This approach is demonstrated on the type-three secretion system needle of Shigella flexneri, where 49 methyl-methyl and methyl-nitrogen distance restraints including 10 unambiguous long-range distance restraints could be collected. By combining this labeling scheme with ultra-fast MAS and proton detection, the assignment of methyl proton chemical shifts was achieved.

Stable δ15N and δ13C isotope ratios in aquatic ecosystems

PubMed Central

Wada, Eitaro

2009-01-01

In the past 20 years, rapid progress in stable isotope (SI) studies has allowed scientists to observe natural ecosystems from entirely new perspectives. This report addresses the fundamental concepts underlying the use of the SI ratio. The unique characteristics of the SI ratio make it an interdisciplinary parameter that acts as a chemical fingerprint of biogenic substances and provides a key to the world of isotopomers. Variations in SI ratios of biogenic substances depend on the isotopic compositions of reactants, the pathways and kinetic modes of reaction dynamics, and the physicochemical conditions. In fact, every biogenic material has its own isotopic composition, its “dynamic SI fingerprint”, which is governed by its function and position in the material flow. For example, the relative SI ratio in biota is determined by dietary lifestyle, e.g., the modes of drinking, eating, and excreting, and appears highly regular due to the physicochemical differences of isotopomers. Our primary goal here is to elucidate the general principals of isotope partitioning in major biophilic elements in molecules, biogenic materials, and ecosystems (Wada, E. et al., 1995). To this end, the nitrogen and carbon SI distribution ratios (δ15N and δ13C, respectively) are used to examine materials cycling, food web structures, and their variability in various kinds of watershed-including aquatic ecosystems to elucidate an “isotopically ordered world”. PMID:19282646

Assessing the statistical robustness of inter- and intra-basinal carbon isotope chemostratigraphic correlation

NASA Astrophysics Data System (ADS)

Hay, C.; Creveling, J. R.; Huybers, P. J.

2016-12-01

Excursions in the stable carbon isotopic composition of carbonate rocks (δ13Ccarb) can facilitate correlation of Precambrian and Phanerozoic sedimentary successions at a higher temporal resolution than radiometric and biostratigraphic frameworks typically afford. Within the bounds of litho- and biostratigraphic constraints, stratigraphers often correlate isotopic patterns between distant stratigraphic sections through visual alignment of local maxima and minima of isotopic values. The reproducibility of this method can prove challenging and, thus, evaluating the statistical robustness of intrabasinal composite carbon isotope curves, and global correlations to these reference curves, remains difficult. To assess the reproducibility of stratigraphic alignment of δ13Ccarb data, and correlations between carbon isotope excursions, we employ a numerical dynamic time warping methodology that stretches and squeezes the time axis of a record to obtain an optimal correlation (in a least-squares sense) between time-uncertain series of data. In particular, we assess various alignments between series of Early Cambrian δ13Ccarb data with respect to plausible matches. We first show that an alignment of these records obtained visually, and published previously, is broadly reproducible using dynamic time warping. Alternative alignments with similar goodness of fits are also obtainable, and their stratigraphic plausibility are discussed. This approach should be generalizable to an algorithm for the purposes of developing a library of plausible alignments between multiple time-uncertain stratigraphic records.

Fine root heterogeneity by branch order: exploring the discrepancy in root turnover estimates between minirhizotron and carbon isotopic methods

Treesearch

Dali Guo; Harbin Li; Robert J. Mitchell; Han Wenxuan; Joseph J. Hendricks; Timothy J. Fahey; Ronald L. Hendrick

2008-01-01

Fine roots constitute a large and dynamic component of the carbon cycles of terrestrial ecosystems. The reported fivefold discrepancy in turnover estimates between median longevity (ML) from minirhizotrons and mean residence time (MRT) using carbon isotopes may have global consequences.

Metal Stable Isotope Tagging: Renaissance of Radioimmunoassay for Multiplex and Absolute Quantification of Biomolecules.

PubMed

Liu, Rui; Zhang, Shixi; Wei, Chao; Xing, Zhi; Zhang, Sichun; Zhang, Xinrong

2016-05-17

The unambiguous quantification of biomolecules is of great significance in fundamental biological research as well as practical clinical diagnosis. Due to the lack of a detectable moiety, the direct and highly sensitive quantification of biomolecules is often a "mission impossible". Consequently, tagging strategies to introduce detectable moieties for labeling target biomolecules were invented, which had a long and significant impact on studies of biomolecules in the past decades. For instance, immunoassays have been developed with radioisotope tagging by Yalow and Berson in the late 1950s. The later languishment of this technology can be almost exclusively ascribed to the use of radioactive isotopes, which led to the development of nonradioactive tagging strategy-based assays such as enzyme-linked immunosorbent assay, fluorescent immunoassay, and chemiluminescent and electrochemiluminescent immunoassay. Despite great success, these strategies suffered from drawbacks such as limited spectral window capacity for multiplex detection and inability to provide absolute quantification of biomolecules. After recalling the sequences of tagging strategies, an apparent question is why not use stable isotopes from the start? A reasonable explanation is the lack of reliable means for accurate and precise quantification of stable isotopes at that time. The situation has changed greatly at present, since several atomic mass spectrometric measures for metal stable isotopes have been developed. Among the newly developed techniques, inductively coupled plasma mass spectrometry is an ideal technique to determine metal stable isotope-tagged biomolecules, for its high sensitivity, wide dynamic linear range, and more importantly multiplex and absolute quantification ability. Since the first published report by our group, metal stable isotope tagging has become a revolutionary technique and gained great success in biomolecule quantification. An exciting research highlight in this area is the development and application of the mass cytometer, which fully exploited the multiplexing potential of metal stable isotope tagging. It realized the simultaneous detection of dozens of parameters in single cells, accurate immunophenotyping in cell populations, through modeling of intracellular signaling network and undoubted discrimination of function and connection of cell subsets. Metal stable isotope tagging has great potential applications in hematopoiesis, immunology, stem cells, cancer, and drug screening related research and opened a post-fluorescence era of cytometry. Herein, we review the development of biomolecule quantification using metal stable isotope tagging. Particularly, the power of multiplex and absolute quantification is demonstrated. We address the advantages, applicable situations, and limitations of metal stable isotope tagging strategies and propose suggestions for future developments. The transfer of enzymatic or fluorescent tagging to metal stable isotope tagging may occur in many aspects of biological and clinical practices in the near future, just as the revolution from radioactive isotope tagging to fluorescent tagging happened in the past.

Use of isotopic spike from Tropical Storm to understand water exchange on large scale: study case of Rafael Storm in the Lesser Antilles archipelago, October 2012.

NASA Astrophysics Data System (ADS)

Lambs, Luc

2014-05-01

Aim The tracking of the rainfall from Tropical Storm Raphael of mid October 2012 was used to better understand how the eco-hydrology and the water cycle function in wet areas, such as mangrove growing in salty ponds on a number of tropical islands. Location Guadeloupe and Saint Martin Islands in the Leeward Islands archipelago, Lesser Antilles. Methods Compared to normal tropical rainfall, tropical storms display distinct depleted heavy stable water isotopes which can be used as isotopic spikes to understand these special rainfall inflows. Rainfall, groundwater, river and pond water were sampled before, during and after the storm. Results In Guadeloupe where the tropical storm started, the rainfall isotopic signal reached values of d18O= -9 to -8 o on October 12-14th 2012, whereas the normal range is d18O= -4 to -2 o as measured from 2009 to 2012. It was possible to detect such a depleted signal in the groundwater and in the mangrove forest during the days after the storm event. Main conclusions The use of such natural isotopic spikes provides an opportunity to obtain a dynamic and time reference on a large scale for the study of the hydro-ecosystems and the effects on the impacted tropical islands. A few days after the cyclone, the isotopic spikes were found in river, groundwater and mangrove water pools with values up to d18O= -8.6 o . For the water basins on the windward side, the downhill salty pond water was almost completely renewed. By contrast, only 20 to 50 % of the water in the ponds located on the leeward side was renewed. No specific elevation in the d-excess values was noted, certainly due to the relatively long distance from the eye of the storm (180 to 300 km), which meant that there was no spray water evaporative process.

Controlling for anthropogenically induced atmospheric variation in stable carbon isotope studies

USGS Publications Warehouse

Long, E.S.; Sweitzer, R.A.; Diefenbach, D.R.; Ben-David, M.

2005-01-01

Increased use of stable isotope analysis to examine food-web dynamics, migration, transfer of nutrients, and behavior will likely result in expansion of stable isotope studies investigating human-induced global changes. Recent elevation of atmospheric CO2 concentration, related primarily to fossil fuel combustion, has reduced atmospheric CO2 ??13C (13C/12C), and this change in isotopic baseline has, in turn, reduced plant and animal tissue ??13C of terrestrial and aquatic organisms. Such depletion in CO2 ??13C and its effects on tissue ??13C may introduce bias into ??13C investigations, and if this variation is not controlled, may confound interpretation of results obtained from tissue samples collected over a temporal span. To control for this source of variation, we used a high-precision record of atmospheric CO2 ??13C from ice cores and direct atmospheric measurements to model modern change in CO2 ??13C. From this model, we estimated a correction factor that controls for atmospheric change; this correction reduces bias associated with changes in atmospheric isotopic baseline and facilitates comparison of tissue ??13C collected over multiple years. To exemplify the importance of accounting for atmospheric CO2 ??13C depletion, we applied the correction to a dataset of collagen ??13C obtained from mountain lion (Puma concolor) bone samples collected in California between 1893 and 1995. Before correction, in three of four ecoregions collagen ??13C decreased significantly concurrent with depletion of atmospheric CO2 ??13C (n ??? 32, P ??? 0.01). Application of the correction to collagen ??13C data removed trends from regions demonstrating significant declines, and measurement error associated with the correction did not add substantial variation to adjusted estimates. Controlling for long-term atmospheric variation and correcting tissue samples for changes in isotopic baseline facilitate analysis of samples that span a large temporal range. ?? Springer-Verlag 2005.

Surface oceanographic fronts influencing deep-sea biological activity: Using fish stable isotopes as ecological tracers

NASA Astrophysics Data System (ADS)

Louzao, Maite; Navarro, Joan; Delgado-Huertas, Antonio; de Sola, Luis Gil; Forero, Manuela G.

2017-06-01

Ecotones can be described as transition zones between neighbouring ecological systems that can be shaped by environmental gradients over a range of space and time scales. In the marine environment, the detection of ecotones is complex given the highly dynamic nature of marine systems and the paucity of empirical data over ocean-basin scales. One approach to overcome these limitations is to use stable isotopes from animal tissues since they can track spatial oceanographic variability across marine systems and, in turn, can be used as ecological tracers. Here, we analysed stable isotopes of deep-sea fishes to assess the presence of ecological discontinuities across the western Mediterranean. We were specifically interested in exploring the connection between deep-sea biological activity and particular oceanographic features (i.e., surface fronts) occurring in the pelagic domain. We collected samples for three different abundant deep-sea species in May 2004 from an experimental oceanographic trawling cruise (MEDITS): the Mictophydae jewel lanternfish Lampanyctus crocodilus and two species of the Gadidae family, the silvery pout Gadiculus argenteus and the blue whiting Micromesistius poutassou. The experimental survey occurred along the Iberian continental shelf and the upper and middle slopes, from the Strait of Gibraltar in the SW to the Cape Creus in the NE. The three deep-sea species were highly abundant throughout the study area and they showed geographic variation in their isotopic values, with decreasing values from north to south disrupted by an important change point around the Vera Gulf. Isotopic latitudinal gradients were explained by pelagic oceanographic conditions along the study area and confirm the existence of an ecotone at the Vera Gulf. This area could be considered as an oceanographic boundary where waters of Atlantic origin meet Mediterranean surface waters forming important frontal structures such as the Almeria-Oran front. In fact, our results relate geographical variation in stable isotopes of deep-sea fishes to regional changes in surface oceanography, highlighting the importance of mesoscale oceanographic features.

Understanding key drivers controlling daily stable isotope variations in precipitation of Costa Rica, Central America

NASA Astrophysics Data System (ADS)

Sanchez-Murillo, Ricardo; Welsh, Kristin; Birkel, Christian; Esquivel-Hernández, Germain; Corrales-Salazar, Jose; Boll, Jan; Brooks, Erin; Roupsard, Olivier; Katchan, Irina; Arce-Mesén, Rafael; Soulsby, Chris; Araguás-Araguás, Luis

2015-04-01

Costa Rica is located on the Central American Isthmus, which receives direct moisture inputs from the Caribbean Sea and the Pacific Ocean. The relatively narrow, but high relief Central American land bridge is characterized by unique mountainous and lowland microclimates. However, only limited knowledge exists about the impact of relief and regional atmospheric circulation patterns on precipitation origin, transport, and isotopic composition in this tropical region. Therefore, the main scope of this study is to identify the key drivers controlling variations in meteoric waters of Costa Rica using stable isotopes based on daily sample collection for the year 2013. The monitoring sites comprise three strategic locations across Costa Rica: Heredia (Central Valley), Turrialba (Caribbean slope), and Caño Seco (South Pacific slope). Sporadic dry season rain is mostly related to isolated enriched events ranging from -5.8‰ d18O up to -0.9‰ d18O. By mid-May, the Intertropical Convergence Zone reaches Costa Rica resulting in a notable depletion in isotope ratios (up to -18.5‰ d18O). HYSPLIT back air mass trajectories indicate the strong influence on the origin and transport of precipitation of two main moisture transport mechanisms, the Caribbean Low Level Jet and the Colombian Low Level Jet as well as localized convection events. Multiple linear regression models constructed based on Random Forests of surface meteorological information and atmospheric sounding profiles suggest that Lifted Condensation Level and surface relative humidity are the main factors controlling isotopic variations. These findings diverge from the recognized 'amount effect' in monthly composite samples across the tropics. Understanding of stable isotope dynamics in tropical precipitation can be used to enhance catchment and groundwater modeling efforts in ungauged basins where scarcity of long-term monitoring data drastically limit current and future water resources management.

The effect of plasma impurities on the sputtering of tungsten carbide

NASA Astrophysics Data System (ADS)

Vörtler, K.; Björkas, C.; Nordlund, K.

2011-03-01

Understanding of sputtering by ion bombardment is needed in a wide range of applications. In fusion reactors, ion impacts originating from a hydrogen-isotope-rich plasma will lead, among other effects, to sputtering of the wall material. To study the effect of plasma impurities on the sputtering of the wall mixed material tungsten carbide molecular dynamics simulations were carried out. Simulations of cumulative D cobombardment with C, W, He, Ne or Ar impurities on crystalline tungsten carbide were performed in the energy range 100-300 eV. The sputtering yields obtained at low fluences were compared to steady state SDTrimSP yields. During bombardment single C atom sputtering was preferentially observed. We also detected significant WxCy molecule sputtering. We found that this molecule sputtering mechanism is of physical origin.

Isotopic Evolution of Soil Organic Matter Affects Paleo-vegetation and Paleo-pCO2 Reconstructions

NASA Astrophysics Data System (ADS)

Bowen, G. J.; Beerling, D. J.

2004-12-01

The stable carbon isotope ratio (\\delta13C) of fossil terrestrial organic matter is used to study several aspects of biosphere/atmosphere coupling in the geologic past. These range from vegetation response to climatic and pCO2 shifts to reconstruction of paleo-pCO2 levels. Although screening for diagenesis is typical in these studies, few have taken into account the ubiquitous but poorly understood phenomenon of progressive 13C-enrichment of soil organic matter during its decay, which is observed in modern soils worldwide. We present a simple model that describes this phenomenon and the interaction of soil organic carbon and CO2 concentrations, fluxes and \\delta13C values. At its most basic level, the model suggests that bulk organic matter from sub-surface soil horizons will be variably enriched in 13C relative to the vegetation living on the soil surface. This complicates interpretation of paleo-isotopic records used in C3/C4 vegetation reconstructions, and may account for anomalously heavy fossil organic carbon isotope values measured in some paleosols pre-dating the end-Miocene expansion of C4 floras. The model also demonstrates that the \\delta13C evolution of soil organic carbon during its decay generates 2 types of biases that may affect soil mineral paleo-pCO2 proxies. The first type of bias results from a steady-state inequality between the \\delta13C of organic carbon at a single depth within the soil and that of respired CO2 in the soil. This bias is present when fossil organic matter is used to reconstruct the \\delta13C of soil-respired carbon, and can be minimized with appropriate sampling methods. The second type of bias results from a dynamic, seasonal imbalance in respiration, which may cause the soil \\delta13CO2 flux during times of soil mineral formation to deviate from that of the annually integrated flux. At present, this bias can not be fully described or corrected for due to inadequacies in our knowledge of soil \\delta13C dynamics and the timing of soil mineral formation. Given the strong dependence of paleo-pCO2 reconstructions on data from soil mineral isotopes, further work on these topics is warranted.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Continual in situ monitoring of pore water stable isotopes in the subsurface

NASA Astrophysics Data System (ADS)

Volkmann, T. H. M.; Weiler, M.

2014-05-01

Stable isotope signatures provide an integral fingerprint of origin, flow paths, transport processes, and residence times of water in the environment. However, the full potential of stable isotopes to quantitatively characterize subsurface water dynamics is yet unfolded due to the difficulty in obtaining extensive, detailed, and repeated measurements of pore water in the unsaturated and saturated zone. This paper presents a functional and cost-efficient system for non-destructive continual in situ monitoring of pore water stable isotope signatures with high resolution. Automatic controllable valve arrays are used to continuously extract diluted water vapor in soil air via a branching network of small microporous probes into a commercial laser-based isotope analyzer. Normalized liquid-phase isotope signatures are then obtained based on a specific on-site calibration approach along with basic corrections for instrument bias and temperature dependent isotopic fractionation. The system was applied to sample depth profiles on three experimental plots with varied vegetation cover in southwest Germany. Two methods (i.e., based on advective versus diffusive vapor extraction) and two modes of sampling (i.e., using multiple permanently installed probes versus a single repeatedly inserted probe) were tested and compared. The results show that the isotope distribution along natural profiles could be resolved with sufficiently high accuracy and precision at sampling intervals of less than four minutes. The presented in situ approaches may thereby be used interchangeably with each other and with concurrent laboratory-based direct equilibration measurements of destructively collected samples. It is thus found that the introduced sampling techniques provide powerful tools towards a detailed quantitative understanding of dynamic and heterogeneous shallow subsurface and vadose zone processes.

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

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

The clumped-isotope geochemistry of exhumed marbles from Naxos, Greece

NASA Astrophysics Data System (ADS)

Ryb, U.; Lloyd, M. K.; Stolper, D. A.; Eiler, J. M.

2017-07-01

Exhumation and accompanying retrograde metamorphism alter the compositions and textures of metamorphic rocks through deformation, mineral-mineral reactions, water-rock reactions, and diffusion-controlled intra- and inter-mineral atomic mobility. Here, we demonstrate that these processes are recorded in the clumped- and single-isotope (δ13 C and δ18 O) compositions of marbles, which can be used to constrain retrograde metamorphic histories. We collected 27 calcite and dolomite marbles along a transect from the rim to the center of the metamorphic core-complex of Naxos (Greece), and analyzed their carbonate single- and clumped-isotope compositions. The majority of Δ47 values of whole-rock samples are consistent with exhumation- controlled cooling of the metamorphic complex. However, the data also reveal that water-rock interaction, deformation driven recrystallization and thermal shock associated with hydrothermal alteration may considerably impact the overall distribution of Δ47 values. We analyzed specific carbonate fabrics influenced by deformation and fluid-rock reaction to study how these processes register in the carbonate clumped-isotope system. Δ47 values of domains drilled from a calcite marble show a bimodal distribution. Low Δ47 values correspond to an apparent temperature of 260 °C and are common in static fabrics; high Δ47 values correspond to an apparent temperature of 200 °C and are common in dynamically recrystallized fabrics. We suggest that the low Δ47 values reflect diffusion-controlled isotopic reordering during cooling, whereas high Δ47 values reflect isotopic reordering driven by dynamic recrystallization. We further studied the mechanism by which dynamic recrystallization may alter Δ47 values by controlled heating experiments. Results show no significant difference between laboratory reactions rates in the static and dynamic fabrics, consistent with a mineral-extrinsic mechanism, in which slip along crystal planes was associated with atomic-scale isotopic reordering in the calcite lattice. An intrinsic mechanism (enhanced isotopic reordering rate in deformed minerals) is contraindicated by these experiments. We suggest that Δ47 values of dynamically recrystallized fabrics that form below the diffusion-controlled blocking-temperature for calcite constrain the temperature of deformation. We find that Δ47-based temperatures of static fabrics from Naxos marbles are ∼60-80 °C higher than commonly observed in slowly cooled metamorphic rocks, and would suggest cooling rates of ∼105 °CMyr-1. A similar thermal history is inferred for dolomite marbles from the core vicinity, which preserve apparent temperatures up to 200 °C higher than a typical blocking temperature (∼300 °C). This finding could be explained by a hydrothermal event driving a brief thermal pulse and locally resetting Δ47 values. Rapid cooling of the core-complex region is consistent with a compilation of published cooling ages and a new apatite U-Th/He age, associating the thermal event with the emplacement of a granodiorite pluton at ∼12 Ma.

Polarization IR spectra of hydrogen bonded pyrazole crystals: self-organization effects in proton and deuteron mixture systems. Long-range H/D isotopic effects

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Machelska, Aleksandra

2002-02-01

This paper deals with experimental studies of the polarization IR spectra of solid-state pyrazole H1345, as well as of its H1D345, D1H345 and D1345 deuterium derivatives. Spectra were measured for the νNH and νND band frequency ranges at temperatures of 298 and 77 K. The spectra were found to strongly change their intensity distribution and their polarization properties with the decrease of temperature. These effects were ascribed to some temperature-induced conformational changes in the hydrogen bond lattices. The studies reported allowed the finding of new kind of isotopic effects H/D in the open-chain hydrogen bond systems, i.e. the self-organization effects. It was found that the spectrally active aggregates of hydrogen bonds remain unchanged despite the growing isotope H/D exchange rate. This statement was supported by analysis of the residual polarized νNH and νND band properties, measured for the isotopically diluted crystalline samples. Analysis of the band shapes of the four hydrogen isotope derivative crystals proved the existence of another kind of H/D isotopic effect, i.e. the long-range isotopic effect. It depends on an influence of the pyrazole ring hydrogen atoms onto the νNH and νND band widths and onto the band fine structures.

Preliminary investigation of electrothermal vaporization sample introduction for inductively coupled plasma time-of-flight mass spectrometry.

PubMed

Mahoney, P P; Ray, S J; Li, G; Hieftje, G M

1999-04-01

The coupling of an electrothermal vaporization (ETV) apparatus to an inductively coupled plasma time-of-flight mass spectrometer (ICP-TOFMS) is described. The ability of the ICP-TOFMS to produce complete elemental mass spectra at high repetition rates is experimentally demonstrated. A signal-averaging data acquisition board is employed to rapidly record complete elemental spectra throughout the vaporization stage of the ETV temperature cycle; a solution containing 34 elements is analyzed. The reduction of both molecular and atomic isobaric interferences through the temperature program of the furnace is demonstrated. Isobaric overlaps among the isotopes of cadmium, tin, and indium are resolved by exploiting differences in the vaporization characteristics of the elements. Figures of merit for the system are defined with several different data acquisition schemes capable of operating at the high repetition rate of the TOF instrument. With the use of both ion counting and a boxcar averager, the dynamic range is shown to be linear over a range of at least 6 orders of magnitude. A pair of boxcar averagers are used to measure the isotope ratio for silver with a precision of 1.9% RSD, despite a cycle-to-cycle precision of 19% RSD. Detection limits of 10-80 fg are calculated for seven elements, based upon a 10-microL injection.

Humpback whale diets respond to variance in ocean climate and ecosystem conditions in the California Current.

PubMed

Fleming, Alyson H; Clark, Casey T; Calambokidis, John; Barlow, Jay

2016-03-01

Large, migratory predators are often cited as sentinel species for ecosystem processes and climate-related changes, but their utility as indicators is dependent upon an understanding of their response to environmental variability. Documentation of the links between climate variability, ecosystem change and predator dynamics is absent for most top predators. Identifying species that may be useful indicators and elucidating these mechanistic links provides insight into current ecological dynamics and may inform predictions of future ecosystem responses to climatic change. We examine humpback whale response to environmental variability through stable isotope analysis of diet over a dynamic 20-year period (1993-2012) in the California Current System (CCS). Humpback whale diets captured two major shifts in oceanographic and ecological conditions in the CCS. Isotopic signatures reflect a diet dominated by krill during periods characterized by positive phases of the North Pacific Gyre Oscillation (NPGO), cool sea surface temperature (SST), strong upwelling and high krill biomass. In contrast, humpback whale diets are dominated by schooling fish when the NPGO is negative, SST is warmer, seasonal upwelling is delayed and anchovy and sardine populations display increased biomass and range expansion. These findings demonstrate that humpback whales trophically respond to ecosystem shifts, and as a result, their foraging behavior is a synoptic indicator of oceanographic and ecological conditions across the CCS. Multi-decadal examination of these sentinel species thus provides insight into biological consequences of interannual climate fluctuations, fundamental to advancing ecosystem predictions related to global climate change. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.

Hf-Nd Isotopic Correlation in the Deccan Flood Basalt Province

NASA Astrophysics Data System (ADS)

Saha, A.; Basu, A. R.; Barling, J.; Anbar, A. D.; Hooper, P. R.

2001-12-01

Hafnium isotopes along with other isotopic and geochemical characteristics, including incompatible trace elements, of several of the lower formations of the Deccan Flood Basalt Province were analyzed to characterize petrogenesis of different tholeiitic lava suites, especially with respect to potential mantle and crustal sources. The rare earth elements of the different formations (from top to bottom- Mahabaleshwar, Ambenali, Bushe, Khandala and Neral) all show an LREE-enriched signature, concentrations varying between 30 to 60 times chondrite for La. (La/Lu)n values range from 4.1 to above 8 with the exception of Ambenali, which has a less LREE-enriched signature with (La/Lu)n values ranging between 3.6 to 5.3. Hafnium isotopic data of the lower formations of the Deccan show initial \\epsilonHf(T) values covering a range from -3 to -28. 176Lu/177Hf varies between 0.20 to 0.70. f(Lu/Hf) varies within a narrow range, between -0.90 to -0.97 while f(Sm/Nd) ranges from -0.84 to -0.86. Bushe gives the lowest range of \\epsilonHf(T) from -21 to -28 with the corresponding \\epsilonNd(T) varying between -4.0 and -16.9, while Khandala for almost the same range of neodymium isotopic values has \\epsilonHf(T) between -11 and -15. The \\epsilonHf(T) values of Neral is in between those of Khandala and Bushe, around -19. Ambenali, has the narrowest range with \\epsilonHf(T) of -3 and \\epsilonNd(T) between 3 and 5. The Ambenali suite reflects the least contaminated of the Deccan suite of lavas as analyzed here and previously confirmed by other isotopic studies. In Hf-Nd isotope correlation plot, the lower Deccan formations of Neral, Khandala and Bushe define individual subparallel arrays that are shallower than the oceanic basalt array and the overall terrestrial array, including the crustal array, although the bulk of the lower formation data fall within the crustal array of Vervoort et al (1999). From these subparallel Hf-Nd arrays, it is evident that the other end-members contributing to the Ambenali-type source magmas are distinctly different for each of these lava suites, and can be characterized by their \\epsilonHf(T) values as mentioned above. Although these end-members are discernible in \\epsilonNd vs \\epsilonSr plot (e.g., Peng et al, 1994) of previous studies, our new Hf-isotopic data provide clear evidence of major contributions from the ancient Indian continental crustal reservoirs in the petrogenesis of the lower lava formations of the Deccan Flood Basalt Province.

Anomalously large isotope effect in the glass transition of water

DOE PAGES

Gainaru, Catalin; Agapov, Alexander L.; Fuentes-Landete, Violeta; ...

2014-11-24

Here we present the discovery of an unusually large isotope effect in the structural relaxation and the glass transition temperature T g of water. Dielectric relaxation spectroscopy of low-density as well as of vapor deposited amorphous water reveal T g differences of 10±2K between H 2O and D 2O, sharply contrasting with other hydrogen bonded liquids for which H/D exchange increases T g by typically less than 1K. We show that the large isotope effect and the unusual variation of relaxation times in water at low temperatures can be explained in terms of quantum effects. Thus, our findings shed newmore » light on water's peculiar low-temperature dynamics and the possible role of quantum effects in its structural relaxation, and possibly in dynamics of other low molecular weight liquids.« less

Uncovering trophic positions and food resources of soil animals using bulk natural stable isotope composition.

PubMed

Potapov, Anton M; Tiunov, Alexei V; Scheu, Stefan

2018-06-19

Despite the major importance of soil biota in nutrient and energy fluxes, interactions in soil food webs are poorly understood. Here we provide an overview of recent advances in uncovering the trophic structure of soil food webs using natural variations in stable isotope ratios. We discuss approaches of application, normalization and interpretation of stable isotope ratios along with methodological pitfalls. Analysis of published data from temperate forest ecosystems is used to outline emerging concepts and perspectives in soil food web research. In contrast to aboveground and aquatic food webs, trophic fractionation at the basal level of detrital food webs is large for carbon and small for nitrogen stable isotopes. Virtually all soil animals are enriched in 13 C as compared to plant litter. This 'detrital shift' likely reflects preferential uptake of 13 C-enriched microbial biomass and underlines the importance of microorganisms, in contrast to dead plant material, as a major food resource for the soil animal community. Soil organic matter is enriched in 15 N and 13 C relative to leaf litter. Decomposers inhabiting mineral soil layers therefore might be enriched in 15 N resulting in overlap in isotope ratios between soil-dwelling detritivores and litter-dwelling predators. By contrast, 13 C content varies little between detritivores in upper litter and in mineral soil, suggesting that they rely on similar basal resources, i.e. little decomposed organic matter. Comparing vertical isotope gradients in animals and in basal resources can be a valuable tool to assess trophic interactions and dynamics of organic matter in soil. As indicated by stable isotope composition, direct feeding on living plant material as well as on mycorrhizal fungi is likely rare among soil invertebrates. Plant carbon is taken up predominantly by saprotrophic microorganisms and channelled to higher trophic levels of the soil food web. However, feeding on photoautotrophic microorganisms and non-vascular plants may play an important role in fuelling soil food webs. The trophic niche of most high-rank animal taxa spans at least two trophic levels, implying the use of a wide range of resources. Therefore, to identify trophic species and links in food webs, low-rank taxonomic identification is required. Despite overlap in feeding strategies, stable isotope composition of the high-rank taxonomic groups reflects differences in trophic level and in the use of basal resources. Different taxonomic groups of predators and decomposers are likely linked to different pools of organic matter in soil, suggesting different functional roles and indicating that trophic niches in soil animal communities are phylogenetically structured. During last two decades studies using stable isotope analysis have elucidated the trophic structure of soil communities, clarified basal food resources of the soil food web and revealed links between above- and belowground ecosystem compartments. Extending the use of stable isotope analysis to a wider range of soil-dwelling organisms, including microfauna, and a larger array of ecosystems provides the perspective of a comprehensive understanding of the structure and functioning of soil food webs. © 2018 Cambridge Philosophical Society.

Isotopic characteristics of canopies in simulated leaf assemblages

NASA Astrophysics Data System (ADS)

Graham, Heather V.; Patzkowsky, Mark E.; Wing, Scott L.; Parker, Geoffrey G.; Fogel, Marilyn L.; Freeman, Katherine H.

2014-11-01

The geologic history of closed-canopy forests is of great interest to paleoecologists and paleoclimatologists alike. Closed canopies have pronounced effects on local, continental and global rainfall and temperature patterns. Although evidence for canopy closure is difficult to reconstruct from the fossil record, the characteristic isotope gradients of the ;canopy effect; could be preserved in leaves and proxy biomarkers. To assess this, we employed new carbon isotopic data for leaves collected in diverse light environments within a deciduous, temperate forest (Maryland, USA) and for leaves from a perennially closed canopy, moist tropical forest (Bosque Protector San Lorenzo, Panamá). In the tropical forest, leaf carbon isotope values range 10‰, with higher δ13Cleaf values occurring both in upper reaches of the canopy, and with higher light exposure and lower humidity. Leaf fractionation (Δleaf) varied negatively with height and light and positively with humidity. Vertical 13C enrichment in leaves largely reflects changes in Δleaf, and does not trend with δ13C of CO2 within the canopy. At the site in Maryland, leaves express a more modest δ13C range (∼6‰), with a clear trend that follows both light and leaf height. Using a model we simulate leaf assemblage isotope patterns from canopy data binned by elevation. The re-sampling (bootstrap) model determined both the mean and range of carbon isotope values for simulated leaf assemblages ranging in size from 10 to over 1000 leaves. For the tropical forest data, the canopy's isotope range is captured with 50 or more randomly sampled leaves. Thus, with a sufficient number of fossil leaves it is possible to distinguish isotopic gradients in an ancient closed canopy forest from those in an open forest. For very large leaf assemblages, mean isotopic values approximate the δ13C of carbon contributed by leaves to soil and are similar to observed δ13Clitter values at forested sites within Panamá, including the site where leaves were sampled. The model predicts a persistent ∼1‰ difference in δ13Clitter for the two sites which is consistent with higher water availability in the tropical forests. This work provides a new framework for linking contemporary ecological observations to the geochemical record using flux-weighted isotope data and lends insights to the effect of forest architecture on organic and isotopic records of ancient terrestrial ecosystems. How many leaves from a litter assemblage are necessary to distinguish the isotopic gradient characteristics of canopy closure? Are mean δ13Cleaf values for a litter assemblage diagnostic of a forest biome? Can we predict the δ13C values of cumulative litter, soil organic matter, and organic carbon in sedimentary archives using litter flux and isotope patterns in canopies? We determined the δ13C range and mean for different sized assemblages of leaves sampled from data for each forest. We re-sampled very high numbers of leaves in order to estimate the isotopic composition of cumulative carbon delivered to soils as litter, and compared these results to available data from forest soils. Modeled leaf and soil organic carbon isotope patterns in this study offer insights to how forest structure can be derived from carbon isotope measurements of fossil leaves, as well as secondary material - such as teeth, hair, paleosol carbonates, or organic soil carbon (van der Merwe and Medina, 1989; Koch, 1998; Secord et al., 2008; Levin et al., 2011).Distinct climate and seasonal difference in the Panamá and Maryland, USA forests are reflected in their canopy isotope gradients. In the tropical forest of Panamá, leaves are produced throughout the year within a canopy that is both extensively and persistently closed (Leigh, 1975; Lowman and Wittman, 1996). In the temperate forest of Maryland leaves are produced during the spring when canopy conditions are relatively open (Korner and Basler, 2010).

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

NASA Technical Reports Server (NTRS)

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

2011-01-01

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

Sum frequency generation and solid-state NMR study of the structure, orientation, and dynamics of polystyrene-adsorbed peptides

PubMed Central

Weidner, Tobias; Breen, Nicholas F.; Li, Kun; Drobny, Gary P.; Castner, David G.

2010-01-01

The power of combining sum frequency generation (SFG) vibrational spectroscopy and solid-state nuclear magnetic resonance (ssNMR) spectroscopy to quantify, with site specificity and atomic resolution, the orientation and dynamics of side chains in synthetic model peptides adsorbed onto polystyrene (PS) surfaces is demonstrated in this study. Although isotopic labeling has long been used in ssNMR studies to site-specifically probe the structure and dynamics of biomolecules, the potential of SFG to probe side chain orientation in isotopically labeled surface-adsorbed peptides and proteins remains largely unexplored. The 14 amino acid leucine-lysine peptide studied in this work is known to form an α-helical secondary structure at liquid-solid interfaces. Selective, individual deuteration of the isopropyl group in each leucine residue was used to probe the orientation and dynamics of each individual leucine side chain of LKα14 adsorbed onto PS. The selective isotopic labeling methods allowed SFG analysis to determine the orientations of individual side chains in adsorbed peptides. Side chain dynamics were obtained by fitting the deuterium ssNMR line shape to specific motional models. Through the combined use of SFG and ssNMR, the dynamic trends observed for individual side chains by ssNMR have been correlated with side chain orientation relative to the PS surface as determined by SFG. This combination provides a more complete and quantitative picture of the structure, orientation, and dynamics of these surface-adsorbed peptides than could be obtained if either technique were used separately. PMID:20628016

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.

The cost of reproduction: differential resource specialization in female and male California sea otters.

PubMed

Smith, Emma A Elliott; Newsome, Seth D; Estes, James A; Tinker, M Tim

2015-05-01

Intraspecific variation in behavior and diet can have important consequences for population and ecosystem dynamics. Here, we examine how differences in reproductive investment and spatial ecology influence individual diet specialization in male and female southern sea otters (Enhydra lutris nereis). We hypothesize that greater reproductive constraints and smaller home ranges of females lead to more pronounced intraspecific competition and increased specialization. We integrate stable carbon (δ(13)C) and nitrogen (δ(15)N) isotope analysis of sea otter vibrissae with long-term observational studies of five subpopulations in California. We define individual diet specialization as low ratios of within-individual variation (WIC) to total population niche width (TNW). We compare isotopic and observational based metrics of WIC/TNW for males and females to data on population densities, and movement patterns using both general linear and linear mixed-effects models. Consistent with our hypothesis, increasing population density is associated with increased individual diet specialization by females but not by males. Additionally, we find the amount of coastline in a sea otter's home range positively related with individual dietary variability, with increased range span resulting in weaker specialization for both males and females. We attribute our results to sex-based differences in movement, with females needing to specialize in their small ranges to maximize energy gain, and posit that the paradigm of individual prey specialization in sea otters with increased intraspecific competition may be a pattern driven largely by females. Our work highlights a potentially broader role of sex in the mechanistic pressures promoting and maintaining diet specialization.

The cost of reproduction: differential resource specialization in female and male California sea otters

USGS Publications Warehouse

Elliott Smith, Emma A.; Newsome, Seth D.; Estes, James A.; Tinker, M. Tim

2015-01-01

Intraspecific variation in behavior and diet can have important consequences for population and ecosystem dynamics. Here, we examine how differences in reproductive investment and spatial ecology influence individual diet specialization in male and female southern sea otters (Enhydra lutris nereis). We hypothesize that greater reproductive constraints and smaller home ranges of females lead to more pronounced intraspecific competition and increased specialization. We integrate stable carbon (δ13C) and nitrogen (δ15N) isotope analysis of sea otter vibrissae with long-term observational studies of five subpopulations in California. We define individual diet specialization as low ratios of within-individual variation (WIC) to total population niche width (TNW). We compare isotopic and observational based metrics of WIC/TNW for males and females to data on population densities, and movement patterns using both general linear and linear mixed-effects models. Consistent with our hypothesis, increasing population density is associated with increased individual diet specialization by females but not by males. Additionally, we find the amount of coastline in a sea otter’s home range positively related with individual dietary variability, with increased range span resulting in weaker specialization for both males and females. We attribute our results to sex-based differences in movement, with females needing to specialize in their small ranges to maximize energy gain, and posit that the paradigm of individual prey specialization in sea otters with increased intraspecific competition may be a pattern driven largely by females. Our work highlights a potentially broader role of sex in the mechanistic pressures promoting and maintaining diet specialization.

Millimeter-scale variations of stable isotope abundances in carbonates from banded iron-formations in the Hamersley Group of Western Australia

NASA Technical Reports Server (NTRS)

Baur, M. E.; Hayes, J. M.; Studley, S. A.; Walter, M. R.

1985-01-01

Several diamond drill cores from formations within the Hamersley Group of Western Australia have been studied for evidence of short-range variations in the isotopic compositions of the carbonates. For a set of 32 adjacent microbands analyzed in a specimen from the Marra Mamba Iron Formation, carbon isotope compositions of individual microbands ranged from -2.8 to -19.8 per mil compared to PDB and oxygen isotope compositions ranged from 10.2 to 20.8 per mil compared to SMOW. A pattern of alternating abundances was present, with the average isotopic contrasts between adjacent microbands being 3.0 per mil for carbon and 3.1 per mil for oxygen. Similar results were obtained for a suite of 34 microbands (in four groups) from the Bruno's Band unit of the Mount Sylvia Formation. Difficulties were experienced in preparing samples of single microbands from the Dales Gorge Member of the Brockman Iron Formation, but overall isotopic compositions were in good agreement with values reported by previous authors. Chemical analyses showed that isotopically light carbon and oxygen were correlated with increased concentrations of iron. The preservation of these millimeter-scale variations in isotopic abundances is interpreted as inconsistent with a metamorphic origin for the isotopically light carbon in the BIF carbonates. A biological origin is favored for the correlated variations in 13C and Fe, and it is suggested that the 13C-depleted carbonates may derive either from fermentative metabolism or from anaerobic respiration. A model is presented in which these processes occur near the sediment-water interface and are coupled with an initial oxidative precipitation of the iron.

Role of Megafauna and Frozen Soil in the Atmospheric CH4 Dynamics

PubMed Central

Zimov, Sergey; Zimov, Nikita

2014-01-01

Modern wetlands are the world’s strongest methane source. But what was the role of this source in the past? An analysis of global 14C data for basal peat combined with modelling of wetland succession allowed us to reconstruct the dynamics of global wetland methane emission through time. These data show that the rise of atmospheric methane concentrations during the Pleistocene-Holocene transition was not connected with wetland expansion, but rather started substantially later, only 9 thousand years ago. Additionally, wetland expansion took place against the background of a decline in atmospheric methane concentration. The isotopic composition of methane varies according to source. Owing to ice sheet drilling programs past dynamics of atmospheric methane isotopic composition is now known. For example over the course of Pleistocene-Holocene transition atmospheric methane became depleted in the deuterium isotope, which indicated that the rise in methane concentrations was not connected with activation of the deuterium-rich gas clathrates. Modelling of the budget of the atmospheric methane and its isotopic composition allowed us to reconstruct the dynamics of all main methane sources. For the late Pleistocene, the largest methane source was megaherbivores, whose total biomass is estimated to have exceeded that of present-day humans and domestic animals. This corresponds with our independent estimates of herbivore density on the pastures of the late Pleistocene based on herbivore skeleton density in the permafrost. During deglaciation, the largest methane emissions originated from degrading frozen soils of the mammoth steppe biome. Methane from this source is unique, as it is depleted of all isotopes. We estimated that over the entire course of deglaciation (15,000 to 6,000 year before present), soils of the mammoth steppe released 300–550 Pg (1015 g) of methane. From current study we conclude that the Late Quaternary Extinction significantly affected the global methane cycle. PMID:24695117

Proper interpretation of dissolved nitrous oxide isotopes, production pathways, and emissions requires a modelling approach.

PubMed

Thuss, Simon J; Venkiteswaran, Jason J; Schiff, Sherry L

2014-01-01

Stable isotopes ([Formula: see text]15N and [Formula: see text]18O) of the greenhouse gas N2O provide information about the sources and processes leading to N2O production and emission from aquatic ecosystems to the atmosphere. In turn, this describes the fate of nitrogen in the aquatic environment since N2O is an obligate intermediate of denitrification and can be a by-product of nitrification. However, due to exchange with the atmosphere, the [Formula: see text] values at typical concentrations in aquatic ecosystems differ significantly from both the source of N2O and the N2O emitted to the atmosphere. A dynamic model, SIDNO, was developed to explore the relationship between the isotopic ratios of N2O, N2O source, and the emitted N2O. If the N2O production rate or isotopic ratios vary, then the N2O concentration and isotopic ratios may vary or be constant, not necessarily concomitantly, depending on the synchronicity of production rate and source isotopic ratios. Thus prima facie interpretation of patterns in dissolved N2O concentrations and isotopic ratios is difficult. The dynamic model may be used to correctly interpret diel field data and allows for the estimation of the gas exchange coefficient, N2O production rate, and the production-weighted [Formula: see text] values of the N2O source in aquatic ecosystems. Combining field data with these modelling efforts allows this critical piece of nitrogen cycling and N2O flux to the atmosphere to be assessed.

The Temporal Dynamics of Terrestrial Organic Matter Transfer to the Oceans: Initial Assessment and Application

DTIC Science & Technology

2007-06-01

2.2.4 A QUALITATIVE VIEW OF OC CYCLING 44 2.2.5 COUPLED ISOTOPE MASS BALANCE CALCULATIONS 47 2.3 CONCLUSIONS 56 ACKNOWLEDGEMENTS 57 REFERENCES 58...METHODS 71 3.2 RESULTS & DISCUSSION 73 3.2.1 CHRONOLOGY DEVELOPMENT 73 3.2.2 ELEMENTAL AND ISOTOPIC PROFILES 77 3.2.3 MASS BALANCE CALCULATIONS 80 3.3...2005). Within this framework, isotopic mass balance calculations used to assess the fractional abundance of modem and ancient OC (Blair et al., 2003

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

USGS Publications Warehouse

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

1993-01-01

Oxygen-isotope compositions of authigenic-layer silicates (<2-micrometer fraction) extracted from Mississippian and Pennsylvanian sandstones in the Lower Peninsula of Michigan were determined. Petrographic and scanning-electron-microscope examinations, and X-ray diffractograms show that chlorite and kaolinite are the most common authigenic-layer silicates in Mississippian sandstones. The range of oxygen-isotope compositions of chlorite and kaolinite are +10.3 to +11.9 and +12.9 to +19.3 pars per thousand (per mil) (relative to Standard Mean Ocean Water), respectively. Kaolinite is the only authigenic-isotopic compositions of kaolinite range from +16.8 to +19.0 per mil.

Compound-specific isotope analysis: Questioning the origins of a trichloroethene plume

USGS Publications Warehouse

Eberts, S.M.; Braun, C.; Jones, S.

2008-01-01

Stable carbon isotope ratios of trichloroethene (TCE), cis-1,2- dichloroethene, and trans-1,2-dichloroethene were determined by use of gas chromatography-combustion-isotope ratio mass spectroscopy to determine whether compound-specific stable carbon isotopes could be used to help understand the origin and history of a TCE groundwater plume in Fort Worth, TX. Calculated ??13C values for total chlorinated ethenes in groundwater samples, which can approximate the ??13C of a spilled solvent if all degradation products are accounted for, were useful for determining whether separate lobes of the plume resulted from different sources. Most notably, values for one lobe, where tetrachloroethene (PCE) has been detected periodically, were outside the range for manufactured TCE but within the range for manufactured PCE, whereas values for a separate lobe, which is downgradient of reported TCE spills, were within the range for manufactured TCE. Copyright ?? Taylor & Francis Group, LLC.

Silicon isotope fractionation by marine sponges and the reconstruction of the silicon isotope composition of ancient deep water

NASA Astrophysics Data System (ADS)

de La Rocha, Christina L.

2003-05-01

The silicon isotope composition (δ30Si) of biogenic opal provides a view of the silica cycle at times in the past. Reconstructions require the knowledge of silicon isotope fractionation during opal biomineralization. The δ30Si of specimens of hexactinellid sponges and demosponges growing in the modern ocean ranged from -1.2‰ to -3.7‰ (n = 6), corresponding to the production of opal that has a δ30Si value 3.8‰ ± 0.8‰ more negative than seawater silicic acid and a fractionation factor (α) of 0.9964. This is three times the fractionation observed during opal formation by marine diatoms and terrestrial plants and is the largest fractionation of silicon isotopes observed for any natural process on Earth. The δ30Si values of sponge spicules across the Eocene-Oligocene boundary at Ocean Drilling Program Site 689 on Maud Rise range from -1.1‰ to -3.0‰, overlapping the range observed for sponges growing in modern seawater.

Isotopic differentiation and sublattice melting in dense dynamic ice

NASA Astrophysics Data System (ADS)

Hermann, Andreas; Ashcroft, N. W.; Hoffmann, Roald

2013-12-01

The isotopes of hydrogen provide a unique exploratory laboratory for examining the role of zero point energy (ZPE) in determining the structural and dynamic features of the crystalline ices of water. There are two critical regions of high pressure: (i) near 1 TPa and (ii) near the predicted onset of metallization at around 5 TPa. At the lower pressure of the two, we see the expected small isotopic effects on phase transitions. Near metallization, however, the effects are much greater, leading to a situation where tritiated ice could skip almost entirely a phase available to the other isotopomers. For the higher pressure ices, we investigate in some detail the enthalpics of a dynamic proton sublattice, with the corresponding structures being quite ionic. The resistance toward diffusion of single protons in the ground state structures of high-pressure H2O is found to be large, in fact to the point that the ZPE reservoir cannot overcome these. However, the barriers toward a three-dimensional coherent or concerted motion of protons can be much lower, and the ensuing consequences are explored.

A City-wide Investigation of the Isotopic Distribution and Source of Tap Waters for Forensic Human Geolocation Ground-truthing.

PubMed

Ueda, Momoko; Bell, Lynne S

2017-05-01

Human geolocation is prefaced on the accuracy of the geographic precision of mapped isotopic values for drinking water. As most people live in cities, it becomes important to understand city water supplies and how the isotopic values uniquely reflect that city. This study investigated the isotopic distribution of δ 2 H and δ 18 O from sourced tap waters that were collected from across the Metro Vancouver (MV) area (n = 135). The results revealed that the isotopic values reflect their water sources with a range of 5.3‰ for δ 18 O tap and 29.3‰ for δ 2 H tap for MV. The results indicate that individual cities need higher resolution studies to determine their tap water isotopic ranges, and a good understanding of the water supply network itself for human geolocation work. With an extended high-resolution understanding of each city, human tissue may be compared with more certainty for geolocation. © 2016 American Academy of Forensic Sciences.

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

König, Stephan; Wille, Martin; Voegelin, Andrea; Schoenberg, Ronny

2016-08-01

This study presents Mo isotope data for arc lavas from different subduction zones that range between δ 98 / 95 Mo = - 0.72 and + 0.07 ‰. Heaviest isotope values are observed for the most slab fluid dominated samples. Isotopically lighter signatures are related to increasing relevance of terrigenous sediment subduction and sediment melt components. Our observation complements previous conclusions that an isotopically heavy Mo fluid flux likely mirrors selective incorporation of isotopically light Mo in secondary minerals within the subducting slab. Analogue to this interpretation, low δ 98 / 95 Mo flux that coincides with terrigenous sediment subduction and sediment melting cannot be simply related to a recycled input signature. Instead, breakdown of the controlling secondary minerals during sediment melting may release the light component and lead to decreasing δ 98 / 95 Mo influx into subarc mantle sources. The natural range between slab dehydration and hydrous sediment melting may thus cause a large spread of δ 98 / 95 Mo in global subduction zone magmas.

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

USDA-ARS?s Scientific Manuscript database

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

Stable iron isotopes and microbial mediation in red pigmentation of the Rosso Ammonitico (mid-late Jurassic, Verona area, Italy).

PubMed

Préat, Alain R; de Jong, Jeroen T M; Mamet, Bernard L; Mattielli, Nadine

2008-08-01

The iron (Fe) isotopic composition of 17 Jurassic limestones from the Rosso Ammonitico of Verona (Italy) have been analyzed by Multiple-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). Such analysis allowed for the recognition of a clear iron isotopic fractionation (mean -0.8 per thousand, ranging between -1.52 to -0.06 per thousand) on a millimeter-centimeter scale between the red and grey facies of the studied formation. After gentle acid leaching, measurements of the Fe isotopic compositions gave delta(56)Fe values that were systematically lower in the red facies residues (median: -0.84 per thousand, range: -1.46 to +0.26 per thousand) compared to the grey facies residues (median: -0.08 per thousand, range: -0.34 to +0.23 per thousand). In addition, the red facies residues were characterized by a lighter delta(56)Fe signal relative to their corresponding leachates. These Fe isotopic fractionations could be a sensitive fingerprint of a biotic process; systematic isotopic differences between the red and grey facies residues, which consist of hematite and X-ray amorphous iron hydroxides, respectively, are hypothesized to have resulted from the oxidizing activity of iron bacteria and fungi in the red facies. The grey Fe isotopic data match the Fe isotopic signature of the terrestrial baseline established for igneous rocks and low-C(org) clastic sedimentary rocks. The Fe isotopic compositions of the grey laminations are consistent with the influx of detrital iron minerals and lack of microbial redox processes at the water-interface during deposition. Total Fe concentration measurements were performed by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) (confirmed by concentration estimations obtained by MC-ICP-MS analyses of microdrilled samples) on five samples, and resultant values range between 0.30% (mean) in the grey facies and 1.31% (mean) in the red facies. No correlation was observed between bulk Fe content and pigmentation or between bulk Fe content and Fe isotopic compositions. The rapid transformation of the original iron oxyhydroxides to hematite could have preserved the original isotopic composition if it had occurred at about the same temperature. This paper supports the use of Fe isotopes as sensitive tracers of biological activities recorded in old sedimentary sequences that contain microfossils of iron bacteria and fungi. However, a careful interpretation of the iron isotopic fractionation in terms of biotic versus abiotic processes requires supporting data or direct observations to characterize the biological, (geo)chemical, or physical context in relation to the geologic setting. This will become even more pertinent when Fe isotopic studies are expanded to the interplanetary realm.

Enzymatic Kinetic Isotope Effects from Path-Integral Free Energy Perturbation Theory.

PubMed

Gao, J

2016-01-01

Path-integral free energy perturbation (PI-FEP) theory is presented to directly determine the ratio of quantum mechanical partition functions of different isotopologs in a single simulation. Furthermore, a double averaging strategy is used to carry out the practical simulation, separating the quantum mechanical path integral exactly into two separate calculations, one corresponding to a classical molecular dynamics simulation of the centroid coordinates, and another involving free-particle path-integral sampling over the classical, centroid positions. An integrated centroid path-integral free energy perturbation and umbrella sampling (PI-FEP/UM, or simply, PI-FEP) method along with bisection sampling was summarized, which provides an accurate and fast convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. The PI-FEP method is illustrated by a number of applications, to highlight the computational precision and accuracy, the rule of geometrical mean in kinetic isotope effects, enhanced nuclear quantum effects in enzyme catalysis, and protein dynamics on temperature dependence of kinetic isotope effects. © 2016 Elsevier Inc. All rights reserved.

Accurate experimental determination of the isotope effects on the triple point temperature of water. I. Dependence on the 2H abundance

NASA Astrophysics Data System (ADS)

Faghihi, V.; Peruzzi, A.; Aerts-Bijma, A. T.; Jansen, H. G.; Spriensma, J. J.; van Geel, J.; Meijer, H. A. J.

2015-12-01

Variation in the isotopic composition of water is one of the major contributors to uncertainty in the realization of the triple point of water (TPW). Although the dependence of the TPW on the isotopic composition of the water has been known for years, there is still a lack of a detailed and accurate experimental determination of the values for the correction constants. This paper is the first of two articles (Part I and Part II) that address quantification of isotope abundance effects on the triple point temperature of water. In this paper, we describe our experimental assessment of the 2H isotope effect. We manufactured five triple point cells with prepared water mixtures with a range of 2H isotopic abundances encompassing widely the natural abundance range, while the 18O and 17O isotopic abundance were kept approximately constant and the 18O  -  17O ratio was close to the Meijer-Li relationship for natural waters. The selected range of 2H isotopic abundances led to cells that realised TPW temperatures between approximately  -140 μK to  +2500 μK with respect to the TPW temperature as realized by VSMOW (Vienna Standard Mean Ocean Water). Our experiment led to determination of the value for the δ2H correction parameter of A2H  =  673 μK / (‰ deviation of δ2H from VSMOW) with a combined uncertainty of 4 μK (k  =  1, or 1σ).

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

NASA Astrophysics Data System (ADS)

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

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

Soil carbon dynamics beneath switchgrass as indicated by stable isotope analysis

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

Garten, C.T. Jr.; Wullschleger, S.D.

2000-04-01

Surface (0--40 cm) soil organic carbon (SOC) dynamics were studied beneath four switchgrass (Panicum virgatum L.) field trails in the southeastern US. Soil organic carbon was partitioned into particulate organic matter (POM) and mineral-associated organic matter (MOM). Most (75--90%) of the SOC at each study site was affiliated with MOM (<0.053 mm). Changes in stable carbon isotope ratios were used to derive carbon inputs to and losses from POM and MOM at each site. Inventories of existing SOC and new C{sub 4}-derived SOC beneath switchgrass decreased with increasing soil depth. Approximately 5 yr after establishment, 19 to 31% of themore » existing SOC inventories beneath switchgrass had been derived from new C{sub 4}-carbon inputs. Calculated turnover times of POM and MOM ranged from 2.4 to 4.3 yr and 26 to 40 yr, respectively. The turnover time of SOC in the POM fraction increased with decreasing mean annual temperature. A simple, two-compartment model was parameterized to predict the potential for soil carbon sequestration under switchgrass. An example calculation with the model indicated a measurable and verifiable recovery of soil carbon (=12% increase) on degraded lands through one decade of switchgrass production. The potential to sequester carbon through switchgrass cultivation will depend on initial soil carbon inventories, prevailing climate, soil types and site management.« less

Soil carbon dynamics beneath switchgrass as indicated by stable isotope analysis

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

Garten Jr, Charles T; Wullschleger, Stan D

2000-04-01

Surface (0-40 cm) soil organic carbon (SOC) dynamics were studied beneath four switchgrass (Panicum virgatum L.) field trials in the southeastern United States. Soil organic carbon was partitioned into particulate organic matter (POM) and mineral-associated organic matter (MOM). Most (75-90%) of the SOC at each study site was affiliated with MOM (<0.053 mm). Changes in stable carbon isotope ratios were used to derive carbon inputs to and losses from POM and MOM at each site. Inventories of existing SOC and new C4-derived SOC beneath switchgrass decreased with increasing soil depth. Approximately 5 yr after establishment, 19 to 31% of themore » existing SOC inventories beneath switchgrass had been derived from new C{sub 4}-carbon inputs. Calculated turnover times of POM and MOM ranged from 2.4 to 4.3 yr and 26 to 40 yr, respectively. The turnover time of SOC in the POM fraction increased with decreasing mean annual temperature. A simple, two-compartment model was parameterized to predict the potential for soil carbon sequestration under switchgrass. An example calculation with the model indicated a measurable and verifiable recovery of soil carbon ({approx}12% increase) on degraded lands through one decade of switchgrass production. The potential to sequester carbon through switchgrass cultivation will depend on initial soil carbon inventories, prevailing climate, soil type, and site management.« less

High-level direct-dynamics variational transition state theory calculations including multidimensional tunneling of the thermal rate constants, branching ratios, and kinetic isotope effects of the hydrogen abstraction reactions from methanol by atomic hydrogen.

PubMed

Meana-Pañeda, Rubén; Truhlar, Donald G; Fernández-Ramos, Antonio

2011-03-07

We report a detailed theoretical study of the hydrogen abstraction reaction from methanol by atomic hydrogen. The study includes the analysis of thermal rate constants, branching ratios, and kinetic isotope effects. Specifically, we have performed high-level computations at the MC3BB level together with direct dynamics calculations by canonical variational transition state theory (CVT) with the microcanonically optimized multidimensional tunneling (μOMT) transmission coefficient (CVT/μOMT) to study both the CH(3)OH+H→CH(2)OH+H(2) (R1) reaction and the CH(3)OH+H→CH(3)O+H(2) (R2) reaction. The CVT/μOMT calculations show that reaction R1 dominates in the whole range 298≤T (K)≤2500 and that anharmonic effects on the torsional mode about the C-O bond are important, mainly at high temperatures. The activation energy for the total reaction sum of R1 and R2 reactions changes substantially with temperature and, therefore, the use of straight-line Arrhenius plots is not valid. We recommend the use of new expressions for the total R1 + R2 reaction and for the R1 and R2 individual reactions. © 2011 American Institute of Physics.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Fontinalis antipyretica as a bioindicator of environmental conditions in freshwater ecosystem from Sava River watershed and Cerknişko Lake, Slovenia

NASA Astrophysics Data System (ADS)

Kanduč, Tjaša; Mechora, Špela; Stibilj, Vekoslava

2014-05-01

Polluted waters recharging from agriculture water systems into watersheds have influence on water quality and living habitat. Stable isotopes of carbon and nitrogen in combination with other minor and trace elements are often used to trace biogeochemical processes and contamination of water systems. The aim of the study was to assess state of environment with minor and trace elements and stable isotopes of C and N in selected Slovenian streams. Ten locations in Notranjska region, Slovenia, with different land use in the catchment (town, village, agricultural areas, farms, dairy farms), including reference point considered as non-polluted site, were sampled. Samples of water and aquatic moss F. antipyretica in Slovenian fresh waters were taken in all four seasons during years 2010 and 2012, but for stable isotope analyses of C and N only in three seasons during years 2010 and 2011. The water chemistry of investigated locations is dominated by hydrogen carbonate - calcium - magnesium, concentrations of nitrate seasonally range from 2.07 mg/l to 6.4 mg/l and at reference site does not exceed 1.3 mg/l. Total alkalinity of water at investigated locations ranges from 2.9 to 6.02 mM. The pH of investigated water range from 7.2 to 8.5, waters are saturated with oxygen (up to 134%) and conductivity ranges from 295 to 525 mikroS/cm, while at reference site conductivity is up to 180 mikroS/cm. The content of minor and trace elements in F. antipyretica ranged for Ni 4-38 mikrog/g, Zn 17-105 mikrog/g, Pb 2-28 mikrog/g, Cd 220-1953 ng/g, Cu 4-27 mikrog/g, Cr 4-49 mikrog/g, As 1-6 mikrog/g and Se 0.33-3.24 mikrog/g. The most polluted watershed was Pšata stream (agricultural areas, cattle farm) with highest values for Ni, Cr, Pb, Zn and As. The highest content of Se, was found in village (dairy farms) in Žerovniščica stream. The highest values were measured in February and October. Isotopic composition of dissolved inorganic carbon seasonally range from -13.3 to -8.1‰, and indicate waters dominated by degradation of organic matter and dissolution of carbonates. At the reference point average measured isotopic composition of dissolved inorganic carbon value is -2.7‰ which confirmed that this is a non-polluted site. Isotopic composition of carbon of F. antipyretica seasonally ranges from -45 to -32.9‰ and isotopic composition of nitrogen from -0.2‰ to 6.5‰, respectively. In comparison to C3 terrestrial plants F. antipyretica has more negative isotopic composition of carbon value, which is probably related with the difference in CO2 plant fixation and depends on isotopic composition of dissolved inorganic carbon in water, which is primarily controlled by geological composition and soil thickness in the watershed. Higher isotopic composition of nitrogen value found in F. antipyretica is related to agricultural activity in watershed, while at the reference site measured isotopic composition of nitrogen value is -4.1 ‰. From our study it is evident that isotopic composition of carbon and nitrogen is useful tracer of natural and anthropogenic inputs from terrestrial (fertilizing, sewage sludge) to water system.

Development and Validation of a Rapid (13)C6-Glucose Isotope Dilution UPLC-MRM Mass Spectrometry Method for Use in Determining System Accuracy and Performance of Blood Glucose Monitoring Devices.

PubMed

Matsunami, Risë K; Angelides, Kimon; Engler, David A

2015-05-18

There is currently considerable discussion about the accuracy of blood glucose concentrations determined by personal blood glucose monitoring systems (BGMS). To date, the FDA has allowed new BGMS to demonstrate accuracy in reference to other glucose measurement systems that use the same or similar enzymatic-based methods to determine glucose concentration. These types of reference measurement procedures are only comparative in nature and are subject to the same potential sources of error in measurement and system perturbations as the device under evaluation. It would be ideal to have a completely orthogonal primary method that could serve as a true standard reference measurement procedure for establishing the accuracy of new BGMS. An isotope-dilution liquid chromatography/mass spectrometry (ID-UPLC-MRM) assay was developed using (13)C6-glucose as a stable isotope analogue to specifically measure glucose concentration in human plasma, and validated for use against NIST standard reference materials, and against fresh isolates of whole blood and plasma into which exogenous glucose had been spiked. Assay performance was quantified to NIST-traceable dry weight measures for both glucose and (13)C6-glucose. The newly developed assay method was shown to be rapid, highly specific, sensitive, accurate, and precise for measuring plasma glucose levels. The assay displayed sufficient dynamic range and linearity to measure across the range of both normal and diabetic blood glucose levels. Assay performance was measured to within the same uncertainty levels (<1%) as the NIST definitive method for glucose measurement in human serum. The newly developed ID UPLC-MRM assay can serve as a validated reference measurement procedure to which new BGMS can be assessed for glucose measurement performance. © 2015 Diabetes Technology Society.

Development and Validation of a Rapid 13C6-Glucose Isotope Dilution UPLC-MRM Mass Spectrometry Method for Use in Determining System Accuracy and Performance of Blood Glucose Monitoring Devices

PubMed Central

Matsunami, Risë K.; Angelides, Kimon; Engler, David A.

2015-01-01

Background: There is currently considerable discussion about the accuracy of blood glucose concentrations determined by personal blood glucose monitoring systems (BGMS). To date, the FDA has allowed new BGMS to demonstrate accuracy in reference to other glucose measurement systems that use the same or similar enzymatic-based methods to determine glucose concentration. These types of reference measurement procedures are only comparative in nature and are subject to the same potential sources of error in measurement and system perturbations as the device under evaluation. It would be ideal to have a completely orthogonal primary method that could serve as a true standard reference measurement procedure for establishing the accuracy of new BGMS. Methods: An isotope-dilution liquid chromatography/mass spectrometry (ID-UPLC-MRM) assay was developed using 13C6-glucose as a stable isotope analogue to specifically measure glucose concentration in human plasma, and validated for use against NIST standard reference materials, and against fresh isolates of whole blood and plasma into which exogenous glucose had been spiked. Assay performance was quantified to NIST-traceable dry weight measures for both glucose and 13C6-glucose. Results: The newly developed assay method was shown to be rapid, highly specific, sensitive, accurate, and precise for measuring plasma glucose levels. The assay displayed sufficient dynamic range and linearity to measure across the range of both normal and diabetic blood glucose levels. Assay performance was measured to within the same uncertainty levels (<1%) as the NIST definitive method for glucose measurement in human serum. Conclusions: The newly developed ID UPLC-MRM assay can serve as a validated reference measurement procedure to which new BGMS can be assessed for glucose measurement performance. PMID:25986627

Gamow-Teller strength and lepton captures rates on 66-71Ni in stellar matter

NASA Astrophysics Data System (ADS)

Nabi, Jameel-Un; Majid, Muhammad

Charge-changing transitions play a significant role in stellar weak-decay processes. The fate of the massive stars is decided by these weak-decay rates including lepton (positron and electron) captures rates, which play a consequential role in the dynamics of core collapse. As per previous simulation results, weak interaction rates on nickel (Ni) isotopes have significant influence on the stellar core vis-à-vis controlling the lepton content of stellar matter throughout the silicon shell burning phases of high mass stars up to the presupernova stages. In this paper, we perform a microscopic calculation of Gamow-Teller (GT) charge-changing transitions, in the β-decay and electron capture (EC) directions, for neutron-rich Ni isotopes (66-71Ni). We further compute the associated weak-decay rates for these selected Ni isotopes in stellar environment. The computations are accomplished by employing the deformed proton-neutron quasiparticle random phase approximation (pn-QRPA) model. A recent study showed that the deformed pn-QRPA theory is well suited for the estimation of GT transitions. The astral weak-decay rates are determined over densities in the range of 10-1011g/cm3 and temperatures in the range of 0.01 × 109-30 × 109K. The calculated lepton capture rates are compared with the previous calculation of Pruet and Fuller (PF). The overall comparison demonstrates that, at low stellar densities and high temperatures, our EC rates are bigger by as much as two orders of magnitude. Our results show that, at higher temperatures, the lepton capture rates are the dominant mode for the stellar weak rates and the corresponding lepton emission rates may be neglected.

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

Moon, Chang-Bum, E-mail: cbmoon@hoseo.edu

This paper outlines the new physics possibilities that fall within the field of nuclear structure and astrophysics based on experiments with radioactive ion beams at the future Rare Isotope Beams Accelerator facility in Korea. This ambitious multi-beam facility has both an Isotope Separation On Line (ISOL) and fragmentation capability to produce rare isotopes beams (RIBs) and will be capable of producing and accelerating beams of wide range mass of nuclides with energies of a few to hundreds MeV per nucleon. The large dynamic range of reaccelerated RIBs will allow the optimization in each nuclear reaction case with respect to crossmore » section and channel opening. The low energy RIBs around Coulomb barrier offer nuclear reactions such as elastic resonance scatterings, one or two particle transfers, Coulomb multiple-excitations, fusion-evaporations, and direct capture reactions for the study of the very neutron-rich and proton-rich nuclides. In contrast, the high energy RIBs produced by in-flight fragmentation with reaccelerated ions from the ISOL enable to explore the study of neutron drip lines in intermediate mass regions. The proposed studies aim at investigating the exotic nuclei near and beyond the nucleon drip lines, and to explore how nuclear many-body systems change in such extreme regions by addressing the following topics: the evolution of shell structure in areas of extreme proton to neutron imbalance; the study of the weak interaction in exotic decay schemes such as beta-delayed two-neutron or two-proton emission; the change of isospin symmetry in isobaric mirror nuclei at the drip lines; two protons or two neutrons radioactivity beyond the drip lines; the role of the continuum states including resonant states above the particle-decay threshold in exotic nuclei; and the effects of nuclear reaction rates triggered by the unbound proton-rich nuclei on nuclear astrophysical processes.« less

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

USGS Publications Warehouse

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

2012-01-01

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

Using combinations of metal isotopes as tracers of tailings pond discharges to subsurface aquifers in the Athabasca Oil Sands area, Canada.

NASA Astrophysics Data System (ADS)

Gammon, P. R.; Savard, M. M.; Ahad, J. M.; Girard, I.

2016-12-01

The Athabasca Oil Sands (AOS) industry in Alberta, Canada deposits voluminous waste streams in Earth's largest tailings ponds (TPs). Detecting and tracing contaminant discharge from TPs to subsurface aquifers has proven difficult because tailings have the same composition as the surrounding environment of unmined oil sand. To trace pond discharge to the subsurface therefore relies on the waste stream hosting additions or alterations induced by mining or industrial processes. Inorganic element or contaminant concentration data have proven ineffective at tracing because there is insufficient alteration of the chemical constituents or their ratios. Metal isotopes have not generally been applied to tracing emissions even though isotopic fractionation is likely induced via the high temperature and pH industrial process. We have generated Mg, Li, Pb and Zn isotopic data for a range of groundwater wells and TPs. Mg isotopes are excellent for distinguishing deep saline brines that are pumped into the waste stream during mine dewatering. Li isotopes appear to be heavily fractionated during processing, which produces a heavy isotopic signature that is an excellent tracer of production water. Pb isotopes discriminate Pb derived from oil-sand versus bedrock carbonate. Juxtapositions of TPs, carbonates and near-surface aquifers are common and of significant regulatory concern, making Pb isotopes particularly useful. Zn isotopic data indicates similarities to Pb isotopes, but are difficult to obtain due to low concentrations. Combining the isotopic data with concentration data and hydrologic models will assist in determining the fluxes of discharges from the TPs to near-surface aquifers. The range of environmental contexts of AOS TPs is limited and thus monitoring discharges to nearby aquifers from TPs could feasibly be accomplished using tailored suites of metal isotopes.

Molten Salts and Isotope Separation

NASA Astrophysics Data System (ADS)

Lantelme, Frédéric

2013-02-01

The work on molten salts and isotope separation performed over the years at Université Pierre et Marie Curie and at Collège de France is critically reviewed. This research, closely related to A. Klemm's pioneering contributions, leads among other things to the discovery of the effect now called the `Chemla effect', after the late Professor Marius Chemla. These studies of ionic motions in melts, and liquids in general, have greatly benefitted from recent advances in molecular simulations. Some recent results of such simulations - molecular dynamics (MD) and Brownian dynamics (BD) - as well as of related theoretical work are discussed.

A New Method to Quantify the Isotopic Signature of Leaf Transpiration: Implications for Landscape-Scale Evapotranspiration Partitioning Studies

NASA Astrophysics Data System (ADS)

Wang, L.; Good, S. P.; Caylor, K. K.

2010-12-01

Characterizing the constituent components of evapotranspiration is crucial to better understand ecosystem-level water budgets and water use dynamics. Isotope based evapotranspiration partitioning methods are promising but their utility lies in the accurate estimation of the isotopic composition of underlying transpiration and evaporation. Here we report a new method to quantify the isotopic signature of leaf transpiration under field conditions. This method utilizes a commercially available laser-based isotope analyzer and a transparent leaf chamber, modified from Licor conifer leaf chamber. The method is based on the water mass balance in ambient air and leaf transpired air. We verified the method using “artificial leaves” and glassline extracted samples. The method provides a new and direct way to estimate leaf transpiration isotopic signatures and it has wide applications in ecology, hydrology and plant physiology.

Applications of an NMHC isotope analysis system on trace gases from plant and CARIBIC samples

NASA Astrophysics Data System (ADS)

Zuiderweg, A.; Holzinger, R.; Röckmann, T.; Brenninkmeijer, C. A. M.

2009-04-01

Isotope analysis can be a useful tool in constraining the budgets (sources and sinks) of atmospheric trace species and is increasingly applied for organic constituents. We present initial results from an automated system for isotope ratio measurements on atmospheric hydrocarbons. The inlet system is flexible and allows analysis of trace gases from medium size to large ambient air samples (5-300L) as well as CO2-concentrates from samples that have been extracted offline. Long-term testing has shown this system to be stable to 1.5‰ vs. VPDB (or better) across all tested C2-C6 compounds, and methyl chloride. This system has now been utilized to analyze emissions rates and isotopic fractionation of 7 NMHCs from Sequoia leaf litter under conditions of UV exposure. These experiments indicate, for example, δ13C depletion in methyl chloride (CH3Cl) In the range of -90 to -113 v. VPDB with continuously increasing emission rates reaching to 3.26 ng/h/gdw after constant UV exposure of 7 hours, in a dynamic reactor. Other experiments with variation in UV exposure were also undertaken, indicating variation in emission rates and δ13C with UV intensity. In addition, first results from analysis of samples from concentrates taken during the CARIBIC II (http://www.caribic-atmospheric.com/) campaign, beginning with flight 26 (return flight, Male, Maldives, to Dusseldorf, Germany, August 2000), which features flight path air originating from over the Atlantic Ocean and the Indian subcontinent, is presented.

Beryllium-10 dating of the duration and retreat of the last pinedale glacial sequence

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

Gosse, J.C.; Klein, J.; Evenson, E.B.

Accurate terrestrial glacial chronologies are needed for comparison with the marine record to establish the dynamics of global climate change during transitions from glacial to interglacial regimes. Cosmogenic beryllium-10 measurements in the Wind River Range indicate that the last glacial maximum (marine oxygen isotope stage 2) was achieved there by 21,700 {+-} 700 beryllium-10 years and lasted 5900 years. Ages of a sequence of recessional moraines and striated bedrock surfaces show that the initial deglaciation was rapid and that the entire glacial system retreated 33 kilometers to the cirque basin by 12,100 {+-} 500 beryllium-10 years.

[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.

Enzymatic Kinetic Isotope Effects from First-Principles Path Sampling Calculations.

PubMed

Varga, Matthew J; Schwartz, Steven D

2016-04-12

In this study, we develop and test a method to determine the rate of particle transfer and kinetic isotope effects in enzymatic reactions, specifically yeast alcohol dehydrogenase (YADH), from first-principles. Transition path sampling (TPS) and normal mode centroid dynamics (CMD) are used to simulate these enzymatic reactions without knowledge of their reaction coordinates and with the inclusion of quantum effects, such as zero-point energy and tunneling, on the transferring particle. Though previous studies have used TPS to calculate reaction rate constants in various model and real systems, it has not been applied to a system as large as YADH. The calculated primary H/D kinetic isotope effect agrees with previously reported experimental results, within experimental error. The kinetic isotope effects calculated with this method correspond to the kinetic isotope effect of the transfer event itself. The results reported here show that the kinetic isotope effects calculated from first-principles, purely for barrier passage, can be used to predict experimental kinetic isotope effects in enzymatic systems.

GasBench/isotope ratio mass spectrometry: a carbon isotope approach to detect exogenous CO(2) in sparkling drinks.

PubMed

Cabañero, Ana I; San-Hipólito, Tamar; Rupérez, Mercedes

2007-01-01

A new procedure for the determination of carbon dioxide (CO(2)) (13)C/(12)C isotope ratios, using direct injection into a GasBench/isotope ratio mass spectrometry (GasBench/IRMS) system, has been developed to improve isotopic methods devoted to the study of the authenticity of sparkling drinks. Thirty-nine commercial sparkling drink samples from various origins were analyzed. Values of delta(13)C(cava) ranged from -20.30 per thousand to -23.63 per thousand, when C3 sugar addition was performed for a second alcoholic fermentation. Values of delta(13)C(water) ranged from -5.59 per thousand to -6.87 per thousand in the case of naturally carbonated water or water fortified with gas from the spring, and delta(13)C(water) ranged from -29.36 per thousand to -42.09 per thousand when industrial CO(2) was added. It has been demonstrated that the addition of C4 sugar to semi-sparkling wine (aguja) and industrial CO(2) addition to sparkling wine (cava) or water can be detected. The new procedure has advantages over existing methods in terms of analysis time and sample treatment. In addition, it is the first isotopic method developed that allows (13)C/(12)C determination directly from a liquid sample without previous CO(2) extraction. No significant isotopic fractionation was observed nor any influence by secondary compounds present in the liquid phase. Copyright (c) 2007 John Wiley & Sons, Ltd.

Impact of topography, climate and moisture sources on isotopic composition (δ18O &δD) of rivers in the Pyrenees: Implications for topographic reconstructions in small orogens

NASA Astrophysics Data System (ADS)

Huyghe, Damien; Mouthereau, Frédéric; Sébilo, Mathieu; Vacherat, Arnaud; Ségalen, Loïc; Richard, Patricia; Biron, Philippe; Bariac, Thierry

2018-02-01

Understanding how orogenic topography controls the spatial distribution and isotopic composition of precipitation is critical for paleoaltitudinal reconstructions. Here, we determine the isotopic composition (δ18O and δD) of 82 small rivers and springs from small catchments in the Pyrenees. Calculation of the deuterium excess (d-excess) parameter allows the distinction of four distinct isotopic provinces with d-excess values of between 15 and 22‰ in the northwest, between 7 and 14‰ in the central northern Pyrenees and between 3 and 11‰ in the northeast. The southern Pyrenees have a homogenous d-excess signature ranging from 7 to 14‰. Our results show significant local moisture recycling and/or rain amount effect in the northwestern Pyrenees, and control by evaporation processes during rainfall events in the southern Pyrenees and for low elevated samples of the northeast of the range. Based on the distribution of d-excess values, we estimate contrasting isotope lapse rates of -2.9/-21.4‰/km (δ18O/δD) in the northwest, -2.7/-21.4‰/km (δ18O/δD) in the north central and -3.7/-31.7‰/km (δ18O/δD) in the northeastern Pyrenees. The southern Pyrenees show distinctly higher lapse rates of -9.5/-77.5‰/km (δ18O/δD), indicating that in this area the altitudinal effect in not the only parameter driving isotopic composition of rivers. Despite their relatively low topographic gradient, the Pyrenees exert a direct control on the isotopic composition of river waters, especially on their northern side. The variations in isotopic composition-elevation relationships documented along the strike of the range are interpreted to reflect an increasing continentality effect driven by wind trajectories parallel to the range, and mixing with Mediterranean air masses. Despite these effects, the measurable orographic effect on precipitation in the Pyrenees proves that the isotopic composition approach for reconstructing past topography is applicable to low-elevation orogens.

Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision.

PubMed

Schnedermann, C; Yang, X; Liebel, M; Spillane, K M; Lugtenburg, J; Fernández, I; Valentini, A; Schapiro, I; Olivucci, M; Kukura, P; Mathies, R A

2018-04-01

Vibronic coupling is key to efficient energy flow in molecular systems and a critical component of most mechanisms invoking quantum effects in biological processes. Despite increasing evidence for coherent coupling of electronic states being mediated by vibrational motion, it is not clear how and to what degree properties associated with vibrational coherence such as phase and coupling of atomic motion can impact the efficiency of light-induced processes under natural, incoherent illumination. Here, we show that deuteration of the H 11 -C 11 =C 12 -H 12 double-bond of the 11-cis retinal chromophore in the visual pigment rhodopsin significantly and unexpectedly alters the photoisomerization yield while inducing smaller changes in the ultrafast isomerization dynamics assignable to known isotope effects. Combination of these results with non-adiabatic molecular dynamics simulations reveals a vibrational phase-dependent isotope effect that we suggest is an intrinsic attribute of vibronically coherent photochemical processes.

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

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

Deng, Jia; McCalley, Carmody K.; Frolking, Steve

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Using stable isotopes to follow excreta N dynamics and N2O emissions in animal production systems.

PubMed

Clough, T J; Müller, C; Laughlin, R J

2013-06-01

Nitrous oxide (N2O) is a potent greenhouse gas and the dominant anthropogenic stratospheric ozone-depleting emission. The tropospheric concentration of N2O continues to increase, with animal production systems constituting the largest anthropogenic source. Stable isotopes of nitrogen (N) provide tools for constraining emission sources and, following the temporal dynamics of N2O, providing additional insight and unequivocal proof of N2O source, production pathways and consumption. The potential for using stable isotopes of N is underutilised. The intent of this article is to provide an overview of what these tools are and demonstrate where and how these tools could be applied to advance the mitigation of N2O emissions from animal production systems. Nitrogen inputs and outputs are dominated by fertiliser and excreta, respectively, both of which are substrates for N2O production. These substrates can be labelled with 15N to enable the substrate-N to be traced and linked to N2O emissions. Thus, the effects of changes to animal production systems to reduce feed-N wastage by animals and fertiliser wastage, aimed at N2O mitigation and/or improved animal or economic performance, can be traced. Further 15N-tracer studies are required to fully understand the dynamics and N2O fluxes associated with excreta, and the biological contribution to these fluxes. These data are also essential for the new generation of 15N models. Recent technique developments in isotopomer science along with stable isotope probing using multiple isotopes also offer exciting capability for addressing the N2O mitigation quest.

Storage dynamics in hydropedological units control hillslope connectivity, runoff generation, and the evolution of catchment transit time distributions

PubMed Central

Tetzlaff, D; Birkel, C; Dick, J; Geris, J; Soulsby, C

2014-01-01

We examined the storage dynamics and isotopic composition of soil water over 12 months in three hydropedological units in order to understand runoff generation in a montane catchment. The units form classic catena sequences from freely draining podzols on steep upper hillslopes through peaty gleys in shallower lower slopes to deeper peats in the riparian zone. The peaty gleys and peats remained saturated throughout the year, while the podzols showed distinct wetting and drying cycles. In this region, most precipitation events are <10 mm in magnitude, and storm runoff is mainly generated from the peats and peaty gleys, with runoff coefficients (RCs) typically <10%. In larger events the podzolic soils become strongly connected to the saturated areas, and RCs can exceed 40%. Isotopic variations in precipitation are significantly damped in the organic-rich soil surface horizons due to mixing with larger volumes of stored water. This damping is accentuated in the deeper soil profile and groundwater. Consequently, the isotopic composition of stream water is also damped, but the dynamics strongly reflect those of the near-surface waters in the riparian peats. “pre-event” water typically accounts for >80% of flow, even in large events, reflecting the displacement of water from the riparian soils that has been stored in the catchment for >2 years. These riparian areas are the key zone where different source waters mix. Our study is novel in showing that they act as “isostats,” not only regulating the isotopic composition of stream water, but also integrating the transit time distribution for the catchment. Key Points Hillslope connectivity is controlled by small storage changes in soil units Different catchment source waters mix in large riparian wetland storage Isotopes show riparian wetlands set the catchment transit time distribution PMID:25506098

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

DOE PAGES

Deng, Jia; McCalley, Carmody K.; Frolking, Steve; ...

2017-06-13

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Storage dynamics in hydropedological units control hillslope connectivity, runoff generation, and the evolution of catchment transit time distributions.

PubMed

Tetzlaff, D; Birkel, C; Dick, J; Geris, J; Soulsby, C

2014-02-01

We examined the storage dynamics and isotopic composition of soil water over 12 months in three hydropedological units in order to understand runoff generation in a montane catchment. The units form classic catena sequences from freely draining podzols on steep upper hillslopes through peaty gleys in shallower lower slopes to deeper peats in the riparian zone. The peaty gleys and peats remained saturated throughout the year, while the podzols showed distinct wetting and drying cycles. In this region, most precipitation events are <10 mm in magnitude, and storm runoff is mainly generated from the peats and peaty gleys, with runoff coefficients (RCs) typically <10%. In larger events the podzolic soils become strongly connected to the saturated areas, and RCs can exceed 40%. Isotopic variations in precipitation are significantly damped in the organic-rich soil surface horizons due to mixing with larger volumes of stored water. This damping is accentuated in the deeper soil profile and groundwater. Consequently, the isotopic composition of stream water is also damped, but the dynamics strongly reflect those of the near-surface waters in the riparian peats. "pre-event" water typically accounts for >80% of flow, even in large events, reflecting the displacement of water from the riparian soils that has been stored in the catchment for >2 years. These riparian areas are the key zone where different source waters mix. Our study is novel in showing that they act as "isostats," not only regulating the isotopic composition of stream water, but also integrating the transit time distribution for the catchment. Hillslope connectivity is controlled by small storage changes in soil unitsDifferent catchment source waters mix in large riparian wetland storageIsotopes show riparian wetlands set the catchment transit time distribution.

IsoBank – Stable isotope ecology in the age of ‘Big Data’

USDA-ARS?s Scientific Manuscript database

Stable isotopes ratios provide valuable information to fish biologists working in a diverse range of fields: e.g. ecologists, population biologists and fishery managers. Ecologists take advantage of stable isotope ratios to provide information on the diet and migration history of consumers or when a...

Using stable isotopes to identify the scaling effects of riparian peatlands on runoff generation processes and DOC mobilisation

NASA Astrophysics Data System (ADS)

Tunaley, Claire; Tetzlaff, Doerthe; Soulsby, Chris

2017-04-01

Knowledge of hydrological sources, flow paths, and their connectivity is fundamental to understanding stream flow generation and surface water quality in peatlands. Stable isotopes are proven tools for tracking the sources and flow paths of runoff. However, relativity few studies have used isotopes in peat-dominated catchments. Here, we combined 13 months (June 2014 - July 2015) of daily isotope measurements in stream water with daily DOC and 15 minute FDOM (fluorescent component of dissolved organic matter) data, at three nested scales in NE Scotland, to identify the hydrological processes occurring in riparian peatlands. We investigated how runoff generation processes in a small, riparian peatland dominated headwater catchment (0.65 km2) propagate to larger scales (3.2 km2 and 31 km2) with decreasing percentage of riparian peatland coverage. Isotope damping was most pronounced in the 0.65 km2 catchment due to high water storage in the organic soils which encouraged tracer mixing and resulted in attenuated runoff peaks. At the largest scale, stream flow and water isotope dynamics showed a more flashy response. Particularly insightful in this study was calculating the deviation of the isotopes from the local meteoric water line, the lc-excess. The lc-excess revealed evaporative fractionation in the peatland dominated catchment, particularly during summer low flows. This implied high hydrological connectivity in the form of constant seepage from the peatlands sustaining high baseflows at the headwater scale. This constant connectivity resulted in high DOC concentrations at the peatland site during baseflow ( 5 mg l-1). In contrast, at the larger scales, DOC was minimal during low flows ( 2 mg l-1) due to increased groundwater influence and the disconnection between DOC sources and the stream. Insights into event dynamics through the analysis of DOC hysteresis loops showed slight dilution on the rising limb, the strong influence of dry antecedent conditions and a quick recovery between events at the riparian peatland site. Again, these dynamics were driven by the tight coupling and high connectivity of the landscape to the stream. At larger scales, the disconnection between the landscape units increased and the variable connectivity controlled runoff generation and DOC dynamics. The results presented here suggest that the hydrological processes occurring in riparian peatlands in headwater catchments are less evident at larger scales which may have implications for the larger scale impact of peatland restoration projects.

Multi-decadal carbon and water relations of African tropical humid forests: a tree-ring stable isotope analysis

NASA Astrophysics Data System (ADS)

Hufkens, Koen; Helle, Gerd; Beeckman, Hans; de Haulleville, Thales; Kearsley, Elizabeth; Boeckx, Pascal

2013-04-01

Little is known about the temporal dynamics of the carbon sequestering capacity and dynamics of African tropical humid forest ecosystems in response to various environmental drivers. This lack of knowledge is mainly due to the absence of ecosystem scale flux measurements of gas exchange. However, tree growth often displays itself as alternating pattern of visible rings due to the seasonally varying growth speed of the vascular cambium. Consequently, analysis of tree growth through tree-ring analysis provides us with insights into past responses of the carbon sequestering capacity of key species to abrupt ecosystem disturbances and, while slower, a changing climate. Not only does the width and density of growth rings reflect annual growth but their isotopic composition of 13C/12C and 18O/16O isotopes also reveal the environmental conditions in which the trees were growing. In particular, stable isotope ratios in tree-rings of carbon are influenced by fractionation through carboxylation during photosynthesis and changes in leaf stomatal conductance. Similarly, fractionation of oxygen isotopes of soil water occurs at the leaf level through evapo-transipiration. As a consequence, 18O/16O (δ18O) values in wood cores will reflect both the signal of the source water as well as that of for example summer humidity. Therefore, both C and O stable isotopes might not only be valuable as proxy data for past climatic conditions but they also serve as an important tool in understanding carbon and water relations within a tropical forest ecosystems. To this end we correlate long term climate records (1961 - present) with tree ring measurement of incremental growth and high resolution analysis of tree-core stable isotope composition(δ13C , δ18O) at a tropical humid forests in the DR Congo. The Yangambi Man And Biosphere (MAB) reserve is located in the north-eastern part of DR Congo, with a distinct tropical rainforest climate. In addition to the tree-core data records and extensive meteorological records collected at both sites, observations on green leaf phenology of key species will provide us with additional information on potential carbon sequestration dynamics. Because, phenology is a first order control on plant productivity. In this unique study, using detailed tree-ring analyses together with auxiliary data, we explore the temporal dynamics of carbon and water relations and the influence on carbon sequestration of key tree species in African tropical humid forests.

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

PubMed Central

Fitzpatrick, Paul F.

2014-01-01

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

Carbon and nitrogen isotopic compositions of particulate organic matter and biogeochemical processes in the eutrophic Danshuei Estuary in northern Taiwan.

PubMed

Liu, Kon-Kee; Kao, Shuh-Ji; Wen, Liang-Saw; Chen, Kuan-Lun

2007-08-15

The Danshuei Estuary is distinctive for the relatively short residence time (1-2 d) of its estuarine water and the very high concentration of ammonia, which is the dominant species of dissolved inorganic nitrogen in the estuary, except near the river mouth. These characteristics make the dynamics of nitrogen cycling distinctively different from previously studied estuaries and result in unusual isotopic compositions of particulate nitrogen (PN). The delta(15)N(PN) values ranging from -16.4 per thousand to 3.8 per thousand lie in the lower end of nitrogen isotopic compositions (-16.4 to +18.7 per thousand) of suspended particulate matter observed in estuaries, while the delta(13)C values of particulate organic carbon (POC) and the C/N (organic carbon to nitrogen) ratios showed rather normal ranges from -25.5 per thousand to -19.0 per thousand and from 6.0 to 11.3, respectively. There were three major types of particulate organic matter (POM) in the estuary: natural terrigenous materials consisting mainly of soils and bedrock-derived sediments, anthropogenic wastes and autochthonous materials from the aquatic system. During the typhoon induced flood period in August 2000, the flux-weighted mean of delta(13)C(POC) values was -24.4 per thousand, that of delta(15)N(PN) values was +2.3 per thousand and that of C/N ratio was 9.3. During non-typhoon periods, the concentration-weighted mean was -23.6 per thousand for delta(13)C(POC), -2.6 per thousand for delta(15)N(PN) and 8.0 for C/N ratio. From the distribution of delta(15)N(PN) values of highly polluted estuarine waters, we identified the waste-dominated samples and calculated their mean properties: delta(13)C(POC) value of -23.6+/-0.7 per thousand, delta(15)N(PN) value of -3.0+/-0.1 per thousand and C/N ratio of 8.0+/-1.4. Using a three end-member mixing model based on delta(15)N(PN) values and C/N ratios, we calculated contributions of the three major allochthonous sources of POC, namely, wastes, soils and bedrock-derived sediments, to the estuary. Their contributions were, respectively, 83%, 12% and 5% under non-typhoon conditions, and 9%, 63% and 28% under typhoon conditions. The autochthonous POM had the most varied isotopic compositions, encompassing the full ranges of delta(13)C(POC) (-25.5 to -19.1 per thousand), delta(15)N(PN) (-16.4-3.8 per thousand) and C/N ratio (6.0-11.3). The heavy end of the carbon isotopic composition reflected the typical marine condition and the lower end the estuarine condition, which probably had elevated concentrations of dissolved inorganic carbon with low delta(13)C values due to input from decomposition of organic matter. The lack of isotopically heavy PN, as found in larger estuaries, was attributed to isotopically light starting materials, namely, anthropogenic wastes, the slow phytoplankton growth within the estuary and the rather short residence time; the latter two factors made (15)N enrichment during ammonia consumption very limited. The most isotopically light PN likely originated from phytoplankton incorporating (15)N-depleted nitrate near the river mouth, where ammonia inhibition of nitrate uptake probably stopped.

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

An Overview of Advanced SILAC-Labeling Strategies for Quantitative Proteomics.

PubMed

Terzi, F; Cambridge, S

2017-01-01

Comparative, quantitative mass spectrometry of proteins provides great insight to protein abundance and function, but some molecular characteristics related to protein dynamics are not so easily obtained. Because the metabolic incorporation of stable amino acid isotopes allows the extraction of distinct temporal and spatial aspects of protein dynamics, the SILAC methodology is uniquely suited to be adapted for advanced labeling strategies. New SILAC strategies have emerged that allow deeper foraging into the complexity of cellular proteomes. Here, we review a few advanced SILAC-labeling strategies that have been published during last the years. Among them, different subsaturating-labeling as well as dual-labeling schemes are most prominent for a range of analyses including those of neuronal proteomes, secretion, or cell-cell-induced stimulations. These recent developments suggest that much more information can be gained from proteomic analyses if the labeling strategies are specifically tailored toward the experimental design. © 2017 Elsevier Inc. All rights reserved.

Production of platinum radioisotopes at Brookhaven Linac Isotope Producer (BLIP)

NASA Astrophysics Data System (ADS)

Smith, Suzanne V.; McCutchan, Elizabeth; Gürdal, Gülhan; Lister, Christopher; Muench, Lisa; Nino, Michael; Sonzogni, Alexandro; Herman, Michal; Nobre, Gustavo; Cullen, Chris; Chillery, Thomas; Chowdury, Partha; Harding, Robert

2017-09-01

The accelerator production of platinum isotopes was investigated at the Brookhaven Linac Isotope Producer (BLIP). In this study high purity natural platinum foils were irradiated at 53.2, 65.7, 105.2, 151.9, 162.9 and 173.3.MeV. The irradiated foils were digested in aqua regia and then converted to their hydrochloride salt with concentrated hydrochloric acid before analyzing by gamma spectrometry periodically for at least 10 days post end of bombardment. A wide range of platinum (Pt), gold (Au) and iridium (Ir) isotopes were identified. Effective cross sections at BLIP for Pt-188, Pt-189, Pt-191 and Pt-195m were compared to literature and theoretical cross sections determined using Empire-3.2. The majority of the effective cross sections (<70 MeV) confirm those reported in the literature. While the absolute values of the theoretical cross sections were up to a factor of 3 lower, Empire 3.2 modeled thresholds and maxima correlated well with experimental values. Preliminary evaluation into a rapid separation of Pt isotopes from high levels of Ir and Au isotopes proved to be a promising approach for large scale production. In conclusion, this study demonstrated that with the use of isotopically enriched target material accelerator production of selected platinum isotopes is feasible over a wide proton energy range.

Reconstructing diet in Napoleon's Grand Army using stable carbon and nitrogen isotope analysis.

PubMed

Holder, Sammantha; Dupras, Tosha L; Jankauskas, Rimantas; Williams, Lana; Schultz, John

2017-05-01

Historical evidence has provided information regarding disease and mortality in Napoleon Bonaparte's Grand Army, but dietary information beyond individual soldier accounts remains scarce. The purpose of this research is to reconstruct the diets of Napoleon's multiethnic army who were associated with the Russian Campaign of 1812. We conducted stable carbon and nitrogen isotope ratio analysis on femoral bone collagen of 78 individuals recovered from a salvage excavation at the mass gravesite of Šiaurės miestelis in Vilnius, Lithuania. These individuals were later discovered to be Napoleonic soldiers and camp followers who participated in the 1812 Russian Campaign. Stable carbon isotope ratios range from -19.2‰ to -11.8‰, with a mean of -17.8‰ ± 1.5‰ (1 σ). Stable nitrogen isotope ratios range from 7.1‰ to 13.6‰, with a mean of 10.5‰ ± 1.4‰ (1 σ). Both δ 13 C and δ 15 N values show a wide range of variation. Stable isotope data indicate considerable dietary variation in this population associated with a multiethnic and socially stratified military population. Diets ranged from predominantly C 3 -based to predominantly C 4 -based, with varying inputs of terrestrial, freshwater, and marine animal protein. Comparison with other European populations further denotes the exceptional range of dietary variation of soldiers and camp followers in Napoleon's army. © 2017 Wiley Periodicals, Inc.

Intra-trophic isotopic discrimination of 15N/14N for amino acids in autotrophs: Implications for nitrogen dynamics in ecological studies

USDA-ARS?s Scientific Manuscript database

Metabolic reactions within heterotrophs cause discrimination in their stable nitrogen isotopic composition of amino acids (d15NAA) compared to their diets. Ecologists have exploited this measurable inter-trophic discrimination in the d15NAA value to estimate the trophic positions of heterotrophic an...

Isotopic and quantum-rovibrational-state effects for the ion-molecule reaction in the collision energy range of 0.03-10.00 eV.

PubMed

Xu, Yuntao; Xiong, Bo; Chang, Yih Chung; Ng, C Y

2017-03-29

We report detailed quantum-rovibrational-state-selected integral cross sections for the formation of H 3 O + via H-transfer (σ HT ) and H 2 DO + via D-transfer (σ DT ) from the reaction in the center-of-mass collision energy (E cm ) range of 0.03-10.00 eV, where (vvv) = (000), (100), and (020) and . The E cm inhibition and rotational enhancement observed for these reactions at E cm < 0.5 eV are generally consistent with those reported previously for H 2 O + + H 2 (D 2 ) reactions. However, in contrast to the vibrational inhibition observed for the latter reactions at low E cm < 0.5 eV, both the σ HT and σ DT for the H 2 O + + HD reaction are found to be enhanced by (100) vibrational excitation, which is not predicted by the current state-of-the-art theoretical dynamics calculations. Furthermore, the (100) vibrational enhancement for the H 2 O + + HD reaction is observed in the full E cm range of 0.03-10.00 eV. The fact that vibrational enhancement is only observed for the reaction of H 2 O + + HD, and not for H 2 O + + H 2 (D 2 ) reactions suggests that the asymmetry of HD may play a role in the reaction dynamics. In addition to the strong isotopic effect favoring the σ HT channel of the H 2 O + + HD reaction at low E cm < 0.5 eV, competition between the σ HT and σ DT of the H 2 O + + HD reaction is also observed at E cm = 0.3-10.0 eV. The present state-selected study of the H 2 O + + HD reaction, along with the previous studies of the H 2 O + + H 2 (D 2 ) reactions, clearly shows that the chemical reactivity of H 2 O + toward H 2 (HD, D 2 ) depends not only on E cm , but also on the rotational and vibrational states of H 2 O + (X 2 B 1 ). The detailed σ HT and σ DT values obtained here with single rovibrational-state selections of the reactant H 2 O + are expected to be valuable benchmarks for state-of-the-art theoretical calculations on the chemical dynamics of the title reaction.

Seasonal and inter-annual dynamics in the stable oxygen isotope compositions of water pools in a temperate humid grassland ecosystem: results from MIBA sampling and MuSICA modelling

NASA Astrophysics Data System (ADS)

Hirl, Regina; Schnyder, Hans; Auerswald, Karl; Vetter, Sylvia; Ostler, Ulrike; Schleip, Inga; Wingate, Lisa; Ogée, Jérôme

2015-04-01

The oxygen isotope composition (δ18O) of water in terrestrial ecosystems usually shows strong and dynamic variations within and between the various compartments. These variations originate from changes in the δ18O of water inputs (e.g. rain or water vapour) and from 18O fractionation phenomena in the soil-plant-atmosphere continuum. Investigations of δ18O in ecosystem water pools and of their main drivers can help us understand water relations at plant, canopy or ecosystem scale and interpret δ18O signals in plant and animal tissues as paleo-climate proxies. During the vegetation periods of 2006 to 2012, soil, leaf and stem water as well as atmospheric humidity, rain water and groundwater were sampled at bi-weekly intervals in a temperate humid pasture of the Grünschwaige Grassland Research Station near Munich (Germany). The sampling was performed following standardised MIBA (Moisture Isotopes in the Biosphere and Atmosphere) protocols. Leaf water samples were prepared from a mixture of co-dominant species in the plant community in order to obtain a canopy-scale leaf water δ18O signal. All samples were then analysed for their δ18O compositions. The measured δ18O of leaf, stem and soil water were then compared with the δ18O signatures simulated by the process-based isotope-enabled ecosystem model MuSICA (Multi-layer Simulator of the Interactions between a vegetation Canopy and the Atmosphere). MuSICA integrates current mechanistic understanding of processes in the soil-plant-atmosphere continuum. Hence, the comparison of modelled and measured data allows the identification of gaps in current knowledge and of questions to be tackled in the future. Soil and plant characteristics for model parameterisation were derived from investigations at the experimental site and supplemented by values from the literature. Eddy-covariance measurements of ecosystem CO2 (GPP, NEE) and energy (H, LE) fluxes and soil temperature data were used for model evaluation. The comparison of measured and predicted ecosystem fluxes showed that the model captured the main features of the diurnal cycles of GPP, NEE, LE and H, as well as the soil temperature dynamics. In this presentation I will present the main results of this model-data comparison, as well as results from a model sensitivity analysis performed over a range of soil, plant and meteorological parameters to evaluate the relative importance of each parameter on the δ18O signatures of the various water pools.

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

NASA Astrophysics Data System (ADS)

Kiczka, Mirjam; Wiederhold, Jan G.; Frommer, Jakob; Voegelin, Andreas; Kraemer, Stephan M.; Bourdon, Bernard; Kretzschmar, Ruben

2011-10-01

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ 56Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ 56Fe. For all soils the lightest isotopic composition was observed in a 1 M NH 2OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

The isotope mass effect on chlorine diffusion in dacite melt, with implications for fractionation during bubble growth

NASA Astrophysics Data System (ADS)

Fortin, Marc-Antoine; Watson, E. Bruce; Stern, Richard

2017-12-01

Previous experimental studies have revealed that the difference in diffusivity of two isotopes can be significant in some media and can lead to an observable fractionation effect in silicate melts based on isotope mass. Here, we report the first characterization of the difference in diffusivities of stable isotopes of Cl (35Cl and 37Cl). Using a piston-cylinder apparatus, we generated quenched melts of dacitic composition enriched in Cl; from these we fabricated diffusion couples in which Cl atoms were induced to diffuse in a chemical gradient at 1200 to 1350 °C and 1 GPa. We analyzed the run products by secondary ion mass spectrometry (SIMS) for their isotopic compositions along the diffusion profiles, and we report a diffusivity ratio for 37Cl/35Cl of 0.995 ± 0.001 (β = 0.09 ± 0.02). No significant effect of temperature on the diffusivity ratio was discernable over the 150 °C range covered by our experiments. The observed 0.5% difference in diffusivity of the two isotopes could affect our interpretation of isotopic measurements of Cl isotopes in bubble-bearing or degassed magmas, because bubble growth is regulated in part by the diffusive supply of volatiles to the bubble from the surrounding melt. Through numerical simulations, we constrain the extent of Cl isotopic fractionation between bubble and host melt during this process. Bubble growth rates vary widely in nature-which implies a substantial range in the expected magnitude of isotopic fractionation-but plausible growth scenarios lead to Cl isotopic fractionations up to about 5‰ enrichment of 35Cl relative to 37Cl in the bubble. This effect should be considered when interpreting Cl isotopic measurements of systems that have experienced vapor exsolution.

The Molybdenum Isotope System as a Tracer of Slab Input in Subduction Zones: An Example From Martinique, Lesser Antilles Arc

NASA Astrophysics Data System (ADS)

Gaschnig, Richard M.; Reinhard, Christopher T.; Planavsky, Noah J.; Wang, Xiangli; Asael, Dan; Chauvel, Catherine

2017-12-01

Molybdenum isotopes are fractionated by Earth-surface processes and may provide a tracer for the recycling of crustal material into the mantle. Here, we examined the Mo isotope composition of arc lavas from Martinique in the Lesser Antilles arc, along with Cretaceous and Cenozoic Deep Sea Drilling Project sediments representing potential sedimentary inputs into the subduction zone. Mo stable isotope composition (defined as δ98Mo in ‰ deviation from the NIST 3134 standard) in lavas older than ˜7 million years (Ma) exhibits a narrow range similar to and slightly higher than MORB, whereas those younger than ˜7 Ma show a much greater range and extend to unusually low δ98Mo values. Sediments from DSDP Leg 78A, Site 543 have uniformly low δ98Mo values whereas Leg 14, Site 144 contains both sediments with isotopically light Mo and Mo-enriched black shales with isotopically heavy Mo. When coupled with published radiogenic isotope data, Mo isotope systematics of the lavas can be explained through binary mixing between a MORB-like end-member and different sedimentary compositions identified in the DSDP cores. The lavas older than ˜7 Ma were influenced by incorporation of isotopically heavy black shales into the mantle wedge. The younger lavas are the product of mixing isotopically light sedimentary material into the mantle wedge. The change in Mo isotope composition of the lavas at ˜7 Ma is interpreted to reflect the removal of the Cretaceous black shale component due to the arrival of younger ocean crust where the age-equivalent Cretaceous sediments were deposited in shallower oxic waters. Isotopic fractionation of Mo during its removal from the slab is not required to explain the observed systematics in this system.

Trace Element and Cu Isotopic Tracers of Subsurface Flow and Transport in Wastewater Irrigated Soils

NASA Astrophysics Data System (ADS)

Carte, J.; Fantle, M. S.

2017-12-01

An understanding of subsurface flow paths is critical for quantifying the fate of contaminants in wastewater irrigation systems. This study investigates the subsurface flow of wastewater by quantifying the distribution of trace contaminants in wastewater irrigated soils. Soil samples were collected from the upper 1m of two wetlands at Penn State University's wastewater irrigation site, at which all effluent from the University's wastewater treatment plant has been sprayed since 1983. Major and trace element and Cu isotopic composition were determined for these samples, in addition to wastewater effluent and bedrock samples. The upper 20 cm of each wetland shows an enrichment of Bi, Cd, Cr, Cu, Mo, Ni, Pb, and Zn concentrations relative to deep (>1m) soils at the site by a factor of 1.7-3.5. Each wetland also has a subsurface clay rich horizon with Bi, Cu, Li, Ni, Pb, and Zn concentrations enriched by a factor of 1.4 to 5 relative to deep soils. These subsurface horizons directly underlie intervals that could facilitate preferential effluent flow: a gravel layer in one wetland, and a silty loam with visible mottling, an indication of dynamic water saturation, in the other. Trace metal concentrations in other horizons from both wetlands fall in the range of the deep soils. Significant variability in Cu isotopic composition is present in soils from both wetlands, with δ65Cu values ranging from 0.74‰ to 5.09‰. Soil δ65Cu correlates well with Cu concentrations, with lighter δ65Cu associated with higher concentrations. The Cu isotopic composition of the zones of metal enrichment are comparable to the ostensible average wastewater effluent δ65Cu value (0.61‰), while other horizons have considerably heavier δ65Cu values. We hypothesize that wastewater is the source of the metal enrichments, as each of the enriched elements are present as contaminants in wastewater, and the enrichments are located in clay-rich horizons conducive to trace metal immobilization due to adsorption. This hypothesis will be further tested by modeling with the reactive transport code CrunchTope. This study provides evidence that trace element and isotopic composition of soils can be useful tracers of subsurface hydrologic pathways and elemental fate and transport.

Late Pleistocene-Holocene deglaciation history in the Baffin Bay from radiogenic isotope provenance studies

NASA Astrophysics Data System (ADS)

Kirillova, V.; Lucassen, F.; Kasemann, S.

2016-12-01

Ice sheets dynamics as well as corresponding meltwater pulses and iceberg calving events play a major role in the delivery and dispersion of continental detritus into the ocean in glaciated environments. To trace Greenland, and potentially, Innuitian and Laurentian ice sheet history and freshwater routing during late Pleistocene to Holocene climate transition, we generate strontium (Sr), neodymium (Nd) and lead (Pb) isotope records as proxies for the provenance of continental detritus on sediment cores from the Baffin Bay: GeoTÜ SL 170, from the Greenland side, covering the last 18.000 years of climate history and GeoTÜ SL 174, close to the western coast, covering 48.000 years. For SL 170, a pronounced shift can be observed in all three isotope systems at 12 ka, what coincides with the Younger Dryas cold event. 87Sr/86Sr is around 0.74 before the event and reaches up to 0.72 during it. Nd isotope composition (IC) changes from ɛNd -32 to -26, and the 206Pb/204Pb values range from 18 to 17. The shift suggests a change in the continental sources from the Archean Southern West Greenland to a slightly younger Proterozoic source of the Nagssugtoqidian Mobile Belt in the Central West Greenland. These results allow us to estimate patterns and timings of deglaciation for different regions of the western Greenland Ice Sheet. In core SL174 variations in ɛNd ( -24 to -30) and 206Pb/204Pb ( 17 to 19) provide no clear evidence for a change of the sediment source within the Younger Dryas, despite the similar range of the values as in core SL 170. 87Sr/86Sr is more radiogenic than in SL 170, reaching values of up to 0.75, but without a systematic relation to the deposition age. Since SL 174 core is located closer to the coast and to the LGM (last glacial maximum) ice sheet border, it was possibly exposed to the direct influence of the marine-terminating ice sheet, which supplied material from enhanced glacial and subglacial erosion. Therefore, radiogenic isotope results for this core could be affected by the variable supply of minerals (e.g., micas) delivering radiogenic Sr signature.

In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems [Urban ecohydrologic dynamics revealed by in situ monitoring of H and O stable isotopes in soil water

DOE PAGES

Oerter, Erik J.; Bowen, Gabriel

2017-04-12

The water cycle in urban and hydrologically managed settings is subject to perturbations that are dynamic on small spatial and temporal scales; the effects of which may be especially profound in soils. We deploy a membrane inlet-based laser spectroscopy system in conjunction with soil moisture and temperature sensors to monitor soil water dynamics and H and O stable isotope ratios (δ 2H and δ 18O values) in a seasonally irrigated urban-landscaped garden soil over the course of 9 months between the cessation of irrigation in the autumn and the onset of irrigation through the summer. Here, we find that soilmore » water δ 2H and δ 18O values predominately reflect seasonal precipitation and irrigation inputs. A comparison of total soil water by cryogenic extraction and mobile soil water measured by in situ water vapor probes reveals that initial infiltration events after long periods of soil drying (the autumn season in this case) emplace water into the soil matrix that is not easily replaced by, or mixed with, successive pulses of infiltrating soil water. Tree stem xylem water H and O stable isotope composition did not match that of available water sources. Our findings suggest that partitioning of soil water into mobile and immobile “pools” and resulting ecohydrologic separation may occur in engineered and hydrologically managed soils and not be limited to natural settings. Furthermore, the laser spectroscopy method detailed here has potential to yield insights in a variety of critical zone and vadose zone studies, potential that is heightened by the simplicity and portability of the system.« less

In situ monitoring of H and O stable isotopes in soil water reveals ecohydrologic dynamics in managed soil systems [Urban ecohydrologic dynamics revealed by in situ monitoring of H and O stable isotopes in soil water

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

Oerter, Erik J.; Bowen, Gabriel

The water cycle in urban and hydrologically managed settings is subject to perturbations that are dynamic on small spatial and temporal scales; the effects of which may be especially profound in soils. We deploy a membrane inlet-based laser spectroscopy system in conjunction with soil moisture and temperature sensors to monitor soil water dynamics and H and O stable isotope ratios (δ 2H and δ 18O values) in a seasonally irrigated urban-landscaped garden soil over the course of 9 months between the cessation of irrigation in the autumn and the onset of irrigation through the summer. Here, we find that soilmore » water δ 2H and δ 18O values predominately reflect seasonal precipitation and irrigation inputs. A comparison of total soil water by cryogenic extraction and mobile soil water measured by in situ water vapor probes reveals that initial infiltration events after long periods of soil drying (the autumn season in this case) emplace water into the soil matrix that is not easily replaced by, or mixed with, successive pulses of infiltrating soil water. Tree stem xylem water H and O stable isotope composition did not match that of available water sources. Our findings suggest that partitioning of soil water into mobile and immobile “pools” and resulting ecohydrologic separation may occur in engineered and hydrologically managed soils and not be limited to natural settings. Furthermore, the laser spectroscopy method detailed here has potential to yield insights in a variety of critical zone and vadose zone studies, potential that is heightened by the simplicity and portability of the system.« less

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

NASA Astrophysics Data System (ADS)

Drożdżewski, Piotr; Brożyna, Anna

2005-11-01

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

New Insights from Zinc and Copper Isotopic Compositions into the Sources of Atmospheric Particulate Matter from Two Major European Cities.

PubMed

Gonzalez, R Ochoa; Strekopytov, S; Amato, F; Querol, X; Reche, C; Weiss, D

2016-09-20

This study reports spatial and temporal variability of Zn and Cu isotopes in atmospheric particulate matter (PM) collected in two major European cities with contrasting atmospheric pollution, Barcelona and London. We demonstrate that nontraditional stable isotopes identify source contributions of Zn and Cu and can play a major role in future air quality studies. In Barcelona, samples of fine PM were collected at street level at sites with variable traffic density. The isotopic signatures ranged between -0.13 ± 0.09 and -0.51 ± 0.05‰ for δ(66)ZnIRMM and between +0.04 ± 0.20 and +0.33 ± 0.15‰ for δ(65)CuAE633. Copper isotope signatures similar to those of Cu sulfides and Cu/Sb ratios within the range typically found in brake wear suggest that nonexhaust emissions from vehicles are dominant. Negative Zn isotopic signatures characteristic for gaseous emissions from smelting and combustion and large enrichments of Zn and Cd suggest contribution from metallurgical industries. In London, samples of coarse PM collected on the top of a building over 18 months display isotope signatures ranging between +0.03 ± 0.04 and +0.49 ± 0.02‰ for δ(66)ZnIRMM and between +0.37 ± 0.17 and +0.97 ± 0.21‰ for δ(65)CuAE633. Heavy Cu isotope signatures (up to +0.97 ± 0.21‰) and higher enrichments and Cu/Sb ratios during winter time indicate important contribution from fossil fuel combustion. The positive δ(66)ZnIRMM signatures are in good agreement with signatures characteristic for ore concentrates used for the production of tires and galvanized materials, suggesting nonexhaust emissions from vehicles as the main source of Zn pollution.

Determination of the origin of groundwater nitrate at an air weapons range using the dual isotope approach.

PubMed

Bordeleau, Geneviève; Savard, Martine M; Martel, Richard; Ampleman, Guy; Thiboutot, Sonia

2008-06-06

Nitrate is one of the most common contaminants in shallow groundwater, and many sources may contribute to the nitrate load within an aquifer. Groundwater nitrate plumes have been detected at several ammunition production sites. However, the presence of multiple potential sources and the lack of existing isotopic data concerning explosive degradation-induced nitrate constitute a limitation when it comes to linking both types of contaminants. On military training ranges, high nitrate concentrations in groundwater were reported for the first time as part of the hydrogeological characterization of the Cold Lake Air Weapons Range (CLAWR), Alberta, Canada. Explosives degradation is thought to be the main source of nitrate contamination at CLAWR, as no other major source is present. Isotopic analyses of N and O in nitrate were performed on groundwater samples from the unconfined and confined aquifers; the dual isotopic analysis approach was used in order to increase the chances of identifying the source of nitrate. The isotopic ratios for the groundwater samples with low nitrate concentration suggested a natural origin with a strong contribution of anthropogenic atmospheric NOx. For the samples with nitrate concentration above the expected background level the isotopic ratios did not correspond to any source documented in the literature. Dissolved RDX samples were degraded in the laboratory and results showed that all reproduced degradation processes released nitrate with a strong fractionation. Laboratory isotopic values for RDX-derived NO(3)(-) produced a trend of high delta(18)O-low delta(15)N to low delta(18)O-high delta(15)N, and groundwater samples with nitrate concentrations above the expected background level appeared along this trend. Our results thus point toward a characteristic field of isotopic ratios for nitrate being derived from the degradation of RDX.

Predicting rates of isotopic turnover across the animal kingdom: a synthesis of existing data.

PubMed

Thomas, Stephen M; Crowther, Thomas W

2015-05-01

The stable isotopes of carbon ((12)C, (13)C) and nitrogen ((14)N, (15)N) represent powerful tools in food web ecology, providing a wide range of dietary information in animal consumers. However, identifying the temporal window over which a consumer's isotopic signature reflects its diet requires an understanding of elemental incorporation, a process that varies from days to years across species and tissue types. Though theory predicts body size and temperature are likely to control incorporation rates, this has not been tested empirically across a morphologically and phylogenetically diverse range of taxa. Readily available estimates of this relationship would, however, aid in the design of stable isotope food web investigations and improve the interpretation of isotopic data collected from natural systems. Using literature-derived turnover estimates from animal species ranging in size from 1 mg to 2000 kg, we develop a predictive tool for stable isotope ecologists, allowing for estimation of incorporation rates in the structural tissues of entirely novel taxa. In keeping with metabolic scaling theory, we show that isotopic turnover rates of carbon and nitrogen in whole organisms and muscle tissue scale allometrically with body mass raised approximately to the power -0.19, an effect modulated by body temperature. This relationship did not, however, apply to incorporation rates in splanchnic tissues, which were instead dependent on the thermoregulation tactic employed by an organism, being considerably faster in endotherms than ectotherms. We believe the predictive turnover equations we provide can improve the design of experiments and interpretation of results obtained in future stable isotopic food web studies. © 2014 The Authors. Journal of Animal Ecology © 2014 British Ecological Society.

Chlorine Isotope Ratios in M Giants and S Stars

NASA Astrophysics Data System (ADS)

Maas, Zachary; Pilachowski, C. A.

2018-01-01

Chlorine is an odd-Z, light element that has been poorly studied in stars. Recently, the first stellar abundance measurements of the isotopologue 35Cl were made and the 35Cl/37Cl ratio was derived in RZ Ari (Maas et al. 2016). Additional abundance measurements are necessary to understand the Galactic chemical evolution and complex nucleosynthesis of Cl. The Cl isotope ratio in particular is important in distinguishing contributions from different nucleosynthesis sites to the surface abundances of stars. For example, current nucloesynthesis models predict that both isotopes of Cl are produced primarily during core collapse supernovae (CCSNe) with the energy and progenitor mass impacting the isotopic ratio of the ejected material. In addition to CCSNe, 37Cl is formed by the s-process both in massive stars and in AGB stars, and 35Cl may be produced from neutrino spallation. Understanding the formation of the Cl isotopes is also important to studies of the interstellar medium (ISM). A range of Cl isotope ratios mainly between 2 - 3.5 have been measured in star forming regions, in the circumstellar envelopes of evolved stars, and in proto-stellar cores using Cl bearing molecules. Additional measurements of the Cl isotope ratio in nearby stars will test nucleosynthesis models and allow comparisons with the range of isotope ratios observed in the ISM.We build on the results of Maas et al. (2016) by measuring the Cl isotope ratio in six M giants and four S stars using R~50,000 resolution spectra from Phoenix on Gemini South. We find no significant difference between the average Cl isotope ratios in the M stars and S stars and our measurements are consistent with the range of values seen in the ISM. We also find the average Cl ratio to be larger than the predicted isotope ratio of 1.8 for the solar neighborhood. Finally, two S stars, GG Pup and WY Pyx, show anomalously strong HCl features with equivalent widths ~3-5 times larger than the HCl features of other stars of similar temperature.

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

EPA Pesticide Factsheets

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

Sulfur concentration and isotopic variation in apatites from granitic to granodioritic plutons of a Cretaceous Cordilleran Batholith

NASA Astrophysics Data System (ADS)

Economos, R. C.

2012-12-01

Apatite is a common igneous accessory mineral with a high saturation temperature which can therefore crystallize over a significant portion of magmatic compositional space. Sulfur presents an opportunity to identify zoning in apatites. Unlike other trace elements, sulfur is relatively immobile in the apatite crystal structure and can be present in typical concentrations up to 1500 - 2000 ppm (or 0.5 to 1 wt% SO3). Sulfur concentration zoning in igneous apatites from ore producing magmatic systems has been identified (Streck and Dilles, 1998), but the interpretation of the cause of this zoning remains an open question. δ34S isotopic ratios of whole apatites have been used to track isotopic evolution associated with changes in magma fO2 and eruptive degassing (Rye, 2005). The presented work combines sulfur concentration mapping in zoned apatite crystals with in-situ SIMS 34S and 32S isotope measurements. Apatites were extracted from granite to granodiorite samples from the Cadiz Valley Batholith in the central Mojave Desert. This batholith is related to the pulse of Cretaceous Cordilleran magmatism that generated large batholiths in the Sierra Nevada and the Penninsular Ranges. The Mojave segment of the Cretaceous arc is unique in their construction into a full thickness of continental crust which exerted a strong influence on magmatic compositions. Apatite grains were mounted parallel to C axes, ground until grains were approximately bisected, and analyzed by Electron Microprobe at UCLA, for CaO, P2O5, SO3 and SiO2. Grains were surveyed and those yielding anomalous SO3 contents were investigated by micron-scale concentration mapping. Typical SO3 concentrations of apatites from all samples were ~0.2 wt%, while 8 to 10% of apatite grains from two samples contained cores with concentrations ranging up to 0.5 wt%. The sulfur zoning in these samples is oscillatory, in some grains representing 5 to 6 repetitions of high and low concentrations. Based on these textures, our initial interpretation is that this zoning is magmatic. Ratios of 32S to 34S in these grains were analyzed by Secondary Ionization Mass Spectrometry at UCLA in multi-collector mode utilizing a Cs+ primary ion beam and two electron multiplier ion counters. Although absolute δ34S values cannot be calculated without further standard, samples were analyzed relative to demonstrably isotopically homogeneous fragments of Durango apatite. Zoned apatite cores displayed δ34S variation well outside of analytical uncertainty. Analytical errors on individual isotopic measurements were ± 1.5‰ and reproducibility on standard grains through the analytical session was ± 0.5‰. Grains mounted parallel and perpendicular to the C axis displayed no discernible isotopic fractionation. Cores with high S concentrations displayed isotopic enrichment in 34S up to 11‰ relative to rims and core-free grains. Concentration variations may track trajectories of S solubility in evolving magmas (Ducea et al., 1994). Meanwhile heavier S isotopic ratios may suggest either dynamic crystallization/resorption behavior of S bearing species or an oxidizing environment for these earliest crystallizing apatites.

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.

Introduction to chemistry and applications in nature of mass independent isotope effects special feature.

PubMed

Thiemens, Mark H

2013-10-29

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented.

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates.

PubMed

Skulan, J; DePaolo, D J

1999-11-23

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the (44)Ca/(40)Ca isotopic ratio, the total range of variation observed is 5.5 per thousand, and as much as 4 per thousand variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers.

Calcium isotope fractionation between soft and mineralized tissues as a monitor of calcium use in vertebrates

PubMed Central

Skulan, Joseph; DePaolo, Donald J.

1999-01-01

Calcium from bone and shell is isotopically lighter than calcium of soft tissue from the same organism and isotopically lighter than source (dietary) calcium. When measured as the 44Ca/40Ca isotopic ratio, the total range of variation observed is 5.5‰, and as much as 4‰ variation is found in a single organism. The observed intraorganismal calcium isotopic variations and the isotopic differences between tissues and diet indicate that isotopic fractionation occurs mainly as a result of mineralization. Soft tissue calcium becomes heavier or lighter than source calcium during periods when there is net gain or loss of mineral mass, respectively. These results suggest that variations of natural calcium isotope ratios in tissues may be useful for assessing the calcium and mineral balance of organisms without introducing isotopic tracers. PMID:10570137

Textural and Rb-Sr isotopic evidence for late Paleozoic mylonitization within the Honey Hill fault zone southeastern Connecticut

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

O'Hara, K.D.; Gromet, L.P.

A petrographic and Rb-Sr isotopic study of rocks within and near the Honey Hill fault zone places important constraints on its history of movement. Rb-Sr apparent ages for micas and plagioclase from these rocks have been reset and range from Permian to Triassic, considerably younger than the minimum stratigraphic age (Ordovician) of the rocks studied or of Acadian (Devonian) regional metamorphism. Permian Rb-Sr ages of dynamically recrystallized muscovite date the development of mylonite fabric. An older age is precluded by the excellent preservation of unrecovered quartz, which indicates that these rocks did not experience temperatures high enough to anneal quartzmore » or thermally reset Rb-Sr isotopic systems in muscovite since the time of mylonitization. Metamorphic mineral assemblages and mineral apparent ages in rocks north of the fault zone indicate recrystallization under similar upper greenschist-lower amphibolite grade conditions during Permian to Triassic time. Collectively these results indicate that the Honey Hill fault zone was active during the Late Paleozoic and that ductile deformation and metamorphism associated with the Alleghanian orogeny extend well into southern Connecticut. An Alleghanian age for mylonitization within the Honey Hill fault zone suggests it should be considered as a possible site for the major Late Paleozoic strike-slip displacements inferred from paleomagnetic studies for parts of coastal New England and maritime Canada.« less

Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers.

PubMed

Davies, James F; Wilson, Kevin R

2016-02-16

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. We present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D2O/H2O) to measure the water diffusion coefficient over a broad range (Dw ≈ 10(-12)-10(-17) m(2)·s(-1)) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO4). For the organic liquids in binary and ternary mixtures, Dw depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, Dw can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.

Raman Spectroscopy of Isotopic Water Diffusion in Ultraviscous, Glassy, and Gel States in Aerosol by Use of Optical Tweezers

DOE PAGES

Davies, James F.; Wilson, Kevin R.

2016-01-11

The formation of ultraviscous, glassy, and amorphous gel states in aqueous aerosol following the loss of water results in nonequilibrium dynamics due to the extended time scales for diffusive mixing. Existing techniques for measuring water diffusion by isotopic exchange are limited by contact of samples with the substrate, and methods applied to infer diffusion coefficients from mass transport in levitated droplets requires analysis by complex coupled differential equations to derive diffusion coefficients. Here, we present a new technique that combines contactless levitation with aerosol optical tweezers with isotopic exchange (D 2O/H 2O) to measure the water diffusion coefficient over amore » broad range (D w ≈ 10 -12-10 -17 m 2s -1) in viscous organic liquids (citric acid, sucrose, and shikimic acid) and inorganic gels (magnesium sulfate, MgSO 4). For the organic liquids in binary and ternary mixtures, D w depends on relative humidity and follows a simple compositional Vignes relationship. In MgSO 4 droplets, water diffusivity decreases sharply with water activity and is consistent with predictions from percolation theory. These measurements show that, by combining micrometer-sized particle levitation (a contactless measurement with rapid mixing times) with an established probe of water diffusion, D w can be simply and directly quantified for amorphous and glassy states that are inaccessible to existing methods.« less

Using tunable diode laser spectroscopy to measure carbon isotope discrimination and mesophyll conductance to CO₂ diffusion dynamically at different CO₂ concentrations.

PubMed

Tazoe, Youshi; VON Caemmerer, Susanne; Estavillo, Gonzalo M; Evans, John R

2011-04-01

In C₃ leaves, the mesophyll conductance to CO₂ diffusion, g(m) , determines the drawdown in CO₂ concentration from intercellular airspace to the chloroplast stroma. Both g(m) and stomatal conductance limit photosynthetic rate and vary in response to the environment. We investigated the response of g(m) to changes in CO₂ in two Arabidopsis genotypes (including a mutant with open stomata, ost1), tobacco and wheat. We combined measurements of gas exchange with carbon isotope discrimination using tunable diode laser absorption spectroscopy with a CO₂ calibration system specially designed for a range of CO₂ and O₂ concentrations. CO₂ was initially increased from 200 to 1000 ppm and then decreased stepwise to 200 ppm and increased stepwise back to 1000 ppm, or the sequence was reversed. In 2% O₂ a step increase from 200 to 1000 ppm significantly decreased g(m) by 26-40% in all three species, whereas following a step decrease from 1000 to 200 ppm, the 26-38% increase in g(m) was not statistically significant. The response of g(m) to CO₂ was less in 21% O₂. Comparing wild type against the ost1 revealed that mesophyll and stomatal conductance varied independently in response to CO₂. We discuss the effects of isotope fractionation factors on estimating g(m) . © 2011 Blackwell Publishing Ltd.

Deciphering Seasonal Variations of Diet and Water in Modern White-Tailed Deer by In Situ Analysis of Osteons in Cortical Bone

NASA Astrophysics Data System (ADS)

Larson, T. E.; Longstaffe, F. J.

2004-12-01

In situ stable carbon and oxygen isotope compositions of biogenic apatite were obtained from longitudinally-cut sections of cortical bone from femurs of modern domesticated sheep and free-range White-Tailed deer, using an IR-laser and a GC-continuous flow interface. Ablation pits averaged 200x50 microns, making it possible to analyze individual osteons. Since cortical bone is remodelled along osteons throughout a mammal's lifetime, isotopic data at this resolution provides information about seasonal variations in diet and drinking water. The O-isotope results were calibrated using laser analyses of NBS-18 and NBS-19, which produced a value of 26.39±0.46 permil (n=27) for WS-1 calcite (accepted value, 26.25 permil). C-isotope results were calibrated using a CO2 reference gas, producing a value of 0.76±0.40permil (n=27) for WS-1, also in excellent agreement with its accepted value of 0.74 permil. Average O- and C-isotope values for a local domestic sheep (southwestern Ontario, Canada) were 12.20±0.58 and -15.70±0.35 permil (n=27), respectively. No isotopic trend occurred along or across individual osteons. This pattern is consistent with the sheep's relatively unchanging food and water sources. The free-range White-Tailed deer came from Pinery Provincial Park (PPP), southwestern Ontario. Its O- and C-isotope compositions varied systematically across individual osteons and were negatively correlated (R2=0.56). O-isotope values ranged from 13.4 to 15.5 permil; the highest values correlated with summer and the lowest values, with winter. The O-isotope compositions of the main water source (Old Ausable River Channel) varied similarly during the deer's lifetime: winter average, -10.7±0.5 permil; summer average, -8.6±0.4 permil. The C-isotope results for the deer osteons varied from -19.7 to -15.9 permil. This variation can be explained by changes in food sources. Summer diets of deer in PPP consist mainly of leafy fractions of C3 vegetation, especially sumac, cedar, oak and pine (average leaf C-isotope value, -28.4±0.8 permil). During winter, when leafy material is unavailable and deep snow inhibits access to vegetation in general, deer strip bark from vegetation (average bark C-isotope value, -25.6±0.8 permil). Certain C4 grasses (little bluestem and sandreed grass, average C-isotope value, -12.7±0.2 permil), which are abundant in unforested dune areas of PPP, commonly stand above the snow cover, and hence are also available for consumption. Deer may also range more widely in the winter, feeding on corn stalks and husks that escaped both harvest and snow cover (average C-isotope value, -11.3±0.2 permil).

Environmental Survey of the B-3 and Ford’s Farm Ranges,

DTIC Science & Technology

1983-08-01

reported have an estimated analytical error of *35% unless noted otherwise. 14 Isotopic Analysis The isotopic uranium analysis procedure used by UST...sulfate buffer and elec- trodeposited on a stainless steel disc, and isotopes of uranium (234U, 23 5U, and 2 38U) were determined by pulse height analysis ...measurements and some environmental sampling. Several special studies were also conducted, including analyses of the isotopic composition of uranium in

Isotopic (d18O/d2H) integrity of water samples collected and stored by automatic samplers

USDA-ARS?s Scientific Manuscript database

Stable water isotopes are increasingly becoming part of routine monitoring programs that utilize automatic samplers. The objectives of this study were to quantify the uncertainty in isotope signatures due to the length of sample storage (1-24 d) inside autosamplers over a range of air temperatures (...

Iron isotope fractionation in marine invertebrates in near shore environments

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Schuessler, J. A.; Vinther, J.; Matthews, A.; von Blanckenburg, F.

2014-04-01

Chitons (Mollusca) are marine invertebrates that produce radula (teeth or rasping tongue) containing high concentrations of biomineralized magnetite and other iron bearing minerals. As Fe isotope signatures are influenced by redox processes and biological fractionation, Fe isotopes in chiton radula might be expected to provide an effective tracer of ambient oceanic conditions and biogeochemical cycling. Here, in a pilot study to measure Fe isotopes in marine invertebrates, we examine Fe isotopes in modern marine chiton radula collected from different locations in the Atlantic and Pacific oceans to assess the range of isotopic values, and to test whether or not the isotopic signatures reflect seawater values. Furthermore, by comparing two species that have very different feeding habits but collected from the same location, we infer a possible link between diet and Fe isotopic signatures. Values of δ56Fe (relative to IRMM-014) in chiton teeth range from -1.90 to 0.00‰ (±0.05‰ (2σ) uncertainty in δ56Fe), probably reflecting a combination of geographical control and biological fractionation processes. Comparison with published local surface seawater Fe isotope data shows a consistent negative offset of chiton teeth Fe isotope compositions relative to seawater. Strikingly, two different species from the same locality in the North Pacific (Puget Sound, Washington, USA) have distinct isotopic signatures. Tonicella lineata, which feeds on red algae, has a mean δ56Fe of -0.65 ± 0.26‰ (2σ, 3 specimens), while Mopalia muscosa, which feeds primarily on green algae, shows lighter isotopic values with a mean δ56Fe of -1.47 ± 0.98‰ (2σ, 5 specimens). Although chitons are not simple recorders of the ambient seawater Fe isotopic signature, these preliminary results suggest that Fe isotopes provide information concerning Fe biogeochemical cycling in near shore environments, and might be used to probe sources of Fe in the diets of different organisms.

Installation of hybrid ion source on the 1-MV LLNL BioAMS spectrometer

PubMed Central

Ognibene, T. J.; Salazar, G. A.

2012-01-01

A second ion source was recently installed onto the LLNL 1-MV AMS spectrometer, which is dedicated to the quantification of 14C and 3H within biochemical samples. This source is unique among the other LLNL cesium sputter ion sources in that it can ionize both gaseous and solid samples. Also, the injection beam line has been designed to directly measure 14C/12C isotope ratios without the need for electrostatic bouncing. Preliminary tests show that this source can ionize transient CO2 gas pulses containing less than 1 ug carbon with approximately 1.5% efficiency. We demonstrate that the measured 14C/12C isotope ratio is largely unaffected by small drifts in the argon stripper gas density. We also determine that a tandem accelerating voltage of 670 kV enables the highest 14C transmission through the system. Finally, we describe a series of performance tests using solid graphite targets spanning nearly 3 orders in magnitude dynamic range and compare the results to our other ion source. PMID:23467295

Pb-Sr-Nd-O isotopic characterization of Mesozoic rocks throughout the northern end of the Peninsular Ranges batholith: Isotopic evidence for the magmatic evolution of oceanic arc–continental margin accretion during the Late Cretaceous of southern California

USGS Publications Warehouse

Kistler, Ronald W.; Wooden, Joseph L.; Premo, Wayne R.; Morton, Douglas M.

2014-01-01

Within the duration of the U.S. Geological Survey (USGS)–based Southern California Areal Mapping Project (SCAMP), many samples from the northern Peninsular Ranges batholith were studied for their whole-rock radioisotopic systematics (rubidium-strontium [Rb-Sr], uranium-thorium-lead [U-Th-Pb], and samarium-neodymium [Sm-Nd]), as well as oxygen (O), a stable isotope. The results of three main studies are presented separately, but here we combine them (>400 analyses) to produce a very complete Pb-Sr-Nd-O isotopic profile of an arc-continent collisional zone—perhaps the most complete in the world. In addition, because many of these samples have U-Pb zircon as well as argon mineral age determinations, we have good control of the timing for Pb-Sr-Nd-O isotopic variations.The ages and isotopic variations help to delineate at least four zones across the batholith from west to east—an older western zone (126–108 Ma), a transitional zone (111–93 Ma), an eastern zone (94–91 Ma), and a much younger allochthonous thrust sheet (ca. 84 Ma), which is the upper plate of the Eastern Peninsular Ranges mylonite zone. Average initial 87Sr/86 Sr (Sri), initial 206Pb/204Pb (206 Pbi), initial 208Pb/204Pb (average 208Pbi), initial epsilon Nd (average εNdi), and δ18O signatures range from 0.704, 18.787, 38.445, +3.1, and 4.0‰–9.0‰, respectively, in the westernmost zone, to 0.7071, 19.199, 38.777, −5, and 9‰–12‰, respectively, in the easternmost zone. The older western zone is therefore the more chemically and isotopically juvenile, characterized mostly by values that are slightly displaced from a mantle array at ca. 115 Ma, and similar to some modern island-arc signatures. In contrast, the isotopic signatures in the eastern zones indicate significant amounts of crustal involvement in the magmatic plumbing of those plutons. These isotopic signatures confirm previously published results that interpreted the Peninsular Ranges batholith as a progressively contaminated magmatic arc. The Peninsular Ranges batholith magmatic arc was initially an oceanic arc built on Panthalassan lithosphere that eventually evolved into a continental margin magmatic arc collision zone, eventually overriding North American cratonic lithosphere. Our Pb-Sr-Nd data further suggest that the western arc rocks represent a nearshore or inboard oceanic arc, as they exhibit isotopic signatures that are more enriched than typical mid-ocean-ridge basalt (MORB). Isotopic signatures from the central zone are transitional and indicate that enriched crustal magma sources were becoming involved in the northern Peninsular Ranges batholith magmatic plumbing. As the oceanic arc–continental margin collision progressed, a mixture of oceanic mantle and continental magmatic sources transpired. Magmatic production in the northern Peninsular Ranges batholith moved eastward and continued to tap enriched crustal magmatic sources. Similar modeling has been previously proposed for two other western margin magmatic arcs, the Sierra Nevada batholith of central California and the Idaho batholith.Calculated initial Nd signatures at ca. 100 Ma for Permian–Jurassic and Proterozoic basement rocks from the nearby San Gabriel Mountains and possible source areas along the southwestern Laurentian margin of southern California, southwestern Arizona, and northern Sonora strongly suggest their involvement with deep crustal magma mixing beneath the eastern zones of the Peninsular Ranges batholith, as well as farther east in continental lithospheric zones.Last, several samples from the allochthonous, easternmost upper-plate zone, which are considerably younger (ca. 84 Ma) than any of the rocks from the northern Peninsular Ranges batholith proper, have even more enriched average Sri, 206Pbi, 208Pbi, and εNdisignatures of 0.7079, 19.344, 38.881, and −6.6, respectively, indicative of the most-evolved magma sources in the northern Peninsular Ranges batholith and similar to radioisotopic values for rocks from the nearby Transverse Ranges, suggesting a genetic connection between the two.

Implications of 187Os isotopic heterogeneities in a mantle plume: evidence from Gorgona Island and Curaçao

NASA Astrophysics Data System (ADS)

Walker, Richard J.; Storey, Michael; Kerr, Andrew C.; Tarney, John; Arndt, Nicholas T.

1999-03-01

Recent work has suggested that the mafic-ultramafic volcanism in evidence throughout portions of the Caribbean, Central America, and northern South America, including the islands of Gorgona and Curaçao, was generated as part of a middle-Cretaceous, large igneous province. New Re-Os isochron results for tholeiitic basalts from Gorgona and Curaçao indicate crystallization ages of 89.2 ± 5.2 and 85.6 ± 8.1 Ma, respectively, consistent with reported Ar ages. The Gorgona ultramafic suite shows a large range in initial Os isotopic composition, with γ Os values ranging from -0.5 to +12.4. This large range reflects isotopic heterogeneities in the mantle source similar to those observed for modern ocean island basalts. In contrast to ocean island basalts, however, Os isotopic compositions do not correlate with variations in Nd, Sr, or Pb isotopic compositions, which are within the range of depleted mid-ocean ridge basalts. The processes that produced these rocks evidently resulted in the decoupling of Os isotopes from the Nd, Sr, and Pb isotopic systems. Picrites from Curaçao have very uniform, chondritic initial Os isotopic compositions, with initial γ Os values ranging only from -0.4 to ±1.4. Basalts from Curaçao, however, define an isochron with a 187Os-enriched initial isotopic composition (γ Os = +9.5). In contrast to the 187Os-enriched ultramafic rocks from Gorgona, the enrichment in these basalts could have resulted from lithospheric contamination. If the Gorgona and Curaçao rocks were derived from the same plume, Os results, combined with Sr, Nd, and Pb data indicate a heterogeneous plume, with multiple compositionally and isotopically distinct domains. The Os isotopic results require derivation of Os from a minimum of two distinct reservoirs, one with a composition very similar to the chondritic average and one with long-term enriched Re/Os. Oceanic crustal recycling has been invoked to explain most of the 187Os enrichments that have been observed in ocean island basalt sources and could potentially apply to the Gorgona suite. Crustal recycling, however, requires large proportions of very ancient recycled basaltic crust in the sources of the 187Os-enriched ultramafic rocks to explain the magnitude of 187Os enrichments observed. For example, addition of 20% oceanic crust to fertile mantle, and nearly 3 billion years are necessary to generate a reservoir with the Os isotopic composition of the most radiogenic komatiites. If the recycled oceanic crust was added to basalt-depleted mantle, as may be indicated by ɛ Nd values for the komatiites averaging about +10, even larger proportions of older crust are required. Large proportions of oceanic mafic crust in the sources of the 187Os-enriched komatiites, although petrologically conceivable under certain melting conditions, is unlikely here given the limited trace element and lithophile isotope system variations. These results raise questions about the efficacy of using Os isotopes to constrain the proportion of recycled oceanic crust in other plumes. Other possible mechanisms for generating 187Os-enriched mantle include invoking the existence of a 187Os-enriched lower mantle, and minor outer core-lower mantle interactions.

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.

A Cerenkov-Range analysis of the isotopic composition of cosmic rays with Z from 6 to 26

NASA Technical Reports Server (NTRS)

Fisher, A. J.; Hagen, F. A.; Maehl, R.; Ormes, J. F.

1975-01-01

High-altitude balloon data on the isotopic composition of heavy cosmic rays are reported. The experiment used a Cerenkov detector, arrays of scintillators, and a digitized wire spark chamber. Peaks assigned to the mono-isotopic elements F and Na indicate that an absolute mass scale can be derived from the data. Even-Z elements in the Z range from 12 through 16 are represented mainly by alpha-particle nuclei. Neutron-rich components dominate in the case of neon present. Mass histograms are plotted for C, O, N, Ne, Mg, and Fe.

Improvement on Fermionic properties and new isotope production in molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Wang, Ning; Wu, Tong; Zeng, Jie; Yang, Yongxu; Ou, Li

2016-06-01

By considering momentum transfer in the Fermi constraint procedure, the stability of the initial nuclei and fragments produced in heavy-ion collisions can be further improved in quantum molecular dynamics simulations. The case of a phase-space occupation probability larger than one is effectively reduced with the proposed procedure. Simultaneously, the energy conservation can be better described for both individual nuclei and heavy-ion reactions. With the revised version of the improved quantum molecular dynamics model, the fusion excitation functions of 16O+186W and the central collisions of Au+Au at 35 AMeV are re-examined. The fusion cross sections at sub-barrier energies and the charge distribution of fragments are relatively better reproduced due to the reduction of spurious nucleon emission. The charge and isotope distribution of fragments in Xe+Sn, U+U and Zr+Sn at intermediate energies are also predicted. More unmeasured extremely neutron-rich fragments with Z = 16-28 are observed in the central collisions of 238U+238U than that of 96Zr+124Sn, which indicates that multi-fragmentation of U+U may offer a fruitful pathway to new neutron-rich isotopes.

Stable Isotope Systematics in Grasshopper Assemblages Along an Elevation Gradient, Colorado

NASA Astrophysics Data System (ADS)

Kohn, M. J.; Evans, S.; Dean, J.; Nufio, C.

2012-12-01

Insects comprise over three quarters of all animal species, yet studies of body water isotopic composition are limited to only the cockroach, the hoverfly, and chironomid flies. These studies suggest that oxygen and hydrogen isotopic compositions in body water are primarily controlled by dietary water sources, with modification from respiratory and metabolic processes. In particular, outward diffusion of isotopically depleted water vapor through insect spiracles at low humidity enriches residual body water in 18O and 2H (D). Stable isotope compositions (δ18O and δD) also respond to gradients in elevation and humidity, but these influences remain poorly understood. In this study, we measured grasshopper body water and local vegetation isotopic compositions along an elevation gradient in Colorado to evaluate three hypotheses: 1) Insect body water isotopic composition is directly related to food source water composition 2) Water vapor transport alters body water isotopic compositions relative to original diet sources, and 3) Elevation gradients influence isotopic compositions in insect body water. Thirty-five species of grasshopper were collected from 14 locations in Colorado grasslands, ranging in elevation from 450 to 800 meters (n=131). Body water was distilled from previously frozen grasshopper specimens using a vacuum extraction line, furnaces (90 °C), and liquid nitrogen traps. Water samples were then analyzed for δ18O and δD on an LGR Liquid Water Isotope Analyzer, housed in the Department of Geosciences, Boise State University. Grasshopper body water isotopic compositions show wide variation, with values ranging between -76.64‰ to +42.82‰ in δD and -3.06‰ to +26.78‰ in δ18O. Precipitation δ18O values over the entire Earth excluding the poles vary by approximately 30‰, comparable to the total range measured in our single study area. Most grasshopper values deviate from the global meteoric water line relating δ18O and δD in precipitation, consistent with evaporative enrichment in food (plants) due to plant transpiration. However, grasshopper body water from any given location is further enriched in 18O and D relative to food. Isotopic values decrease slightly with increasing elevation, but some specific grasshopper species appear more sensitive to elevation. Overall, evaporative enrichment of 18O and D in this relatively dry environment appears the strongest factors influencing grasshopper compositions.

Compound-Specific Hydrogen Isotopic Records of Holocene Climate Dynamics in the Northeastern U.S.

NASA Astrophysics Data System (ADS)

Stefanescu, I.; Shuman, B. N.

2017-12-01

The northeastern United States, located between the location of Laurentide ice sheet and the dynamic North Atlantic Ocean, is an ideal region for studying paleoclimate changes on centennial to multi-millennial time scales because the region experienced multiple abrupt climate changes and variations over the past 14 ka. Over the Holocene, the region's long-term climate trend was influenced by isolation changes, the retreat of the Laurentide Ice Sheet (LIS), changes in atmospheric composition and changes in the North Atlantic Meridional Overturning Circulation (AMOC). Hydrological and pollen records show that multiple abrupt climate changes punctuate the long-term trends, even after the widely recognized events associated with the LIS and AMOC, but the mechanisms behind the abrupt climate changes observed are not well understood. To understand the mechanisms behind abrupt climate shifts, their impact on hydrology, ecosystems, regional and local climates, additional insights are needed. Compound-specific hydrogen isotope (D/H) ratios derived from terrestrial and aquatic leaf waxes and preserved in lake sediments, have been shown to record D/H ratios of environmental water and we use such data to further investigate the regional climate history. Here we present hydrogen isotope records of precipitation using compound specific hydrogen isotope of leaf wax n-alkanes derived from aquatic and terrestrial leaf waxes from three lakes: Twin Ponds, Vermont; Blanding Pond, Pennsylvania; and Crooked Pond, Massachusetts. We use the results to evaluate common climate trends across the region from an isotopic perspective and to assess changes in the spatial isotopic gradients across the northeastern US during the Holocene.

Magnesium isotope geochemistry in arc volcanism.

PubMed

Teng, Fang-Zhen; Hu, Yan; Chauvel, Catherine

2016-06-28

Incorporation of subducted slab in arc volcanism plays an important role in producing the geochemical and isotopic variations in arc lavas. The mechanism and process by which the slab materials are incorporated, however, are still uncertain. Here, we report, to our knowledge, the first set of Mg isotopic data for a suite of arc lava samples from Martinique Island in the Lesser Antilles arc, which displays one of the most extreme geochemical and isotopic ranges, although the origin of this variability is still highly debated. We find the δ(26)Mg of the Martinique Island lavas varies from -0.25 to -0.10, in contrast to the narrow range that characterizes the mantle (-0.25 ± 0.04, 2 SD). These high δ(26)Mg values suggest the incorporation of isotopically heavy Mg from the subducted slab. The large contrast in MgO content between peridotite, basalt, and sediment makes direct mixing between sediment and peridotite, or assimilation by arc crust sediment, unlikely to be the main mechanism to modify Mg isotopes. Instead, the heavy Mg isotopic signature of the Martinique arc lavas requires that the overall composition of the mantle wedge is buffered and modified by the preferential addition of heavy Mg isotopes from fluids released from the altered subducted slab during fluid-mantle interaction. This, in turn, suggests transfer of a large amount of fluid-mobile elements from the subducting slab to the mantle wedge and makes Mg isotopes an excellent tracer of deep fluid migration.

Influence of Cenozoic Plateau Growth on Precipitation and Atmospheric Dynamics

NASA Astrophysics Data System (ADS)

Insel, N.; Poulsen, C. J.; Rowley, D. B.

2011-12-01

Large mountain ranges exhibit a first-order control on climate, but it is unclear how climate may have changed over time as topography developed. In this work we use global and regional general circulation models (Genesis3.0, RegCM4) to evaluate dynamical and physical atmospheric changes associated with variations in the Andean and Himalayan topography during the Cenozoic. Our model results show that orogenic plateaus play a critical role in the evolution of climate by affecting atmospheric circulation and precipitation patterns. The influence of high topography on regional climate is not purely mechanical through orographic lifting, but also due to modifications of dynamical processes. The uplift of the Andes and Himalaya influence atmospheric flow in the following ways: (1) Orogens act as a barrier to atmospheric flow, thereby changing low-level (800 mbar) wind patterns by causing a reversal and/or significant strengthening of the prevailing winds. The establishment and strength of low-level jets is directly related to mountain elevations. (2) In contrast, monsoonal circulations form without the existence of a plateau, but are modified by high topography through thermal and mechanical effects (e.g. sensible or latent heating, orographic blocking). (3) An increase in the surface pressure gradient between high mountain ranges and the foreland enhances convergence of low-level flow and draws in moisture from adjacent regions. The increase in moisture transport provides the latent heat required to drive convective updrafts and enhances convection and precipitation along the windward flanks of high topography. (4) Regional atmospheric circulation similar to modern are established and amplify as the mountains rise to ~50-75% of their modern elevation. Our model results are largely consistent with proxy evidence of regional climate change, and have implications for the timing and rate of surface plateau uplift. Most importantly, simulated changes in paleoclimate alter oxygen isotope compositions (δ18O) in meteoric water by substantially influencing isotopic source and amount effects. Thus, it is important to distinguish changes in paleo δ18O previously interpreted only to reflect significant surface uplift from orographic thresholds that abruptly change regional climate.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Silicon isotope fractionation in rice and cucumber plants over a life cycle: Laboratory studies at different external silicon concentrations

NASA Astrophysics Data System (ADS)

Sun, Yan; Wu, Lianghuan; Li, Xiaoyan; Sun, Li; Gao, Jianfei; Ding, Tiping

2016-11-01

Understanding the variations of silicon isotopes in terrestrial higher plants can be helpful toward elucidating the global biogeochemical silicon cycle. We studied silicon isotope fractionation in rice and cucumber plants over their entire life cycles. These two different silicon-absorbing plants were grown hydroponically at different external silicon concentrations. The ranges of δ30Si values in rice were -1.89‰ to 1.69‰, -1.81‰ to 1.96‰, and -2.08‰ to 2.02‰ at 0.17 mM, 1.70 mM, and 8.50 mM silicon concentrations, respectively. The ranges of δ30Si values in cucumber were -1.38‰ to 1.21‰, -1.33‰ to 1.26‰, and -1.62‰ to 1.40‰ at 0.085 mM, 0.17 mM, and 1.70 mM external silicon concentrations, respectively. A general increasing trend in δ30Si values from lower to upper plant parts reflected the preferential incorporation of lighter silicon isotopes from transpired water to biogenic opal. Furthermore, the active uptake mechanism regulated by several transporters might have also played an important role in the preferential transport of heavy silicon isotopes into aboveground plant parts. This suggested that silicon isotope fractionation in both rice and cucumber was a Rayleigh-like process. The data on δ30Si values for the whole plants and nutrient solutions indicated that biologically mediated silicon isotope fractionation occurred during silicon uptake by roots. At lower external silicon concentrations, heavy silicon isotopes entered plants more readily than light silicon isotopes. Conversely, at higher external silicon concentrations, light silicon isotopes entered plants more readily than heavy silicon isotopes.

Power Systems for Future Missions: Appendices A-L

NASA Technical Reports Server (NTRS)

Gill, S. P.; Frye, P. E.; Littman, Franklin D.; Meisl, C. J.

1994-01-01

Selection of power system technology for space applications is typically based on mass, readiness of a particular technology to meet specific mission requirements, and life cycle costs (LCC). The LCC is typically used as a discriminator between competing technologies for a single mission application. All other future applications for a given technology are usually ignored. As a result, development cost of a technology becomes a dominant factor in the LCC comparison. Therefore, it is common for technologies such as DIPS and LMR-CBC to be potentially applicable to a wide range of missions and still lose out in the initial LCC comparison due to high development costs. This collection of appendices (A through L) contains the following power systems technology plans: CBC DIPS Technology Roadmap; PEM PFC Technology Roadmap; NAS Battery Technology Roadmap; PV/RFC Power System Technology Roadmap; PV/NAS Battery Technology Roadmap; Thermionic Reactor Power System Technology Roadmap; SP-100 Power System Technology Roadmap; Dynamic SP-100 Power System Technology Roadmap; Near-Term Solar Dynamic Power System Technology Roadmap; Advanced Solar Dynamic Power System Technology Roadmap; Advanced Stirling Cycle Dynamic Isotope Power System Technology Roadmap; and the ESPPRS (Evolutionary Space Power and Propulsion Requirements System) User's Guide.

Factors affecting individual foraging specialization and temporal diet stability across the range of a large “generalist” apex predator

USGS Publications Warehouse

Rosenblatt, Adam E.; Nifong, James C.; Heithaus, Michael R.; Mazzotti, Frank J.; Cherkiss, Michael S.; Jeffery, Brian M.; Elsey, Ruth M.; Decker, Rachel A.; Silliman, Brian R.; Guillette, Louis J.; Lowers, Russell H.; Larson, Justin C.

2015-01-01

Individual niche specialization (INS) is increasingly recognized as an important component of ecological and evolutionary dynamics. However, most studies that have investigated INS have focused on the effects of niche width and inter- and intraspecific competition on INS in small-bodied species for short time periods, with less attention paid to INS in large-bodied reptilian predators and the effects of available prey types on INS. We investigated the prevalence, causes, and consequences of INS in foraging behaviors across different populations of American alligators (Alligator mississippiensis), the dominant aquatic apex predator across the southeast US, using stomach contents and stable isotopes. Gut contents revealed that, over the short term, although alligator populations occupied wide ranges of the INS spectrum, general patterns were apparent. Alligator populations inhabiting lakes exhibited lower INS than coastal populations, likely driven by variation in habitat type and available prey types. Stable isotopes revealed that over longer time spans alligators exhibited remarkably consistent use of variable mixtures of carbon pools (e.g., marine and freshwater food webs). We conclude that INS in large-bodied reptilian predator populations is likely affected by variation in available prey types and habitat heterogeneity, and that INS should be incorporated into management strategies to efficiently meet intended goals. Also, ecological models, which typically do not consider behavioral variability, should include INS to increase model realism and applicability.

Factors affecting individual foraging specialization and temporal diet stability across the range of a large "generalist" apex predator.

PubMed

Rosenblatt, Adam E; Nifong, James C; Heithaus, Michael R; Mazzotti, Frank J; Cherkiss, Michael S; Jeffery, Brian M; Elsey, Ruth M; Decker, Rachel A; Silliman, Brian R; Guillette, Louis J; Lowers, Russell H; Larson, Justin C

2015-05-01

Individual niche specialization (INS) is increasingly recognized as an important component of ecological and evolutionary dynamics. However, most studies that have investigated INS have focused on the effects of niche width and inter- and intraspecific competition on INS in small-bodied species for short time periods, with less attention paid to INS in large-bodied reptilian predators and the effects of available prey types on INS. We investigated the prevalence, causes, and consequences of INS in foraging behaviors across different populations of American alligators (Alligator mississippiensis), the dominant aquatic apex predator across the southeast US, using stomach contents and stable isotopes. Gut contents revealed that, over the short term, although alligator populations occupied wide ranges of the INS spectrum, general patterns were apparent. Alligator populations inhabiting lakes exhibited lower INS than coastal populations, likely driven by variation in habitat type and available prey types. Stable isotopes revealed that over longer time spans alligators exhibited remarkably consistent use of variable mixtures of carbon pools (e.g., marine and freshwater food webs). We conclude that INS in large-bodied reptilian predator populations is likely affected by variation in available prey types and habitat heterogeneity, and that INS should be incorporated into management strategies to efficiently meet intended goals. Also, ecological models, which typically do not consider behavioral variability, should include INS to increase model realism and applicability.

System and method for high precision isotope ratio destructive analysis

DOEpatents

Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

2013-07-02

A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

Production of platinum radioisotopes at Brookhaven Linac Isotope Producer (BLIP)

DOE PAGES

Smith, Suzanne V.; Mccutchan, Elizabeth; Gurdal, Gulhan; ...

2017-09-13

The accelerator production of platinum isotopes was investigated at the Brookhaven Linac Isotope Producer (BLIP). In this paper high purity natural platinum foils were irradiated at 53.2, 65.7, 105.2, 151.9, 162.9 and 173.3 MeV. The irradiated foils were digested in aqua regia and then converted to their hydrochloride salt with concentrated hydrochloric acid before analyzing by gamma spectrometry periodically for at least 10 days post end of bombardment. A wide range of platinum (Pt), gold (Au) and iridiu m (Ir) isotopes were identified. Effective cross sections at BLIP for Pt-188, Pt-189, Pt-191 and Pt-195m were compared to literature and theoreticalmore » cross sections determined using Empire-3.2. The majority of the effective cross sections (<70 MeV) confirm those reported in the literature. While the absolute values of the theoretical cross sections were up to a factor of 3 lower, Empire 3.2 modeled thresholds and maxima correlated well with experimental values. Preliminary evaluation into a rapid separation of Pt isotopes from high levels of Ir and Au isotopes proved to be a promising approach for large scale production. In conclusion, this study demonstrated that with the use of isotopically enriched target material accelerator production of selected platinum isotopes is feasible over a wide proton energy range.« less

Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model.

PubMed

Voronin, Victor; Ivlev, Alexander A; Oskolkov, Vladimir; Boettger, Tatjana

2012-05-30

Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively "light" δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable "depletion" events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. The abrupt 13C depletion recorded by all tested trees for the period from June to July provides clear evidence of the transition from the dominant role of reserve carbohydrate pool (RCP) during the first half of the growth season to the preferable current year carbohydrate pool (CCP) consumption by new needles during its second half. The investigation of the isotopic signatures of Pinus sylvestris L. emphasizes the pivotal role of the intra-seasonal dynamics in carbon metabolism through the transport of assimilates from autotrophic (needles) to heterotrophic (twigs) organs of the studied trees. This provides an explanation for changes of carbon isotopic values observed within the growth season. The CMOM-based results support the hypothesis of the integration of three carbohydrate pools by photosynthesizing cells. The fluctuations of the carbon isotope ratios in different carbohydrate pools underlie various physiological processes in the tree metabolism. The possible mechanisms and pathways of formation of these carbohydrate pools are further discussed. Hence, CMOM provides a reasonable explanation for the absence of the impact of environmental conditions on the needle isotopic variables, the 12C-depletion effects and the use of RCP in needles. The model explains the negative connections between δ13C and δ18O values in all studied variables.

Intra-seasonal dynamics in metabolic processes of 13C/12C and 18O/16O in components of Scots pine twigs from southern Siberia interpreted with a conceptual framework based on the Carbon Metabolism Oscillatory Model

PubMed Central

2012-01-01

Background Carbon isotope data from conifer trees play an important role in research on the boreal forest carbon reservoir in the global carbon cycle. Carbon isotopes are routinely used to study interactions between the environment and tree growth. Moreover, carbon isotopes became an essential tool for the evaluation of carbon assimilation and transport from needles into reserve pools, as well as the allocation of stored assimilates within a tree. The successful application and interpretation of carbon isotopes rely on the coherence of isotopic fractionation modeling. This study employs a new Carbon Metabolism Oscillatory Model (CMOM) to interpret the experimental data sets on metabolic seasonal dynamics of 13C/12 C and 18O/16O ratios measured in twig components of Scots pine growing in southern Siberia (Russia). Results The dynamics of carbon isotopic variables were studied in components of Pinus sylvestris L. in light and in dark chambers during the vegetation period from 14 June to 28 July 2006. At the beginning of this period water-soluble organic matter, mostly labile sugars (including sucrose as the main component) and newly formed bulk needle material, displayed relatively “light” δ13C values (depletion in 13 C). Then, 13 C content increased again with noticeable “depletion” events in the middle of the growth period. A gradual 13 C accumulation took place in the second half of the vegetation period. Similar effects were observed both in the light and in the dark with some temporal shifts. Environmental factors did not influence the δ13C values. A gradual 12C-depletion effect was noticed in needles of the previous year. The δ13C values of sucrose and proteins from needle biomass altered independently from each other in the light chamber. A distinct negative correlation between δ13C and δ18O values was revealed for all studied variables. Conclusions The abrupt 13C depletion recorded by all tested trees for the period from June to July provides clear evidence of the transition from the dominant role of reserve carbohydrate pool (RCP) during the first half of the growth season to the preferable current year carbohydrate pool (CCP) consumption by new needles during its second half. The investigation of the isotopic signatures of Pinus sylvestris L. emphasizes the pivotal role of the intra-seasonal dynamics in carbon metabolism through the transport of assimilates from autotrophic (needles) to heterotrophic (twigs) organs of the studied trees. This provides an explanation for changes of carbon isotopic values observed within the growth season. The CMOM-based results support the hypothesis of the integration of three carbohydrate pools by photosynthesizing cells. The fluctuations of the carbon isotope ratios in different carbohydrate pools underlie various physiological processes in the tree metabolism. The possible mechanisms and pathways of formation of these carbohydrate pools are further discussed. Hence, CMOM provides a reasonable explanation for the absence of the impact of environmental conditions on the needle isotopic variables, the 12C-depletion effects and the use of RCP in needles. The model explains the negative connections between δ13C and δ18O values in all studied variables. PMID:22646756

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

Toner, Brandy M.; Rouxel, Olivier J.; Santelli, Cara M.

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffractionmore » (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ 57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Iron Transformation Pathways and Redox Micro-Environments in Seafloor Sulfide-Mineral Deposits: Spatially Resolved Fe XAS and δ(57/54)Fe Observations.

PubMed

Toner, Brandy M; Rouxel, Olivier J; Santelli, Cara M; Bach, Wolfgang; Edwards, Katrina J

2016-01-01

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ(57)Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. These micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.

Relating isotopic composition of precipitation to atmospheric patterns and local moisture recycling

NASA Astrophysics Data System (ADS)

Logan, K. E.; Brunsell, N. A.; Nippert, J. B.

2016-12-01

Local land management practices such as irrigation significantly alter surface evapotranspiration (ET), regional boundary layer development, and potentially modify precipitation likelihood and amount. How strong this local forcing is in comparison to synoptic-scale dynamics, and how much ET is recycled locally as precipitation are areas of great uncertainty and are especially important when trying to forecast the impact of local land management strategies on drought mitigation. Stable isotope analysis has long been a useful tool for tracing movement throughout the water cycle. In this study, reanalysis data and stable isotope samples of precipitation events are used to estimate the contribution of local moisture recycling to precipitation at the Konza Prairie LTER - located in the Great Plains, downwind of intensive agricultural areas. From 2001 to 2014 samples of all precipitation events over 5mm were collected and 18O and D isotopes measured. Comparison of observed precipitation totals and MERRA and ERA-interim reanalysis totals is used to diagnose periods of strong local moisture contribution (especially from irrigation) to precipitation. Large discrepancies in precipitation between observation and reanalysis, particularly MERRA, tend to follow dry periods during the growing season, presumably because while ERA-Interim adjusts soil moisture using observed surface temperature and humidity, MERRA includes no such local soil moisture adjustment and therefore lacks potential precipitation feedbacks induced by irrigation. The δ18O and δD signature of local irrigation recycling is evaluated using these incongruous observations. Self-organizing maps (SOM) are then used to identify a comprehensive range of synoptic conditions that result in precipitation at Konza LTER. Comparison of isotopic signature and SOM classification of rainfall events allows for identification of the primary moisture source and estimation of the contribution of locally recycled moisture. The climatology of precipitation source and changes in the influence of local moisture over the course of 14 years of observation are explored.

Tracing biogeochemical subsidies from glacier runoff into Alaska's coastal marine food webs

USGS Publications Warehouse

Arimitsu, Mayumi L.; Hobson, Keith A.; Webber, D'Arcy N.; Piatt, John F.; Hood, Eran W.; Fellman, Jason B.

2018-01-01

Nearly half of the freshwater discharge into the Gulf of Alaska originates from landscapes draining glacier runoff, but the influence of the influx of riverine organic matter on the trophodynamics of coastal marine food webs is not well understood. We quantified the ecological impact of riverine organic matter subsidies to glacier-marine habitats by developing a multi-trophic level Bayesian three-isotope mixing model. We utilized large gradients in stable (δ13C, δ15N, δ2H) and radiogenic (Δ14C) isotopes that trace riverine and marine organic matter sources as they are passed from lower to higher trophic levels in glacial-marine habitats. We also compared isotope ratios between glacial-marine and more oceanic habitats. Based on isotopic measurements of potential baseline sources, ambient water and tissues of marine consumers, estimates of the riverine organic matter source contribution to upper trophic-level species including fish and seabirds ranged from 12% to 44%. Variability in resource use among similar taxa corresponded to variation in species distribution and life histories. For example, riverine organic matter assimilation by the glacier-nesting seabirds Kittlitz's murrelet (Brachyramphus brevirostris) was greater than that of the forest-nesting marbled murrelet (B. marmoratus). The particulate and dissolved organic carbon in glacial runoff and near surface coastal waters was aged (12100–1500 years BP 14C-age) but dissolved inorganic carbon and biota in coastal waters were young (530 years BP 14C-age to modern). Thus terrestrial-derived subsidies in marine food webs were primarily composed of young organic matter sources released from glacier ecosystems and their surrounding watersheds. Stable isotope compositions also revealed a divergence in food web structure between glacial-marine and oceanic sites. This work demonstrates linkages between terrestrial and marine ecosystems, and facilitates a greater understanding of how climate-driven changes in freshwater runoff have the potential to alter food web dynamics within coastal marine ecosystems in Alaska.

Specific 13C labeling of leucine, valine and isoleucine methyl groups for unambiguous detection of long-range restraints in protein solid-state NMR studies.

PubMed

Fasshuber, Hannes Klaus; Demers, Jean-Philippe; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

2015-03-01

Here we present an isotopic labeling strategy to easily obtain unambiguous long-range distance restraints in protein solid-state NMR studies. The method is based on the inclusion of two biosynthetic precursors in the bacterial growth medium, α-ketoisovalerate and α-ketobutyrate, leading to the production of leucine, valine and isoleucine residues that are exclusively (13)C labeled on methyl groups. The resulting spectral simplification facilitates the collection of distance restraints, the verification of carbon chemical shift assignments and the measurement of methyl group dynamics. This approach is demonstrated on the type-three secretion system needle of Shigella flexneri, where 49 methyl-methyl and methyl-nitrogen distance restraints including 10 unambiguous long-range distance restraints could be collected. By combining this labeling scheme with ultra-fast MAS and proton detection, the assignment of methyl proton chemical shifts was achieved. Copyright © 2015 Elsevier Inc. All rights reserved.

Stable isotope biogeochemistry of seabird guano fertilization: results from growth chamber studies with maize (Zea mays).

PubMed

Szpak, Paul; Longstaffe, Fred J; Millaire, Jean-François; White, Christine D

2012-01-01

Stable isotope analysis is being utilized with increasing regularity to examine a wide range of issues (diet, habitat use, migration) in ecology, geology, archaeology, and related disciplines. A crucial component to these studies is a thorough understanding of the range and causes of baseline isotopic variation, which is relatively poorly understood for nitrogen (δ(15)N). Animal excrement is known to impact plant δ(15)N values, but the effects of seabird guano have not been systematically studied from an agricultural or horticultural standpoint. This paper presents isotopic (δ(13)C and δ(15)N) and vital data for maize (Zea mays) fertilized with Peruvian seabird guano under controlled conditions. The level of (15)N enrichment in fertilized plants is very large, with δ(15)N values ranging between 25.5 and 44.7‰ depending on the tissue and amount of fertilizer applied; comparatively, control plant δ(15)N values ranged between -0.3 and 5.7‰. Intraplant and temporal variability in δ(15)N values were large, particularly for the guano-fertilized plants, which can be attributed to changes in the availability of guano-derived N over time, and the reliance of stored vs. absorbed N. Plant δ(13)C values were not significantly impacted by guano fertilization. High concentrations of seabird guano inhibited maize germination and maize growth. Moreover, high levels of seabird guano greatly impacted the N metabolism of the plants, resulting in significantly higher tissue N content, particularly in the stalk. The results presented in this study demonstrate the very large impact of seabird guano on maize δ(15)N values. The use of seabird guano as a fertilizer can thus be traced using stable isotope analysis in food chemistry applications (certification of organic inputs). Furthermore, the fertilization of maize with seabird guano creates an isotopic signature very similar to a high-trophic level marine resource, which must be considered when interpreting isotopic data from archaeological material.

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

PubMed Central

Navarrete, Jesica U.; Borrok, David M.; Viveros, Marian; Ellzey, Joanne T.

2011-01-01

Copper isotopes may prove to be a useful tool for investigating bacteria–metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu–bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5–6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution–solid = δ65Cusolution – δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to –0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution–solid ranging from ~+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable. PMID:21785492

Predictions on the modes of decay of even Z superheavy isotopes within the range 104 ≤ Z ≤ 136

NASA Astrophysics Data System (ADS)

Santhosh, K. P.; Nithya, C.

2018-01-01

The decay modes and half lives of all the even Z isotopes of superheavy elements within the range 104 ≤ Z ≤ 136 have been predicted by comparing the alpha decay half-lives with the spontaneous fission half-lives. The Coulomb and proximity potential model for deformed nuclei (CPPMDN) and the shell-effect-dependent formula of Santhosh et al. are used to calculate the alpha half-lives and spontaneous fission half-lives respectively. For theoretical comparison the alpha decay half-lives are also calculated using Coulomb and proximity potential model (CPPM), the Viola-Seaborg-Sobiczewski semi-empirical (VSS) relation, the universal (UNIV) curve of Poenaru et al., the analytical formula of Royer and the universal decay law (UDL) of Qi et al. Another tool used for the evaluation of spontaneous fission half-lives is the semi-empirical formula of Xu et al. The nuclei with alpha decay half-lives less than spontaneous fission half-lives will survive fission and hence decay through alpha emission. The predicted half lives and decay modes are compared with the available experimental results. The one-proton and two-proton separation energies of all the isotopes are calculated to find nuclei which lie beyond the proton drip line. Among 1119 even Z nuclei within the range 104 ≤ Z ≤ 136, 164 nuclei show sequential alpha emission followed by subsequent spontaneous fission. Since the isotopes decay through alpha decay chain and the half-lives are in measurable range, these isotopes are predicted to be synthesized and detected in laboratory via alpha decay. 2 nuclei will decay by alpha decay followed by proton emission, 54 nuclei show full alpha chains, 642 nuclei will decay through spontaneous fission, 166 nuclei exhibit proton decay and 91 isotopes are found to be stable against alpha decay. All the isotopes are tabulated according to their decay modes. The study is intended to enhance further experimental investigations in superheavy region.

Investigating the Influence of Vegetation Type on Modern Leaf Wax Hydrogen Isotopes from a High Latitude Ombrotrophic Bog to Inform Paleoclimate Interpretation

NASA Astrophysics Data System (ADS)

Balascio, N.; D'Andrea, W. J.; Anderson, R. S.

2016-12-01

Leaf wax hydrogen isotopes have been used to track changes in the isotopic composition of meteoric waters in a variety of locations. However, leaf wax compounds preserved in sedimentary environments reflect a mix of plant sources that can have a large range of molecular distributions and biosynthetic fractionation factors potentially complicating paleoclimate interpretations. Here we attempt to constrain the influence of vegetation type on leaf wax hydrogen isotope values at an ombrotrophic bog in northern Norway. We present: (i) δD values of n-alkanes from modern bog vegetation to establish the influence of vegetation type on n-alkane distributions and to provide a site-specific assessment of the biosynthetic isotopic fractionation, and (ii) δD values of n-alkanes from a sediment core spanning the last 10 ka where vegetation changes have been reconstructed based on pollen analysis. We found 14 different vegetation types growing on the bog surface that have average chain lengths from 25 to 30.5 and δD values of n-C25 to n-C33 ranging from -197‰ to -116‰. These samples also have a range of δD values among n-alkane homologues, from 1‰ to 33‰. Based on isotopic measurements of modern bog water, we calculate the average apparent fractionation of n-alkanes to be -108 ± 22‰. Sedimentary δD values of n-C25 to n-C33 over the last 10 ka range from -229 to -158‰ with distinct trends among mid- and long-chain length homologues. Changes in chain lengths and δD values, at times, correspond to vegetation shifts documented by pollen data, but also show unique trends that we interpret to represent variations in local precipitation isotopes related to past hydroclimate change.

STABLE ISOTOPE STUDIES ON THE USE OF MARINE-DERIVED NUTRIENTS BY COHO SALMON JUVENILES IN AN OREGON COAST RANGE STREAM

EPA Science Inventory

We are using stable isotopes (13C, 15N, 34S) to study the use of salmon carcasses, eggs and fry by over-wintering coho juveniles in two streams of the Oregon Coast Range. Our work is paired with detailed data gathering on stream habitat condition, temperature, chemistry and PIT-t...

Urban water - a new frontier in isotope hydrology.

PubMed

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

2016-01-01

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

Effect of Isotope Mass in Simulations of JET H-mode Discharges

NASA Astrophysics Data System (ADS)

Snyder, S. E.; Onjun, T.; Kritz, A. H.; Bateman, G.; Parail, V.

2004-11-01

In JET type-I ELMy H-mode discharges, it is found that the height of the pressure pedestal increases and the frequency of the ELMs decreases with increasing isotope mass. These experimentally observed trends are obtained in these simulations only if the pedestal width increases with isotope mass. Simulations are carried out using the JETTO integrated modeling code with a dynamic model for the H-mode pedestal and the ELMs.(T. Onjun et al, Phys. Plasmas 11 (2004) 1469 and 3006.) The HELENA and MISHKA stability codes are applied to calibrate the stability criteria used to trigger ELM crashes in the JETTO code and to explore possible access to second stability in the pedestal. In the simulations, transport in the pedestal is given by the ion thermal neoclassical diffusivity, which increases with isotope mass. Consequently, as the isotope mass is increased, the pressure gradient and the bootstrap current in the pedestal rebuild more slowly after each ELM crash. Several models are explored in which the pedestal width increases with isotope mass.

Mass Dependent Fractionation of Hg Isotopes in Source Rocks, Mineral Deposits and Spring Waters of the California Coast Ranges, USA

NASA Astrophysics Data System (ADS)

Smith, C. N.; Kesler, S. E.; Blum, J. D.; Rytuba, J. J.

2007-12-01

We present here the first study of the isotopic composition of Hg in rocks, ore deposits, and active hydrothermal systems from the California Coast Ranges, one of Earth's largest Hg-depositing systems. The Franciscan Complex and Great Valley Sequence, which form the bedrock in the California Coast Ranges, are intruded and overlain by Tertiary volcanic rocks including the Clear Lake Volcanic Sequence. These rocks contain two types of Hg deposits, hot-spring deposits that form at shallow depths (<300 m) and silica-carbonate deposits that extend to greater depths (200 to 1000 m), as well as active springs and geothermal systems that release Hg to the present surface. The Franciscan Complex and Great Valley Sequence contain clastic sedimentary rocks with higher concentrations of Hg than volcanic rocks of the Clear Lake Volcanic Field. Mean Hg isotope compositions for all three rock units are similar, although the range of values in Franciscan Complex rocks is greater than in either Great Valley or Clear Lake rocks. Hot spring and silica-carbonate Hg deposits have similar average isotopic compositions that are indistinguishable from averages for the three rock units, although δ202Hg values for the Hg deposits have a greater variance than the country rocks. Precipitates from dilute spring and saline thermal waters in the area have similarly large variance and a mean δ202Hg value that is significantly lower than the ore deposits and rocks. These observations indicate there is little or no isotopic fractionation during release of Hg from its source rocks into hydrothermal solutions. Isotopic fractionation does appear to take place during transport and concentration of Hg in deposits, especially in their uppermost parts. Boiling of hydrothermal fluids is likely the most important process causing of the observed Hg isotope fractionation. This should result in the release of Hg with low δ202Hg values into the atmosphere from the top of these hydrothermal systems and a consequent enrichment in heavy Hg isotopes in the upper crust through time.

Methane transport mechanisms and isotopic fractionation in emergent macrophytes of an Alaskan tundra lake

NASA Technical Reports Server (NTRS)

Chanton, Jeffrey P.; Martens, Christopher S.; Kelley, Cheryl A.; Crill, Patrick M.; Showers, William J.

1992-01-01

The stable carbon isotopic composition of methane associated with and emitted by the two dominant emergent macrophytes abundant in the many Alaskan tundra lakes, Carex rostrata and Arctophila fulva, is determined. The carbon isotopic composition of the methane was -58.6 +/- 0.5 (n=2) for Arctophila and -66.6 +/- 2.5 (n=6) for Carex. The methane emitted by these species is depleted in C-13 by 12 per mil for Arctophila and 18 per mil for Carex relative to methane withdrawn from plant stems 1-2 cm below the waterline. The results suggest more rapid transport of (C-12)H4 relative to (C-13)H4 through plants to the atmosphere. Plant stem methane concentrations ranged from 0.2 to 4.0 percent in Arctophila, with an isotopic composition of -46.1 +/- 4.3 percent (n=8). Carex stem methane concentrations ranged from 150 to 1200 ppm, with an isotopic composition of -48.3 +/- 1.4 per mil (n=3).

Re-Os isotopic evidence for an enriched-mantle source for the Noril'sk-type, ore-bearing intrusions, Siberia

USGS Publications Warehouse

Walker, R.J.; Morgan, J.W.; Horan, M.F.; Czamanske, G.K.; Krogstad, E.J.; Fedorenko, V.A.; Kunilov, V.E.

1994-01-01

Magmatic Cu-Ni sulfide ores and spatially associated ultramafic and mafic rocks from the Noril'sk I, Talnakh, and Kharaelakh intrusions are examined for Re-Os isotopic systematics. Neodymium and lead isotopic data also are reported for the ultramafic and mafic rocks. The Re-Os data for most samples indicate closed-system behavior since the ca. 250 Ma igneous crystallization age of the intrusions. There are small but significant differences in the initial osmium isotopic compositions of samples from the three intrusions. Ores from the Noril'sk I intrusion have ??Os values that vary from +0.4 to +8.8, but average +5.8. Ores from the Talnakh intrusion have ??Os values that range from +6.7 to +8.2, averaging +7.7. Ores from the Kharaelakh intrusion have ??Os values that range from +7.8 to +12.9, with an average value of +10.4. The osmium isotopic compositions of the ore samples from the Main Kharaelakh orebody exhibit minimal overlap with those for the Noril'sk I and Talnakh intrusions, indicating that these Kharaelakh ores were derived from a more radiogenic source of osmium than the other ores. Combined osmium and lead data for major orebodies in the three intrusions plot in three distinct fields, indicating derivation of osmium and lead from at least three isotopically distinct sources. Some of the variation in lead isotopic compositions may be the result of minor lower-crustal contamination. However, in contrast to most other isotopic and trace element data, Os-Pb variations are generally inconsistent with significant crustal contamination or interaction with the subcontinental lithosphere. Thus, the osmium and lead isotopic compositions of these intrusions probably reflect quite closely the compositions of their mantle source, and suggest that these two isotope systems were insensitive to lithospheric interaction. Ultramafic and mafic rocks have osmium and lead isotopic compositions that range only slightly beyond the compositions of the ores. These rocks also have relatively uniform ??{lunate}Nd values that range only from -0.8 to + 1.1. This limited variation in neodymium isotopic composition may reflect the characteristics of the mantle sources of the rocks, or it may indicate that somehow similar proportions of crust contaminated the parental melts. The osmium, lead, and neodymium isotopic data for these rocks most closely resemble the mantle sources of certain ocean island basalts (OIB), such as some Hawaiian basalts. Hence, these data are consistent with derivation of primary melts from a mantle source similar to that of some types of hotspot activity. The long-term Re/Os enrichment of this and similar mantle sources, relative to chondritic upper mantle, may reflect 1. (1) incorporation of recycled oceanic crust into the source more than 1 Ga ago, 2. (2) derivation from a mantle plume that originated at the outer core-lower mantle interface, or 3. (3) persistence of primordial stratification of rhenium and osmium in the mantle. ?? 1994.

Isospin degree of freedom in even-even 68-76Ge and 62-70Zn isotopes

NASA Astrophysics Data System (ADS)

Jalili Majarshin, A.

2018-01-01

The introduction of isotopic spin is significant in light nuclei as Ge and Zn isotopes in order to take into account isospin effects on energy spectra. Dynamical symmetries in spherical, γ-soft limits and transition in the interacting boson model IBM-3 are analyzed. Analytic expressions and exact eigenenergies, electromagnetic transitions probabilities are obtained for the transition between spherical and γ-soft shapes by using the Bethe ansatz within an infinite-dimensional Lie algebra in light mass nuclei. The corresponding algebraic structure and reduction chain are studied in IBM-3. For examples, the nuclear structure of the 68-76Ge and 62-70Zn isotopes is calculated in IBM-3 and compared with experimental results.

Biochemical and physiological bases for the use of carbon and nitrogen isotopes in environmental and ecological studies

NASA Astrophysics Data System (ADS)

Ohkouchi, Naohiko; Ogawa, Nanako O.; Chikaraishi, Yoshito; Tanaka, Hiroyuki; Wada, Eitaro

2015-12-01

We review the biochemical and physiological bases of the use of carbon and nitrogen isotopic compositions as an approach for environmental and ecological studies. Biochemical processes commonly observed in the biosphere, including the decarboxylation and deamination of amino acids, are the key factors in this isotopic approach. The principles drawn from the isotopic distributions disentangle the complex dynamics of the biosphere and allow the interactions between the geosphere and biosphere to be analyzed in detail. We also summarize two recently examined topics with new datasets: the isotopic compositions of individual biosynthetic products (chlorophylls and amino acids) and those of animal organs for further pursuing the basis of the methodology. As a tool for investigating complex systems, compound-specific isotopic analysis compensates the intrinsic disadvantages of bulk isotopic signatures. Chlorophylls provide information about the particular processes of various photoautotrophs, whereas amino acids provide a precise measure of the trophic positions of heterotrophs. The isotopic distributions of carbon and nitrogen in a single organism as well as in the whole biosphere are strongly regulated, so that their major components such as amino acids are coordinated appropriately rather than controlled separately.

Kinetic 15N-isotope effects on algal growth

NASA Astrophysics Data System (ADS)

Andriukonis, Eivydas; Gorokhova, Elena

2017-03-01

Stable isotope labeling is a standard technique for tracing material transfer in molecular, ecological and biogeochemical studies. The main assumption in this approach is that the enrichment with a heavy isotope has no effect on the organism metabolism and growth, which is not consistent with current theoretical and empirical knowledge on kinetic isotope effects. Here, we demonstrate profound changes in growth dynamics of the green alga Raphidocelis subcapitata grown in 15N-enriched media. With increasing 15N concentration (0.37 to 50 at%), the lag phase increased, whereas maximal growth rate and total yield decreased; moreover, there was a negative relationship between the growth and the lag phase across the treatments. The latter suggests that a trade-off between growth rate and the ability to adapt to the high 15N environment may exist. Remarkably, the lag-phase response at 3.5 at% 15N was the shortest and deviated from the overall trend, thus providing partial support to the recently proposed Isotopic Resonance hypothesis, which predicts that certain isotopic composition is particularly favorable for living organisms. These findings confirm the occurrence of KIE in isotopically enriched algae and underline the importance of considering these effects when using stable isotope labeling in field and experimental studies.

Tracing the spatial and temporal variability of different water sources in a glacierized Alpine catchment (Eastern Italian Alps)

NASA Astrophysics Data System (ADS)

Engel, Michael; Penna, Daniele; Comiti, Francesco; Vignoli, Gianluca; Simoni, Silvia; Dinale, Roberto

2016-04-01

Glacierized catchments are important sources of fresh water. Although recent tracer-based studies have been carried out in these environments, more investigations are needed to understand more in detail the complex dynamics of snowmelt, glacier melt and groundwater contributions to stream water, the spatial and temporal variability of these sources of runoff and suspended sediment. In this study we used stable isotopes of water and electrical conductivity (EC) as tracers to identify the origin of different waters in the glacierized Sulden/Solda catchment (130 km², Eastern Italian Alps). The site ranges in elevation between 1112 and 3905 m a.s.l. and includes two major sub-catchments. Rainfall samples were taken from bulk collectors placed along an elevation gradient (905-2585 m a.s.l.). Winter-integrated snowmelt samples were collected from passive capillary samplers installed at different elevations (1600-2825 m a.s.l.), whereas snowmelt was sampled from dripping snow patches. Glacier melt samples were taken in summer from small rivulets on the glacier surface. Samples from the two main streams were collected monthly in 2014 and 2015 at different stream sections, major tributaries and springs. At the outlet, stream water was sampled daily by an automatic sampler, and EC, turbidity and water stage were measured every 5 minutes. Meteorological data were measured by two weather stations at 1600 and 2825 m a.s.l.. Manual samples were taken from February 2014 to November 2015 while the automatic sampling at the outlet was carried out from May to October 2014 and 2015. Results indicate that precipitation originated from air masses coming from the Atlantic Ocean, with limited influence of Mediterrean air masses. Snowmelt showed a pronounced isotopic enrichment during summer, which was also found for glacier melt, but less strong. Spring water from both sub-catchments seemed to be affected by infiltrating snowmelt during summer and represented the major stream component during winter baseflow. The tracer-based comparison of stream locations in both sub-catchments showed similar isotopic and EC dynamics during summer, highlighting that meltwater dynamics may hide the hydrochemical impact of different geology in both sub-catchments. However, EC dynamics in the left sub-catchment during winter indicated a spatial gradient of increasing solute concentrations along the stream. In contrast, an inverse spatial gradient of solute concentrations was found in the right sub-catchment, revealing a different geological setting and highlighting the impact of intensive subglacial weathering. At the outlet, EC and isotopic composition could identify clear seasonal melt water dynamics with periods of pronounced snowmelt contributions in early summer followed by dominant glacier melt contributions. Rainfall events seemed to play a major role on stream water composition in autumn. Also the impact of early snowfall and its melting in autumn 2015 could be traced and well distinguished from early summer snowmelt water. Turbidity showed strong oscillations at the daily scale during summer melt periods and markedly responded to rainfall events, which could be attributed to rapid mobilization of fine sediments and suspended sediment transport in the study catchment.

Probing the effect of neutron excess on the dynamics of Hf compound system

NASA Astrophysics Data System (ADS)

Sharma, Ishita; Kumar, Raj; Sharma, Manoj K.

2018-05-01

The reaction dynamics of 170Hf* and 174Hf* compound systems formed in 46,50Ti +124Sn reactions have been analyzed within the framework of Dynamical Cluster-decay Model (DCM) over an energy range of Ec.m.=115-156 MeV. The experimental data of fusion evaporation cross sections for 170,174Hf* systems is successfully addressed by optimizing the value of neck length ΔR. It is to be noted that calculations are performed by taking quadrupole deformations β2 with the optimum orientation of decaying fragments. Here, the effect of neutron excess has been examined on the structural properties of decaying fragments via fragmentation potential and preformation probability. The observation depicts that the isotopic effect prevails at fission region and as we move from lighter nucleus i.e. 170Hf* to heavier nucleus i.e. 174Hf*, the heavy mass fragments (HMF) start contributing along with fission fragments which are equally evident for 170Hf* as well. The ΔR values so obtained are compared at center of mass-energies which consequently provides information regarding the relative time scale of decaying fragments.

A double-stage tube furnace--acid-trapping protocol for the pre-concentration of mercury from solid samples for isotopic analysis.

PubMed

Sun, Ruoyu; Enrico, Maxime; Heimbürger, Lars-Eric; Scott, Clint; Sonke, Jeroen E

2013-08-01

High-precision mercury (Hg) stable isotopic analysis requires relatively large amounts of Hg (>10 ng). Consequently, the extraction of Hg from natural samples with low Hg concentrations (<1-20 ng/g) by wet chemistry is challenging. Combustion-trapping techniques have been shown to be an appropriate alternative. Here, we detail a modified off-line Hg pre-concentration protocol that is based on combustion and trapping. Hg in solid samples is thermally reduced and volatilized in a pure O2 stream using a temperature-programmed combustion furnace. A second furnace, kept at 1,000 °C, decomposes combustion products into H2O, CO2, SO2, etc. The O2 carrier gas, including combustion products and elemental Hg, is then purged into a 40% (v/v) acid-trapping solution. The method was optimized by assessing the variations of Hg pre-concentration efficiency and Hg isotopic compositions as a function of acid ratio, gas flow rate, and temperature ramp rate for two certified reference materials of bituminous coals. Acid ratios of 2HNO3/1HCl (v/v), 25 mL/min O2 flow rate, and a dynamic temperature ramp rate (15 °C/min for 25-150 and 600-900 °C; 2.5 °C/min for 150-600 °C) were found to give optimal results. Hg step-release experiments indicated that significant Hg isotopic fractionation occurred during sample combustion. However, no systematic dependence of Hg isotopic compositions on Hg recovery (81-102%) was observed. The tested 340 samples including coal, coal-associated rocks, fly ash, bottom ash, peat, and black shale sediments with Hg concentrations varying from <5 ng/g to 10 μg/g showed that most Hg recoveries were within the acceptable range of 80-120%. This protocol has the advantages of a short sample processing time (∼3.5 h) and limited transfer of residual sample matrix into the Hg trapping solution. This in turn limits matrix interferences on the Hg reduction efficiency of the cold vapor generator used for Hg isotopic analysis.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

In situ strontium and sulfur isotope investigation of the Ni-Cu-(PGE) sulfide ore-bearing Kevitsa intrusion, northern Finland

NASA Astrophysics Data System (ADS)

Luolavirta, Kirsi; Hanski, Eero; Maier, Wolfgang; Lahaye, Yann; O'Brien, Hugh; Santaguida, Frank

2018-01-01

The 2.06-Ga Kevitsa mafic-ultramafic intrusion in northern Finland hosts a large disseminated Ni-Cu-PGE deposit. The deposit occurs in the ultramafic olivine-pyroxene cumulates and shows a range in Ni tenors varying from 4-7 wt% (regular ore) to > 10 wt% (Ni-PGE ore). There are also a metal-poor sulfide mineralization (false ore) and contact mineralization that are uneconomic (Ni tenor < 4 wt%). The obtained 87Sr/86Sr(i) values of the Kevitsa ultramafic cumulates are highly radiogenic (> 0.7045) in comparison to the estimated depleted mantle Sr isotope ratio of 0.702 at 2.06 Ga. The sulfur δ 34S values are generally higher than + 2‰, which together with the Sr isotope data imply involvement of crustal material in the genesis of the Kevitsa intrusion and its ores. The 87Sr/86Sr(i) values obtained from the ore-bearing domain of the intrusion show stratigraphic variation and exceed 0.7050, with the maximum value reaching up to 0.7109. In contrast, in rocks around the ore domain, the initial Sr isotope compositions remain more or less constant (0.7047-0.7060) throughout the intrusive stratigraphy. The isotope data suggest that the ore-bearing domain of the intrusion represents a dynamic site with multiple injections of variably contaminated magma, whereas the surrounding part of the intrusion experienced a less vigorous emplacement history. No correlation is observed between the strontium and sulfur isotope compositions. This is explained by bulk assimilation of the silicate magma in a deeper staging magma chamber and variable assimilation of sulfur during magma transport into the Kevitsa magma chamber. The low level of metals in false ore and the Ni-depleted nature of its olivine suggest that some sulfides may have precipitated and deposited in the feeder conduit during the initial stage of magma emplacement. Cannibalization of early-formed sulfides by later magma injections may have been important in the formation of the economic ore deposit.

Atmospheric Trace Gas Abundances and Stable Isotope Ratios via IR-LIF

NASA Technical Reports Server (NTRS)

Blake, Geoffrey A.

2004-01-01

We propose to develop new technologies with support provided by PIDDP that will enable the in situ measurements of abundances and stable isotope ratios in important radiatively and biogenically active gases such as carbon dioxide, carbon monoxide, water, methane, nitrous oxide, and hydrogen sulfide to very high precision (0.1 per mil or better for the isotopic ratios, for example). Such measurements, impossible at present, could provide pivotal new constraints on the global (bio)geochemical budgets of these critical species, and could also be used to examine the dynamics of atmospheric transport on Mars, Titan, and other solar system bodies. We believe the combination of solid state light sources with imaging of the IR laser induced fluorescence (IR-LIF) via newly available detector arrays will make such in situ measurements possible for the first time. Even under ambient terrestrial conditions, the LIF yield from vibrational excitation of species such as water and carbon dioxide should produce emission measures well in excess of ten billion photons/sec from samples volumes of order 1 c.c. These count rates can, in principle, yield detection limits into the sub-ppt range that are required for the in situ isotopic study of atmospheric trace gases. While promising, such technologies are relatively immature, but developing rapidly, and there are a great many uncertainties regarding their applicability to in situ IR-LIF planetary studies. We therefore feel PIDDP support will be critical to developing these new tools, and propose a three-year program to combine microchip near-IR lasers with low background detection axes and state-of-the-art HgCdTe detectors developed for astronomical spectroscopy to investigate the sensitivity of IR-LIF under realistic planetary conditions, to optimize the optical pumping and filtering schemes for important species, and to apply the spectrometer to the non-destructive measurement of stable isotopes in a variety of test samples. These studies form the necessary precursors to the development of compact, lightweight stable isotope/trace gas sensors for future planetary missions.

Time-dependent wave-packet quantum dynamics study of the Ne + D2(+) (v0 = 0-2, j0 = 0) → NeD(+) + D reaction: including the coriolis coupling.

PubMed

Yao, Cui-Xia; Zhang, Pei-Yu

2014-07-10

The dynamics of the Ne + D2(+) (v0 = 0-2, j0 = 0) → NeD(+) + D reaction has been investigated in detail by using an accurate time-dependent wave-packet method on the ground 1(2)A' potential energy surface. Comparisons between the Coriolis coupling results and the centrifugal-sudden ones reveal that Coriolis coupling effect can influence reaction dynamics of the NeD2(+) system. Integral cross sections have been evaluated for the Ne + D2(+) reaction and its isotopic variant Ne + H2(+), and a considerable intermolecular isotopic effect has been found. Also obvious is the great enhancement of the reactivity due to the reagent vibrational excitation. Besides, a comparison with previous theoretical results is also presented and discussed.

Measurement of plutonium isotope ratios in nuclear fuel samples by HPLC-MC-ICP-MS

NASA Astrophysics Data System (ADS)

Günther-Leopold, I.; Waldis, J. Kobler; Wernli, B.; Kopajtic, Z.

2005-04-01

Radioactive isotopes are traditionally quantified by means of radioactivity counting techniques ([alpha], [beta], [gamma]). However, these methods often require extensive matrix separation and sample purification before the identification of specific isotopes and their relative abundance is possible as it is necessary in the frame of post-irradiation examinations on nuclear fuel samples. The technique of multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is attracting much attention because it permits the precise measurement of the isotope compositions for a wide range of elements combined with excellent limits of detection due to high ionization efficiencies. The present paper describes one of the first applications of an online high-performance liquid chromatographic separation system coupled to a MC-ICP-MS in order to overcome isobaric interferences for the determination of the plutonium isotope composition and concentrations in irradiated nuclear fuels. The described chromatographic separation is sufficient to prevent any isobaric interference between 238Pu present at trace concentrations and 238U present as the main component of the fuel samples. The external reproducibility of the uncorrected plutonium isotope ratios was determined to be between 0.04 and 0.2% (2 s) resulting in a precision in the [per mille sign] range for the isotopic vectors of the irradiated fuel samples.

Introduction to Chemistry and Applications in Nature of Mass Independent Isotope Effects Special Feature

PubMed Central

Thiemens, Mark H.

2013-01-01

Stable isotope ratio variations are regulated by physical and chemical laws. These rules depend on a relation with mass differences between isotopes. New classes of isotope variation effects that deviate from mass dependent laws, termed mass independent isotope effects, were discovered in 1983 and have a wide range of applications in basic chemistry and nature. In this special edition, new applications of these effects to physical chemistry, solar system origin models, terrestrial atmospheric and biogenic evolution, polar paleo climatology, snowball earth geology, and present day atmospheric sciences are presented. PMID:24167299

Relative and accurate measurement of protein abundance using 15N stable isotope labeling in Arabidopsis (SILIA).

PubMed

Guo, Guangyu; Li, Ning

2011-07-01

In the quantitative proteomic studies, numerous in vitro and in vivo peptide labeling strategies have been successfully applied to measure differentially regulated protein and peptide abundance. These approaches have been proven to be versatile and repeatable in biological discoveries. (15)N metabolic labeling is one of these widely adopted and economical methods. However, due to the differential incorporation rates of (15)N or (14)N, the labeling results produce imperfectly matched isotopic envelopes between the heavy and light nitrogen-labeled peptides. In the present study, we have modified the solid Arabidopsis growth medium to standardize the (15)N supply, which led to a uniform incorporation of (15)N into the whole plant protein complement. The incorporation rate (97.43±0.11%) of (15)N into (15)N-coded peptides was determined by correlating the intensities of peptide ions with the labeling efficiencies according to Gaussian distribution. The resulting actual incorporation rate (97.44%) and natural abundance of (15)N/(14)N-coded peptides are used to re-calculate the intensities of isotopic envelopes of differentially labeled peptides, respectively. A modified (15)N/(14)N stable isotope labeling strategy, SILIA, is assessed and the results demonstrate that this approach is able to differentiate the fold change in protein abundance down to 10%. The machine dynamic range limitation and purification step will make the precursor ion ratio deriving from the actual ratio fold change. It is suggested that the differentially mixed (15)N-coded and (14)N-coded plant protein samples that are used to establish the protein abundance standard curve should be prepared following a similar protein isolation protocol used to isolate the proteins to be quantitated. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Zooplankton trophic niches respond to different water types of the western Tasman Sea: A stable isotope analysis

NASA Astrophysics Data System (ADS)

Henschke, Natasha; Everett, Jason D.; Suthers, Iain M.; Smith, James A.; Hunt, Brian P. V.; Doblin, Martina A.; Taylor, Matthew D.

2015-10-01

The trophic relationships of 21 species from an oceanic zooplankton community were studied using stable isotopes of carbon and nitrogen. Zooplankton and suspended particulate organic matter (POM) were sampled in three different water types in the western Tasman Sea: inner shelf (IS), a cold core eddy (CCE) and a warm core eddy (WCE). δ15N values ranged from 3.9‰ for the parasitic copepod Sapphirina augusta to 10.2‰ for the euphausiid, Euphausia spinifera. δ13C varied from -22.6 to -19.4‰ as a result of the copepod Euchirella curticauda and E. spinifera. The isotopic composition of POM varied significantly among water types; as did the trophic enrichment of zooplankton over POM, with the lowest enrichment in the recently upwelled IS water type (0.5‰) compared to the warm core eddy (1.6‰) and cold core eddy (2.7‰). The WCE was an oligotrophic environment and was associated with an increased trophic level for omnivorous zooplankton (copepods and euphausiids) to a similar level as carnivorous zooplankton (chaetognaths). Therefore carnivory in zooplankton can increase in response to lower abundance and reduced diversity in their phytoplankton and protozoan prey. Trophic niche width comparisons across three zooplankton species: the salp Thalia democratica, the copepod Eucalanus elongatus and the euphausiid Thysanoessa gregaria, indicated that both niche partitioning and competition can occur within the zooplankton community. We have shown that trophic relationships among the zooplankton are dynamic and respond to different water types. The changes to the zooplankton isotopic niche, however, were still highly variable as result of oceanographic variation within water types.

Near-Continuous Isotopic Characterization of Soil N2O Fluxes from Maize Production

NASA Astrophysics Data System (ADS)

Anex, R. P.; Francis Clar, J.

2015-12-01

Isotopomer ratios of N2O and especially intramolecular 15N site preference (SP) have been proposed as indicators of the sources of N2O and for providing insight into the contributions of different microbial processes. Current knowledge, however, is mainly based on pure culture studies and laboratory flask studies using mass spectrometric analysis. Recent development of laser spectroscopic methods has made possible high-precision, in situ measurements. We present results from a maize production field in Columbia County, Wisconsin, USA. Data were collected from the fertilized maize phase of a maize-soybean rotation. N2O mole fractions and isotopic composition were determined using an automatic gas flux measurement system comprising a set of custom-designed automatic chambers, circulating gas paths and an OA-ICOS N2O Isotope Analyzer (Los Gatos Research, Inc., Model 914-0027). The instrument system allows for up to 15 user programmable soil gas chambers. Wide dynamic range and parts-per-billion precision of OA-ICOS laser absorption instrument allows for extremely rapid estimation of N2O fluxes. Current operational settings provide measurements of N2O and its isotopes every 20 seconds with a precision of 0.1 ± 0.050 PPB. Comparison of measurements from four chambers (two between row and two in-row) show very different aggregate N2O flux, but SP values suggest similar sources from nitrifier denitrification and incomplete bacterial denitrification. SP values reported are being measured throughout the current growing season. To date, the majority of values are consistent with an origin from bacterial denitrification and coincide with periods of high water filled pore space.

Quantification of isotopic turnover in agricultural systems

NASA Astrophysics Data System (ADS)

Braun, A.; Auerswald, K.; Schnyder, H.

2012-04-01

The isotopic turnover, which is a proxy for the metabolic rate, is gaining scientific importance. It is quantified for an increasing range of organisms, from microorganisms over plants to animals including agricultural livestock. Additionally, the isotopic turnover is analyzed on different scales, from organs to organisms to ecosystems and even to the biosphere. In particular, the quantification of the isotopic turnover of specific tissues within the same organism, e.g. organs like liver and muscle and products like milk and faeces, has brought new insights to improve understanding of nutrient cycles and fluxes, respectively. Thus, the knowledge of isotopic turnover is important in many areas, including physiology, e.g. milk synthesis, ecology, e.g. soil retention time of water, and medical science, e.g. cancer diagnosis. So far, the isotopic turnover is quantified by applying time, cost and expertise intensive tracer experiments. Usually, this comprises two isotopic equilibration periods. A first equilibration period with a constant isotopic input signal is followed by a second equilibration period with a distinct constant isotopic input signal. This yields a smooth signal change from the first to the second signal in the object under consideration. This approach reveals at least three major problems. (i) The input signals must be controlled isotopically, which is almost impossible in many realistic cases like free ranging animals. (ii) Both equilibration periods may be very long, especially when the turnover rate of the object under consideration is very slow, which aggravates the first problem. (iii) The detection of small or slow pools is improved by large isotopic signal changes, but large isotopic changes also involve a considerable change in the input material; e.g. animal studies are usually carried out as diet-switch experiments, where the diet is switched between C3 and C4 plants, since C3 and C4 plants differ strongly in their isotopic signal. The additional change in nutrition induces changes in physiology that are likely to bias the estimation of the isotopic turnover. We designed an experiment with lactating cows which were successively exposed to the diet's natural isotopic variation and a diet-switch. We examined whether the same turnover information can be obtained from the natural (uncontrolled, short-term) isotopic variation as from the diet-switch experiment. Statistical methods to retrieve the turnover characteristics comprised multi-pool compartmental modeling for the diet-switch experiment as well as correlation analysis to perform wiggle-matching and quantification of autocorrelation (geostatistics) for the analysis of the natural variation. All three methods yielded similar results but differed in their strengths and weaknesses that will be highlighted. Combining the strengths of the new methods can make this tool even more advantageous than diet-switch experiments in many cases. In particular, the new approach empowers studying isotope turnover under a wider range of keepings, wildlife conditions and species, yielding turnover estimates that are not biased by changes in nutrition.

Strontium isotope systematics of scheelite and apatite from the Felbertal tungsten deposit, Austria - results of in-situ LA-MC-ICP-MS analysis

NASA Astrophysics Data System (ADS)

Kozlik, Michael; Gerdes, Axel; Raith, Johann G.

2016-02-01

The in-situ Sr isotopic systematics of scheelite and apatite from the Felbertal W deposit and a few regional Variscan orthogneisses ("Zentralgneise") have been determined by LA-MC-ICP-MS. The 87Sr/86Sr ratios of scheelite and apatite from the deposit are highly radiogenic and remarkably scattering. In the early magmatic-hydrothermal scheelite generations (Scheelite 1 and 2) the 87Sr/86Sr ratios range from 0.72078 to 0.76417 and from 0.70724 to 0.76832, respectively. Metamorphic Scheelite 3, formed by recrystallisation and local mobilisation of older scheelite, is characterised by even higher 87Sr/86Sr values between 0.74331 and 0.80689. Statistics allows discriminating the three scheelite generations although there is considerable overlap between Scheelite 1 and 2; they could be mixtures of the same isotopic reservoirs. The heterogeneous and scattering 87Sr/86Sr ratios of the two primary scheelite generations suggest modification of the Sr isotope system due to fluid-rock interaction and isotopic disequilibrium. Incongruent release of 87Sr from micas in the Early Palaeozoic host rocks of the Habach Complex contributed to the solute budget of the hydrothermal fluids and may explain the radiogenic Sr isotope signature of scheelite. Spatially resolved analyses revealed isotopic disequilibrium even on a sub-mm scale within zoned Scheelite 2 crystals indicating scheelite growth in an isotopic dynamical hydrothermal system. Zoned apatite from the W mineralised Early Carboniferous K1-K3 orthogneiss in the western ore field yielded 87Sr/86Sr of 0.72044-0.74514 for the cores and 0.74535-0.77937 for the rims. Values of magmatic apatite cores from the K1-K3 orthogneiss are comparable to those of primary Scheelite 1; they are too radiogenic to be magmatic. The Sr isotopic composition of apatite cores was therefore equally modified during the hydrothermal mineralisation processes, therefore supporting the single-stage genetic model in which W mineralisation is associated with the intrusion of the K1-K3 metagranitoid at Felbertal. The subsequent regional metamorphic overprint of the deposit caused redistribution of 87Sr as a consequence of metamorphic reactions involving Rb and Sr-bearing minerals. Metamorphic Scheelite 3 and apatite rims (e.g., in the K1-K3 orthogneiss) generally became more radiogenic during this process. However, local recrystallisation of primary scheelite under closed conditions (without addition of 87Sr by the metamorphic fluid) is also documented. The latter process resulted in a homogenisation of the isotope composition of Scheelite 3. Further increase in 87Sr/86Sr ratios in Scheelite 3 and apatite rims is attributed to Late Alpine (?) metamorphic recrystallisation and redistribution of 87Sr by metamorphic fluids.

Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

NASA Astrophysics Data System (ADS)

Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.

2011-11-01

The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. A further part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the soil profile. Finally, we highlight state-of-the-art stable isotope methodologies and their latest developments. From the presented evidence we conclude that there exists a tight coupling of physical, chemical and biological processes involved in C cycling and C isotope fluxes in the plant-soil-atmosphere system. Generally, research using information from C isotopes allows an integrated view of the different processes involved. However, complex interactions among the range of processes complicate or currently impede the interpretation of isotopic signals in CO2 or organic compounds at the plant and ecosystem level. This review tries to identify present knowledge gaps in correctly interpreting carbon stable isotope signals in the plant-soil-atmosphere system and how future research approaches could contribute to closing these gaps.

Tracing thallium contamination in soils using isotopes

NASA Astrophysics Data System (ADS)

Vaněk, Aleš; Grösslová, Zuzana; Mihaljevič, Martin; Ettler, Vojtěch; Trubač, Jakub; Teper, Leslaw; Cabala, Jerzy; Rohovec, Jan; Penížek, Vít; Zádorová, Tereza; Pavlů, Lenka; Holubík, Ondřej; Drábek, Ondřej; Němeček, Karel; Houška, Jakub; Ash, Christopher

2017-04-01

We report the thallium (Tl) isotope record in moderately contaminated soils, which have been historically affected by emissions from coal-fired power plants. Our findings clearly demonstrate that Tl of anthropogenic (high-temperature) origin with light isotope composition was deposited onto the studied soils, where heavier Tl (ɛ205Tl -1) naturally occurs. The results show a positive linear relationship (R2 = 0.71) between 1/Tl and the isotope record, as determined for all the soils and bedrocks, also indicative of binary Tl mixing between two dominant reservoirs. We also identified significant Tl isotope variations within the products from coal combustion and thermo-desorption experiments with local Tl-rich coal pyrite. Bottom ash exhibited the heaviest Tl isotope composition (ɛ205Tl 0), followed by fly ash (ɛ205Tl between -2.5 and -2.8) and volatile Tl fractions (ɛ205Tl between -6.2 and -10.3), suggesting partial Tl isotope fractionations. Despite the evident role of soil processes in the isotope redistribution, we demonstrate that Tl contamination can be traced in soils, and propose that the isotope data represent a possible tool to aid our understanding of post-depositional Tl dynamics in surface environments for the future. This research was supported by the Czech Science Foundation (grant no. 14-01866S and 17-03211S).

Continental sedimentary processes decouple Nd and Hf isotopes

NASA Astrophysics Data System (ADS)

Garçon, Marion; Chauvel, Catherine; France-Lanord, Christian; Huyghe, Pascale; Lavé, Jérôme

2013-11-01

The neodymium and hafnium isotopic compositions of most crustal and mantle rocks correlate to form the "Terrestrial Array". However, it is now well established that whereas coarse detrital sediments follow this trend, fine-grained oceanic sediments have high Hf ratios relative to their Nd isotopic ratios. It remains uncertain whether this "decoupling" of the two isotopic systems only occurs in the oceanic environment or if it is induced by sedimentary processes in continental settings. In this study, the hafnium and neodymium isotopic compositions of sediments in large rivers is expressly used to constrain the behavior of the two isotopic systems during erosion and sediment transport from continent to ocean. We report major and trace element concentrations together with Nd and Hf isotopic compositions of bedloads, suspended loads and river banks from the Ganges River and its tributaries draining the Himalayan Range i.e. the Karnali, the Narayani, the Kosi and the Marsyandi Rivers. The sample set includes sediments sampled within the Himalayan Range in Nepal, at the Himalayan mountain front, and also downstream on the floodplain and at the outflow of the Ganges in Bangladesh. Results show that hydrodynamic sorting of minerals explains the entire Hf isotopic range, i.e. more than 10 εHf units, observed in the river sediments but does not affect the Nd isotopic composition. Bedloads and bank sediments have systematically lower εHf values than suspended loads sampled at the same location. Coarse-grained sediments lie below or on the Terrestrial Array in an εHf vs. εNd diagram. In contrast, fine-grained sediments, including most of the suspended loads, deviate from the Terrestrial Array toward higher εHf relative to their εNd, as is the case for oceanic terrigenous clays. The observed Nd-Hf decoupling is explained by mineralogical sorting processes that enrich bottom sediments in coarse and dense minerals, including unradiogenic zircons, while surface sediments are enriched in fine material with radiogenic Hf signatures. The data also show that Nd-Hf isotopic decoupling increases with sediment transport in the floodplain to reach its maximum at the river mouth. This implies that the Nd-Hf isotopic decoupling observed in worldwide oceanic clays and river sediments is likely to have the same origin. Finally, we estimated the Nd-Hf isotopic composition of the present-day mantle if oceanic sediments had never been subducted and conclude that the addition of oceanic sediments with their anomalous Nd-Hf isotopic compositions has slowly shifted the composition of the Earth's mantle towards more radiogenic Hf values through time.

Forensic utility of the carbon isotope ratio of PVC tape backings

NASA Astrophysics Data System (ADS)

Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.

2008-12-01

Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting materials and recycling reactants during manufacture; as a result, tapes may be otherwise physically and chemical indistinguishable, but may have distinct carbon isotope ratios. We compared the carbon isotope ratios of 6 pairs of pre- and post-blast samples of PVC tapes adhered to explosive charges. The carbon isotope ratios of the post-blast samples were 0 to 0.5 ‰ higher than the corresponding pre-blast samples. Possible causes of this carbon isotope increase may be the reaction of the plasticizer and/or adhesive with the PVC backing during the explosion or the addition of debris to the tape backing during the explosion. Even with these minor explosive-induced carbon isotope alterations, the δ13C values of post-blast PVC tape backings were similar enough to the starting material to make carbon isotope ratios of post-blast tape a useful forensic tool. The range of carbon isotope ratios that would be used to exclude potential matches would have to be larger for post-blast samples, but with a 17 ‰ range in the population, this approach may still be useful for post-blast tape samples.

Chemical and isotopic data collected from groundwater, surface-water, and atmospheric precipitation sites in Upper Kittitas County, Washington, 2010-12

USGS Publications Warehouse

Hinkle, Stephen R.; Ely, D. Matthew

2013-01-01

As part of a multidisciplinary U.S. Geological Survey study of water resources in Upper Kittitas County, Washington, chemical and isotopic data were collected from groundwater, surface-water, and atmospheric precipitation sites from 2010 to 2012. These data are documented here so that interested parties can quickly and easily find those chemical and isotopic data related to this study. The locations of the samples are shown on an interactive map of the study area. This report is dynamic; additional data will be added to it as they become available.

Linking protein motion to enzyme catalysis.

PubMed

Singh, Priyanka; Abeysinghe, Thelma; Kohen, Amnon

2015-01-13

Enzyme motions on a broad range of time scales can play an important role in various intra- and intermolecular events, including substrate binding, catalysis of the chemical conversion, and product release. The relationship between protein motions and catalytic activity is of contemporary interest in enzymology. To understand the factors influencing the rates of enzyme-catalyzed reactions, the dynamics of the protein-solvent-ligand complex must be considered. The current review presents two case studies of enzymes-dihydrofolate reductase (DHFR) and thymidylate synthase (TSase)-and discusses the role of protein motions in their catalyzed reactions. Specifically, we will discuss the utility of kinetic isotope effects (KIEs) and their temperature dependence as tools in probing such phenomena.

Determination of lithium isotopes at natural abundance levels by atomic absorption spectrometry

USGS Publications Warehouse

Meier, A.L.

1982-01-01

The relationships of the absorption of 6Li and 7Li hollow cathode lamp emissions are used to determine lithium isotopic composition in the natural abundance range of geologic materials. Absorption was found to have a nonlinear dependence upon total lithium concentration and isotopic composition. A method using nonlinear equations to describe the relationship of the absorption of 6Li and 7Li lamp radiation is proposed as a means of calculating isotopic composition that is independent of total lithium concentration.

Further analysis of the IRIS iron isotope experiment

NASA Technical Reports Server (NTRS)

Tarle, G.; Ahlen, S. P.; Cartwright, B. G.; Solarz, M.

1980-01-01

The IRIS Fe isotope experiment was extended to atomic charges of Z = 19, with isotopic distributions for 500 events ranging from 18 to 28. Normalization of the detector response functions at Fe-56 produced a single well resolved peak at Sc-45, establishing the resolution and mass scale of the device over the entire charge region. The abundance distributions for the predominantly primary isotopes Ca-40, Fe-54, Fe-56, Ni-58, and Ni-60 do not indicate a large admixture of material with distinctly nonsolar abundances.

The chlorine isotope composition of the moon and implications for an anhydrous mantle.

PubMed

Sharp, Z D; Shearer, C K; McKeegan, K D; Barnes, J D; Wang, Y Q

2010-08-27

Arguably, the most striking geochemical distinction between Earth and the Moon has been the virtual lack of water (hydrogen) in the latter. This conclusion was recently challenged on the basis of geochemical data from lunar materials that suggest that the Moon's water content might be far higher than previously believed. We measured the chlorine isotope composition of Apollo basalts and glasses and found that the range of isotopic values [from -1 to +24 per mil (per thousand) versus standard mean ocean chloride] is 25 times the range for Earth. The huge isotopic spread is explained by volatilization of metal halides during basalt eruption--a process that could only occur if the Moon had hydrogen concentrations lower than those of Earth by a factor of approximately 10(4) to 10(5), implying that the lunar interior is essentially anhydrous.

New reference materials for nitrogen-isotope-ratio measurements

USGS Publications Warehouse

Böhlke, John Karl; Gwinn, C. J.; Coplen, T. B.

1993-01-01

Three new reference materials were manufactured for calibration of relative stable nitrogen-isotope-ratio measurements: USGS25 (ammonium sulfate) d15N' = -30 per mil; USGS26 (ammonium sulfate) d15N' = +54 per mil; USGS32 (potassium nitrate) d15N' = +180 per mil, where d15N', relative to atmospheric nitrogen, is an approximate value subject to change following interlaboratory comparisons. These materials are isotopically homogeneous in aliquots at least as small as 10 µmol N2 (or about 1-2 mg of salt). The new reference materials greatly extend the range of d15N values of internationally distributed standards, and they allow normalization of d15N measurements over almost the full range of known natural isotope variation on Earth. The methods used to produce these materials may be adapted to produce homogeneous local laboratory standards for routine use.

Development of particle induced gamma-ray emission methods for nondestructive determination of isotopic composition of boron and its total concentration in natural and enriched samples.

PubMed

Chhillar, Sumit; Acharya, Raghunath; Sodaye, Suparna; Pujari, Pradeep K

2014-11-18

We report simple particle induced gamma-ray emission (PIGE) methods using a 4 MeV proton beam for simultaneous and nondestructive determination of the isotopic composition of boron ((10)B/(11)B atom ratio) and total boron concentrations in various solid samples with natural isotopic composition and enriched with (10)B. It involves measurement of prompt gamma-rays at 429, 718, and 2125 keV from (10)B(p,αγ)(7)Be, (10)B(p, p'γ)(10)B, and (11)B(p, p'γ)(11)B reactions, respectively. The isotopic composition of boron in natural and enriched samples was determined by comparing peak area ratios corresponding to (10)B and (11)B of samples to natural boric acid standard. An in situ current normalized PIGE method, using F or Al, was standardized for total B concentration determination. The methods were validated by analyzing stoichiometric boron compounds and applied to samples such as boron carbide, boric acid, carborane, and borosilicate glass. Isotopic compositions of boron in the range of 0.247-2.0 corresponding to (10)B in the range of 19.8-67.0 atom % and total B concentrations in the range of 5-78 wt % were determined. It has been demonstrated that PIGE offers a simple and alternate method for total boron as well as isotopic composition determination in boron based solid samples, including neutron absorbers that are important in nuclear technology.

Stable isotope evidence for hydrologic conditions during regional metamorphism in the Panamint Mountains, California

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

Bergfeld, D.; Nabelek, P.I.; Labotka, T.C.

1992-01-01

The Kingston Peak Formation forms part of the Panamint Mountains, California, metamorphic core-complex. Peak tremolite-grade metamorphism as exhibited in Wildrose Canyon occurred in the Jurassic; a retrograde thermal event may have occurred in the Cretaceous. The formation consists dominantly of interbedded siliceous limestones and graphitic calcareous schists. Stable isotopic analysis shows two distinct groups of data. delta O-18 values of calcite from the limestones range between 15.3 and 17.3[per thousand], probably reflecting their original Proterozoic depositional values. Likewise the delta C-13 values are also unshifted, ranging from +1% to +3.8%o. In contrast, delta O-18 values of calcite from the schistsmore » are for the most part > 20[per thousand]. These high values could reflect the original depostional conditions; however, they may be due to equilibration with silicate minerals which range from 14.9 to 17.9[per thousand]. Overall, the combined oxygen and carbon isotopic data indicate that most isotopic changes can be explained by closed-system equilibration. Only a limited amount of interaction with externally-derived fluids during metamorphism is evident in the isotopic data. The interaction may have been confined to vicinities of faults and fractures which are common in Wildrose Canyon.« less

Fluid inclusion and sulphur isotope evidence for syntectonic mineralisation at the Elura mine, southeastern Australia

NASA Astrophysics Data System (ADS)

Seccombe, P. K.

1990-10-01

Fluid inclusion and sulphur isotope data for the discordant, metasediment-hosted massive sulphide deposit at Elura are consistent with a syntectonic origin of the orebodies. Thermometric and laser Raman microprobe analyses indicate that two-phase, primary fluid inclusions are low salinity and H2O-CO2-CH4 types. Inclusion fluids from quartz in ore yield homogenisation temperatures (Th) ranging from 298 ° to 354 °C (mean 320 °C). They are likely to have been trapped close to the solvus of the H2O-CO2-(CH4-NaCl) system and thus should give temperatures of the mineralising fluid. An additional, low Th population of later fluid inclusions is recognised in quartz from ore and syntectonic extension veins in the adjacent wallrock. Th's for these low CO2bearing inclusions range from 150 to 231 °C (mean 190 °C), and should be considerably lower than true trapping temperatures. Sulphur isotopic composition (δ34S) of pyrite, sphalerite, pyrrhotite and galena ranges from 4.7 to 12.6% and indicates a sulphur source from underlying Cobar Supergroup metasediments. An average temperature of 275 °C from the sphalerite-galena sulphur isotopic thermometer suggests isotopic re-equilibration below peak metamorphic temperatures.

Strontium and neodymium isotopic evidence for the heterogeneous nature and development of the mantle beneath Afar (Ethiopia)

NASA Astrophysics Data System (ADS)

Betton, P. J.; Civetta, L.

1984-11-01

Neodymium isotope and REE analyses of recent volcanic rocks and spinel lherzolite nodules from the Afar area are reported. The 143Nd/ 144Nd ratios of the volcanic rocks range from 0.51286 to 0.51304, similar to the range recorded from Iceland. However, the 87Sr/ 86Sr ratios display a distinctly greater range (0.70328-0.70410) than those reported from the primitive rocks of Iceland. Whole rock samples and mineral separates from the spinel lherzolite nodules exhibit uniform 143Nd/ 144Nd ratios (ca. 0.5129) but varied 87Sr/ 86Sr ratios in the range 0.70427-0.70528. The Sr sbnd Nd isotope variations suggest that the volcanic rocks may have been produced by mixing between two reservoirs with distinct isotopic compositions. Two possible magma reservoirs in this area are the source which produced the "MORB-type" volcanics in the Red Sea and Gulf of Aden and the anomalous source represented by the nodule suite. The isotopic composition of the volcanics is compatible with mixing between these two reservoirs. It is shown that the anomalous source with a high 87Sr/ 86Sr ratio cannot have been produced by simple processes of partial melting and mixing within normal mantle. Instead the high 87Sr/ 86Sr is equated with a fluid phase. A primitive cognate fluid, subducted seawater or altered oceanic lithosphere may have been responsible for the generation of the source with a high 87Sr/ 86Sr ratio.

Stable Mercury Isotopes in Polished Rice (Oryza sativa L.) and Hair from Rice Consumers

PubMed Central

2017-01-01

Mercury (Hg) isotopic signatures were characterized in polished rice samples from China, U.S., and Indonesia (n = 45). Hg isotopes were also analyzed in paired hair samples for participants from China (n = 21). For the latter, we also quantified the proportion of methylmercury intake through rice (range: 31–100%), and the weekly servings of fish meals (range: 0–5.6 servings/weekly). For these participants, 29% (n = 6) never ingested fish, 52% (n = 11) ingested fish < twice/weekly, and 19% (n = 4) ingested fish ≥ twice/weekly. In rice and hair, both mass-dependent fractionation (MDF, reported as δ202Hg) and mass-independent fractionation (MIF, reported as Δ199Hg) of Hg isotopes were observed. Compared to rice, hair δ202Hg values were enriched on average (±1 standard deviation) by 1.9 ± 0.61‰, although the range was wide (range: 0.45‰, 3.0‰). Hair Δ199Hg was significantly inversely associated with %methylmercury intake from rice (Spearman’s rho = −0.61, p < 0.01, n = 21), i.e., as the proportion of methylmercury intake from rice increased, MIF decreased. Additionally, hair Δ199Hg was significantly higher for participants ingesting fish ≥ twice/weekly compared to those who did not ingest fish or ingested fish < twice/weekly (ANOVA, p < 0.05, n = 21); Overall, results suggest that Hg isotopes (especially MIF) in human hair can be used to distinguish methylmercury intake from rice versus fish. PMID:28482656

Precession and glacial-cycle controls of monsoon precipitation isotope changes over East Asia during the Pleistocene

NASA Astrophysics Data System (ADS)

Huang, Enqing; Chen, Yunru; Schefuß, Enno; Steinke, Stephan; Liu, Jingjing; Tian, Jun; Martínez-Méndez, Gema; Mohtadi, Mahyar

2018-07-01

Precipitation isotope reconstructions derived from speleothems and plant waxes are important archives for understanding hydroclimate dynamics. Their climatic significance in East Asia, however, remains controversial. Here we present terrestrial plant-wax stable hydrogen isotope (δDwax) records over periods covering the last four interglacials and glacial terminations from sediment cores recovered from the northern South China Sea (SCS) as an archive of regionally-integrated precipitation isotope changes in Southeast China. Combined with previous precipitation isotope reconstructions from China, we find that the SCS δDwax and Southwest-Central China stalagmite δ18O records show relatively enriched and depleted isotopic values, respectively, during interglacial peaks; but relatively similar isotopic variations during most sub-interglacials and glacial periods over the past 430 thousand years. During interglacial peaks, strong summer insolation should have intensified the convection intensity, the isotopic fractionation along moisture trajectories and the seasonality, which are all in favor of causing isotopically-depleted rainfall over the East Asian monsoon regime. These effects in combination with a relatively high proportion of Indian Ocean- versus Pacific-sourced moisture influx should have resulted in strongly depleted precipitation isotopes (stalagmite δ18O) over most parts of China. However, Southeast China should have been affected by a relatively low ratio of Indian Ocean- versus Pacific-sourced moisture influx, which dominated over effects yielding depleted precipitation isotopes and led to enriched precipitation isotopes (δDwax). It is thus concluded that glacial boundary conditions and insolation forcing are the two most important factors for causing regional differences in precipitation isotope compositions over subtropical East Asia on orbital timescales.

Evaluating sulfur dynamics during storm events for three watersheds in the northeastern USA: a combined hydrological, chemical and isotopic approach

Treesearch

Myron J. Mitchell; Scott W. Bailey; James B. Shanley; Bernhard. Mayer

2008-01-01

Concerns related to climate change have resulted in an increasing interest in the importance of hydrological events such as droughts in affecting biogeochemical responses of watersheds. The effects of an unusually dry summer in 2002 had a marked impact on the biogeochemistry of three watersheds in the north-eastern USA. Chemical, isotopic and hydrological responses...

Brome isotope selective control of CF3Br molecule clustering by IR laser radiation in gas-dynamic expansion of CF3Br - Ar mixture

NASA Astrophysics Data System (ADS)

Apatin, V. M.; Lokhman, V. N.; Makarov, G. N.; Ogurok, N.-D. D.; Ryabov, E. A.

2018-02-01

We report the results of research on the experimental control of CF3Br molecule clustering under gas-dynamic expansion of the CF3Br - Ar mixture at a nozzle exit by using IR laser radiation. A cw CO2 laser is used for exciting molecules and clusters in the beam and a time-of-flight mass-spectrometer with laser UV ionisation of particles for their detection. The parameters of the gas above the nozzle are determined (compositions and pressure) at which intensive molecule clustering occurs. It is found that in the case of the CF3Br gas without carrier when the pressure P0 above the nozzle does not exceed 4 atm, molecular clusters actually are not generated in the beam. If the gas mixture of CF3Br with argon is used at a pressure ratio 1 : N, where N >= 3, and the total pressure above the nozzle is P0 >= 2 atm, then there occurs molecule clustering. We study the dependences of the efficiency of suppressing the molecule clustering on parameters of the exciting pulse, gas parameters above the nozzle, and on a distance of the molecule irradiation zone from the nozzle exit section. It is shown that in the case of resonant vibrational excitation of gas-dynamically cooled CF3Br molecules at the nozzle exit one can realise isotope-selective suppression of molecule clustering with respect to bromine isotopes. With the CF3Br - Ar mixtures having the pressure ratio 1 : 3 and 1 : 15, the enrichment factors obtained with respect to bromine isotopes are kenr ≈ 1.05 ± 0.005 and kenr ≈ 1.06 ± 0.007, respectively, under jet irradiation by laser emission in the 9R(30) line (1084.635 cm-1). The results obtained let us assume that this method can be used to control clustering of molecules comprising heavy element isotopes, which have a small isotopic shift in IR absorption spectra.

Assessing the Role of Sewers and Atmospheric Deposition as Nitrate Contamination Sources to Urban Surface Waters using Stable Nitrate Isotopes

NASA Astrophysics Data System (ADS)

Sikora, M. T.; Elliott, E. M.

2009-12-01

Excess nitrate (NO3-) contributes to the overall degraded quality of streams in many urban areas. These systems are often dominated by impervious surfaces and storm sewers that can route atmospherically deposited nitrogen, from both wet and dry deposition, to waterways. Moreover, in densely populated watersheds there is the potential for interaction between urban waterways and sewer systems. The affects of accumulated nitrate in riverine and estuary systems include low dissolved oxygen, loss of species diversity, increased mortality of aquatic species, and general eutrophication of the waterbody. However, the dynamics of nitrate pollution from each source and it’s affect on urban waterways is poorly constrained. The isotopes of nitrogen and oxygen in nitrate have been proven effective in helping to distinguish contamination sources to ground and surface waters. In order to improve our understanding of urban nitrate pollution sources and dynamics, we examined nitrate isotopes (δ15N and δ18O) in base- and stormflow samples collected over a two-year period from a restored urban stream in Pittsburgh, Pennsylvania (USA). Nine Mile Run drains a 1,600 hectare urban watershed characterized by 38% impervious surface cover. Prior work has documented high nitrate export from the watershed (~19 kg NO3- ha-1 yr-1). Potential nitrate sources to the watershed include observed sewer overflows draining directly to the stream, as well as atmospheric deposition (~23 kg NO3- ha-1 yr-1). In this and other urban systems with high percentages of impervious surfaces, there is likely minimal input from nitrate derived from soil or fertilizer. In this presentation, we examine spatial and temporal patterns in nitrate isotopic composition collected at five locations along Nine Mile Run characterized by both sanitary and combined-sewer cross-connections. Preliminary isotopic analysis of low-flow winter streamwater samples suggest nitrate export from Nine Mile Run is primarily influenced by inputs of human waste despite high rates of atmospheric nitrate deposition. Further isotopic analysis of nitrate will examine seasonal variations in nitrate sources; compare nitrate dynamics and sources during low- versus high-flows, and the influence of interannual climatic variability on nitrate export.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Using Stable Isotope Geochemistry to Determine Changing Paleohydrology and Diagenetic Alteration in the Late Cretaceous Kaiparowits Formation, UT USA

NASA Astrophysics Data System (ADS)

Yamamura, Daigo

The Western Interior Basin of the North America preserves one of the best sedimentary and paleontological records of the Cretaceous in the world. The Upper Cretaceous Kaiparowits Formation is a rapidly deposited fluvial sequence and preserves one of the most complete terrestrial fossil record of the North America. Such a unique deposit provides an opportunity to investigate the interaction between the physical environment and ecology. In an effort to decipher such interaction, stable isotope composition of cements in sedimentary rocks, concretions and vertebrate fossils were analyzed. Despite the difference in facies and sedimentary architecture, the isotope composition does not change significantly at 110 m from the base of the formation. Among the well-preserved cement samples, stable isotope composition indicates a significant hydrologic change within the informal Middle unit; a 6.37‰ depletion in delta13C and 3.30‰ enrichment in delta 18O occurs at 300 m above the base of the formation. The isotope values indicate that the sandstone cements below 300 m were precipitated in a mixing zone between marine and terrestrial groundwater, whereas the cements in upper units were precipitated in a terrestrial groundwater. Despite the difference in physical appearance (i.e. color and shape), the isotopic compositions of cements in concretions are similar to well-cemented sandstone bodies in similar stratigraphic positions. Isotope compositions of the host rock are similar to that of mudrock and weathered sandstone, suggesting the origin of cementing fluids for the sandstone and concretions were the same indicating that: 1) the concretions were formed in shallow groundwater and not related to the groundwater migration, or 2) all cements in upper Kaiparowits Formation are precipitated or altered during later stage groundwater migration. Average delta18Oc from each taxon show the same trend as the delta18Op stratigraphic change, suggesting delta18Oc is still useful as a paleoclimatic proxy. Compared to other Campanian formations, fossil delta18O p are depleted for their paleolatitude, suggesting the Kaiparowits Plateau had higher input from high-elevation runoff, consistent with other paleoclimatic studies. Estimated delta18Ow ranged between vadose influenced dry season values of -8.88‰ to high elevation runoff values of -13.76‰ suggesting dynamic hydrologic interactions.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

A 1000-year record of dry conditions in the eastern Canadian prairies reconstructed from oxygen and carbon isotope measurements on Lake Winnipeg sediment organics

USGS Publications Warehouse

Buhay, W.M.; Simpson, S.; Thorleifson, H.; Lewis, M.; King, J.; Telka, A.; Wilkinson, Philip M.; Babb, J.; Timsic, S.; Bailey, D.

2009-01-01

A short sediment core (162 cm), covering the period AD 920-1999, was sampled from the south basin of Lake Winnipeg for a suite of multi-proxy analyses leading towards a detailed characterisation of the recent millennial lake environment and hydroclimate of southern Manitoba, Canada. Information on the frequency and duration of major dry periods in southern Manitoba, in light of the changes that are likely to occur as a result of an increasingly warming atmosphere, is of specific interest in this study. Intervals of relatively enriched lake sediment cellulose oxygen isotope values (??18Ocellulose) were found to occur from AD 1180 to 1230 (error range: AD 1104-1231 to 1160-1280), 1610-1640 (error range: AD 1571-1634 to 1603-1662), 1670-1720 (error range: AD 1643-1697 to 1692-1738) and 1750-1780 (error range: AD 1724-1766 to 1756-1794). Regional water balance, inferred from calculated Lake Winnipeg water oxygen isotope values (??18Oinf-lw), suggest that the ratio of lake evaporation to catchment input may have been 25-40% higher during these isotopically distinct periods. Associated with the enriched d??18Ocellulose intervals are some depleted carbon isotope values associated with more abundantly preserved sediment organic matter (d??13COM). These suggest reduced microbial oxidation of terrestrially derived organic matter and/or subdued lake productivity during periods of minimised input of nutrients from the catchment area. With reference to other corroborating evidence, it is suggested that the AD 1180-1230, 1610-1640, 1670-1720 and 1750-1780 intervals represent four distinctly drier periods (droughts) in southern Manitoba, Canada. Additionally, lower-magnitude and duration dry periods may have also occurred from 1320 to 1340 (error range: AD 1257-1363), 1530-1540 (error range: AD 1490-1565 to 1498-1572) and 1570-1580 (error range: AD 1531-1599 to 1539-1606). ?? 2009 John Wiley & Sons, Ltd.

Using stable isotopes to assess surface water source dynamics and hydrological connectivity in a high-latitude wetland and permafrost influenced landscape

NASA Astrophysics Data System (ADS)

Ala-aho, P.; Soulsby, C.; Pokrovsky, O. S.; Kirpotin, S. N.; Karlsson, J.; Serikova, S.; Vorobyev, S. N.; Manasypov, R. M.; Loiko, S.; Tetzlaff, D.

2018-01-01

Climate change is expected to alter hydrological and biogeochemical processes in high-latitude inland waters. A critical question for understanding contemporary and future responses to environmental change is how the spatio-temporal dynamics of runoff generation processes will be affected. We sampled stable water isotopes in soils, lakes and rivers on an unprecedented spatio-temporal scale along a 1700 km transect over three years in the Western Siberia Lowlands. Our findings suggest that snowmelt mixes with, and displaces, large volumes of water stored in the organic soils and lakes to generate runoff during the thaw season. Furthermore, we saw a persistent hydrological connection between water bodies and the landscape across permafrost regions. Our findings help to bridge the understanding between small and large scale hydrological studies in high-latitude systems. These isotope data provide a means to conceptualise hydrological connectivity in permafrost and wetland influenced regions, which is needed for an improved understanding of future biogeochemical changes.

Ultra low-level measurements of actinides by sector field ICP-MS.

PubMed

Pointurier, F; Baglan, N; Hémet, P

2004-01-01

In the present work, a double-focusing sector field inductively coupled plasma-mass spectrometer was optimised for ultra trace and isotopic analyses of actinide long-lived isotopes in low concentration solutions of the fgml(-1) to the ngml(-1) range. Sensitivities of about 3GHz/(microgml(-1)), with as low a background as 0.1cps, were obtained for U using a conventional concentric pneumatic nebuliser. Detection limits are below the fg range for 239Pu and 240Pu. With natural U, a precision lower than 0.5% RSD is currently obtained for 235U/238U isotopic ratio at the 200pgml(-1) level.

Lignin methoxyl hydrogen isotope ratios in a coastal ecosystem

NASA Astrophysics Data System (ADS)

Feakins, Sarah J.; Ellsworth, Patricia V.; Sternberg, Leonel da Silveira Lobo

2013-11-01

Stable hydrogen isotope ratios of plant lignin methoxyl groups have recently been shown to record the hydrogen isotopic composition of meteoric water. Here we extend this technique towards tracing water source variations across a saltwater to freshwater gradient in a coastal, subtropical forest ecosystem. We measure the hydrogen isotopic composition of xylem water (δDxw) and methoxyl hydrogen (δDmethoxyl) to calculate fractionations for coastal mangrove, buttonwood and hammock tree species in Sugarloaf Key, as well as buttonwoods from Miami, both in Florida, USA. Prior studies of the isotopic composition of cellulose and plant leaf waxes in coastal ecosystems have yielded only a weak correlation to source waters, attributed to leaf water effects. Here we find δDmethoxyl values range from -230‰ to -130‰, across a 40‰ range in δDxw with a regression equation of δDmethoxyl ‰ = 1.8 * δDxw - 178‰ (R2 = 0.48, p < 0.0001, n = 74). This is comparable within error to the earlier published relationship for terrestrial trees which was defined across a much larger 125‰ isotopic range in precipitation. Analytical precision for measurements of δD values of pure CH3I by gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is σ = 6‰ (n = 31), which is considerably better than for CH3I liberated through cleavage with HI from lignin with σ = 18‰ (n = 26). Our results establish that δDmethoxyl can record water sources and salinity incursion in coastal ecosystems, where variations sufficiently exceed method uncertainties (i.e., applications with δD excursions >50‰). For the first time, we also report yields of propyl iodide, which may indicate lignin synthesis of propoxyl groups under salt-stress.

Multi-scale heterogeneity in the temporal origin of water taken up by trees water uptake inferred using stable isotopes

NASA Astrophysics Data System (ADS)

Allen, S. T.; Kirchner, J. W.; Braun, S.; Siegwolf, R. T.; Goldsmith, G. R.

2017-12-01

Xylem water isotopic composition can reveal how water moves through soil and is subsequently taken up by plants. By examining how xylem water isotopes vary across distinct climates and soils, we test how these site characteristics control critical-zone water movement and tree uptake. Xylem water was collected from over 900 trees at 191 sites across Switzerland during a 10-day period in mid-summer 2015. Sites contained oak, beech and/or spruce trees and ranged in elevation from 260 to 1870 m asl with mean annual precipitation from 700 to 2060 mm. Xylem water samples were analyzed for 2H and 18O using isotope ratio mass spectrometry. Patterns in the temporal origin of xylem water showed regional differences. For example, trees in the southern and alpine regions had xylem water isotopic signatures that more closely resembled summer precipitation. The isotopic spatial range observed for mid-summer xylem waters was similar to the seasonal range of precipitation; that is, mid-summer xylem water at some sites resembled summer precipitation, and at other sites resembled winter precipitation. Xylem water from spruces, oaks, and beeches at the same sites did not differ from each other, despite these species having different rooting habits. Across all sites and species, precipitation amount correlated positively with xylem δ18O. In higher-precipitation areas, summer rain apparently displaces or mixes with older (winter) stored waters, thus reducing the winter-water isotopic signal in xylem water. Alternatively, in areas with limited precipitation, xylem water more closely matched winter water, indicating greater use of older stored water. We conclude that regional variations in precipitation deficits determine variations in the turnover rate of plant-available soil water and storage.

Tracking Urban Air Deterioration in San Francisco: Carbon and Nitrogen Isotope Study of Weedy Plants.

NASA Astrophysics Data System (ADS)

Colman, A. S.; Wessells, A.; Swaine, M. E.; Fogel, M. L.

2003-12-01

Stable isotopes of carbon and nitrogen have long been used as indicators of ecosystem structure and nutrient cycling in natural and anthropogenically disturbed terrestrial ecosytems. However, relatively few of these studies have targeted urban environments, where nitrogen and CO2 emissions dramatically impact atmospheric composition. Here we present the results of carbon and nitrogen isotope analyses of herbaceous plants growing in and around San Francisco. These plants were collected mainly as part of a public outreach walking tour of San Francisco ("The Weed Walk - Concrete Jungle") sponsored by the San Francisco Exploratorium. In all cases, the plants were sampled in areas with negligible forest canopy. A consortium of species was collected at each of several distinct sites to examine the localized and regional impact of automobile traffic and proximity to the ocean on isotopic compositions of carbon and nitrogen. δ 13C measurements trend towards relatively light values in the range of --26 to --36 permil. In comparison, the leaves from similar types of herbaceous species in relatively unpolluted and unforested environments typically have δ 13C values in the range of --22 to --28 permil. The observed light carbon isotopic compositions potentially reflect input of isotopically light CO2 emissions from fossil fuel burning, boosting atmospheric CO2 concentrations to >10 % above background. δ 15N values range from +4 to +9 permil. This is substantially offset from the --4 to +1 permil values that typify vegetation in regions where nitrogen oxides from fossil fuel combustion dominate the nitrogen inputs. The nitrogen isotope compositions might suggest nitrogen contributions from a marine source (typically +6 permil).

Cosmogenic effects on Cu isotopes in IVB iron meteorites

NASA Astrophysics Data System (ADS)

Chen, Heng; Moynier, Frédéric; Humayun, Munir; Bishop, M. Cole; Williams, Jeffrey T.

2016-06-01

We measured Cu isotope compositions of 12 out of the 14 known IVB iron meteorites. Our results show that IVB iron meteorites display a very large range of δ65Cu values (-5.84‰ < δ65Cu < -0.24‰; defined as per mil deviation of the 65Cu/63Cu ratio from the NIST-976 standard). These Cu isotopic data display clear correlations with W, Pt, and Os isotope ratios, which are very sensitive to secondary neutron capture due to galactic cosmic ray (GCR) irradiation. This demonstrates that δ65Cu in IVB irons is majorly modified by neutron capture by the reaction 62Ni(n,γ)63Ni followed by beta decay to 63Cu. Using correlations with Pt and Os neutron dosimeters, we calculated a pre-exposure δ65Cu of -0.3 ± 0.8‰ (95% conf.) of IVB irons that agrees well with the Cu isotopic compositions of other iron meteorite groups and falls within the range of chondrites. This shows that the volatile depletion of the IVB parent body is not due to evaporation that should have enriched IVB irons in the heavy Cu isotopes.

Stable isotope ratios of tap water in the contiguous United States

NASA Astrophysics Data System (ADS)

Bowen, Gabriel J.; Ehleringer, James R.; Chesson, Lesley A.; Stange, Erik; Cerling, Thure E.

2007-03-01

Understanding links between water consumers and climatological (precipitation) sources is essential for developing strategies to ensure the long-term sustainability of water supplies. In pursing this understanding a need exists for tools to study and monitor complex human-hydrological systems that involve high levels of spatial connectivity and supply problems that are regional, rather than local, in nature. Here we report the first national-level survey of stable isotope ratios in tap water, including spatially and temporally explicit samples from a large number of cities and towns across the contiguous United States. We show that intra-annual ranges of tap water isotope ratios are relatively small (e.g., <10‰ for δ2H) at most sites. In contrast, spatial variation in tap water isotope ratios is very large, spanning ranges of 163‰ for δ2H and 23.6‰ for δ18O. The spatial distribution of tap water isotope ratios at the national level is similar to that of stable isotope ratios of precipitation. At the regional level, however, pervasive differences between tap water and precipitation isotope ratios can be attributed to hydrological factors in the water source to consumer chain. These patterns highlight the potential for monitoring of tap water isotope ratios to contribute to the study of regional water supply stability and provide warning signals for impending water resource changes. We present the first published maps of predicted tap water isotope ratios for the contiguous United States, which will be useful in guiding future research on human-hydrological systems and as a tool for applied forensics and traceability studies.

Isotopic ratios D/H and 15N/14N in giant planets

NASA Astrophysics Data System (ADS)

Marboeuf, Ulysse; Thiabaud, Amaury; Alibert, Yann; Benz, Willy

2018-04-01

The determination of isotopic ratios in planets is important since it allows us to investigate the origins and initial composition of materials. The present work aims to determine the possible range of values for isotopic ratios D/H and 15N/14N in giant planets. The main objective is to provide valuable theoretical assumptions on the isotopic composition of giant planets, their internal structure, and the main reservoirs of species. We use models of ice formation and planet formation that compute the composition of ices and gas accreted in the core and the envelope of planets. Assuming a single initial value for isotopic ratios in volatile species, and disruption of planetesimals in the envelope of gaseous planets, we obtain a wide variety of D/H and 15N/14N ratios in low-mass planets (≤100 Mearth) due to the migration pathway of planets, the accretion time of gas species whose relative abundance evolves with time, and isotope exchanges among species. If giant planets with mass greater than 100 Mearth have solar isotopic ratios such as Jupiter and Saturn due to their higher envelope mass, Neptune-type planets present values ranging between one and three times the solar value. It seems therefore difficult to use isotopic ratios in the envelope of these planets to get information about their formation in the disc. For giant planets, the ratios allow us to constrain the mass fraction of volatile species in the envelope needed to reproduce the observational data by assuming initial values for isotopic ratios in volatile species.

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

NASA Astrophysics Data System (ADS)

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

2017-11-01

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

Zirconium isotope constraints on the composition of Theia and current Moon-forming theories

NASA Astrophysics Data System (ADS)

Akram, W.; Schönbächler, M.

2016-09-01

The giant impact theory is the most widely recognized formation scenario of the Earth's Moon. Giant impact models based on dynamical simulations predict that the Moon acquired a significant amount of impactor (Theia) material, which is challenging to reconcile with geochemical data for O, Si, Cr, Ti and W isotopes in the Earth and Moon. Three new giant impact scenarios have been proposed to account for this discrepancy - hit-and-run impact, impact with a fast-spinning protoEarth and massive impactors - each one reducing the proportion of the impactor in the Moon compared to the original canonical giant impact model. The validity of each theory and their different dynamical varieties are evaluated here using an integrated approach that considers new high-precision Zr isotope measurements of lunar rocks, and quantitative geochemical modelling of the isotopic composition of the impactor Theia. All analysed lunar samples (whole-rock, ilmenite and pyroxene separates) display identical Zr isotope compositions to that of the Earth within the uncertainty of 13 ppm for 96Zr/90Zr (2σ weighted average). This 13 ppm upper limit is used to infer the most extreme isotopic composition that Theia could have possessed, relative to the Earth, for each of the proposed giant impact theories. The calculated Theian composition is compared with the Zr isotope compositions of different solar system materials in order to constrain the source region of the impactor. As a first order approximation, we show that all considered models (including the canonical) are plausible, alleviating the initial requirement for the new giant impact models. Albeit, the canonical and hit-and-run models are the most restrictive, suggesting that the impactor originated from a region close to the Earth. The fast-spinning protoEarth and massive impactor models are more relaxed and increase the allowed impactor distance from the Earth. Similar calculations carried out for O, Cr, Ti and Si isotope data support these conclusions but exclude a CI- and enstatite chondrite-like composition for Theia. Thus, the impactor Theia most likely had a Zr isotope composition close to that of the Earth, and this suggests that a large part of the inner solar system (or accretion region of the Earth, Theia and enstatite chondrites) had a uniform Zr isotope composition.

Seasonal and inter-annual dynamics of growth, non-structural carbohydrates and C stable isotopes in a Mediterranean beech forest.

PubMed

Scartazza, Andrea; Moscatello, Stefano; Matteucci, Giorgio; Battistelli, Alberto; Brugnoli, Enrico

2013-07-01

Seasonal and inter-annual dynamics of growth, non-structural carbohydrates (NSC) and carbon isotope composition (δ(13)C) of NSC were studied in a beech forest of Central Italy over a 2-year period characterized by different environmental conditions. The net C assimilated by forest trees was mainly used to sustain growth early in the season and to accumulate storage carbohydrates in trunk and root wood in the later part of the season, before leaf shedding. Growth and NSC concentration dynamics were only slightly affected by the reduced soil water content (SWC) during the drier year. Conversely, the carbon isotope analysis on NSC revealed seasonal and inter-annual variations of photosynthetic and post-carboxylation fractionation processes, with a significant increase in δ(13)C of wood and leaf soluble sugars in the drier summer year than in the wetter one. The highly significant correlation between δ(13)C of leaf soluble sugars and SWC suggests a decrease of the canopy C isotope discrimination and, hence, an increased water-use efficiency with decreasing soil water availability. This may be a relevant trait for maintaining an acceptable plant water status and a relatively high C sink capacity during dry seasonal periods. Our results suggest a short- to medium-term homeostatic response of the Collelongo beech stand to variations in water availability and solar radiation, indicating that this Mediterranean forest was able to adjust carbon-water balance in order to prevent C depletion and to sustain plant growth and reserve accumulation during relatively dry seasons.

The sapphire backscattering monochromator at the Dynamics beamline P01 of PETRA III

DOE PAGES

Alexeev, P.; Asadchikov, V.; Bessas, D.; ...

2016-02-23

Here, we report on a high resolution sapphire backscattering monochromator installed at the Dynamics beamline P01 of PETRA III. The device enables nuclear resonance scattering experiments on M ossbauer isotopes with transition energies between 20 and 60 keV with sub-meV to meV resolution. In a first performance test with 119Sn nuclear resonance at a X-ray energy of 23.88 keV an energy resolution of 1.34 meV was achieved. Moreover, the device extends the field of nuclear resonance scattering at the PETRA III synchrotron light source to many further isotopes like 151Eu, 149Sm, 161Dy, 125Te and 121Sb.

Isotope-labeled aspartate sidechain as a non-perturbing infrared probe: Application to investigate the dynamics of a carboxylate buried inside a protein

NASA Astrophysics Data System (ADS)

Abaskharon, Rachel M.; Brown, Stephen P.; Zhang, Wenkai; Chen, Jianxin; Smith, Amos B.; Gai, Feng

2017-09-01

Because of their negatively charged carboxylates, aspartate and glutamate are frequently found at the active or binding site of proteins. However, studying a specific carboxylate in proteins that contain multiple aspartates and/or glutamates via infrared spectroscopy is difficult due to spectral overlap. We show, herein, that isotopic-labeling of the aspartate sidechain can overcome this limitation as the resultant 13COO- asymmetric stretching vibration resides in a transparent region of the protein IR spectrum. Applicability of this site-specific vibrational probe is demonstrated by using it to assess the dynamics of an aspartate ion buried inside a small protein via two-dimensional infrared spectroscopy.

Assessment of the origin and geothermal potential of the thermal waters by hydro-isotope geochemistry: Eskisehir province, Turkey.

PubMed

Yuce, Galip; Italiano, Francesco; Yasin, Didem; Taskiran, Lutfi; Gulbay, Ahmet Hilmi

2017-05-01

The thermal fluids vented over Eskisehir province have been investigated for their origin and to estimate the geothermal potential of the area. Thermal waters as well as bubbling and dissolved gases were collected and analysed for their chemical and isotopic features. Their isotopic composition varies in the range from -11.5 to -7.7 ‰ for δ 18 O, -84 and -57 ‰ for δ 2 H, and 0-7.2 TU for tritium. The gases (bubbling and dissolved) are mostly N 2 -dominated with a significant amount of CO 2 . The helium isotopic ratios are in the range of 0.2-0.66 R/Rac, indicate remarkable mantle-He contribution ranging between 2 and 10 % in the whole study area. Considering the estimated geothermal gradient about three times higher than the normal gradient, and the reservoir temperatures estimated to be between 50 and 100 °C using quartz and chalcedony geothermometers, a circulation model was built where possible mixing with shallow waters cool down the uprising geothermal fluids.

Hydrogenetic Ferromanganese Crusts of the California Continental Margin

NASA Astrophysics Data System (ADS)

Conrad, Tracey A.

Hydrogenetic Ferromanganese (Fe-Mn) crusts grow from seawater and in doing so sequester elements of economic interest and serve as archives of past seawater chemistry. Ferromanganese crusts have been extensively studied in open-ocean environments. However, few studies have examined continent-proximal Fe-Mn crusts especially from the northeast Pacific. This thesis addresses Fe-Mn crusts within the northeast Pacific California continental margin (CCM), which is a dynamic geological and oceanographic environment. In the first of three studies, I analyzed the chemical and mineralogical composition of Fe-Mn crusts and show that continental-proximal processes greatly influence the chemistry and mineralogy of CCM Fe-Mn crusts. When compared to global open-ocean Fe-Mn crusts, CCM crusts have higher concentrations of iron, silica, and thorium with lower concentrations of many elements of economic interest including manganese, cobalt, and tellurium, among other elements. The mineralogy of CCM Fe-Mn crusts is also unique with more birnessite and todorokite present than found in open-ocean samples. Unlike open-ocean Fe-Mn crusts, carbonate-fluorapatite is not present in CCM crusts. This lack of phosphatization makes CCM Fe-Mn crusts excellent candidates for robust paleoceanography records. The second and third studies in this thesis use isotope geochemistry on select CCM Fe-Mn crusts from four seamounts in the CCM to study past terrestrial inputs into the CCM and sources and behavior of Pb and Nd isotopes over the past 7 million years along the northeast Pacific margin. The second study focuses on riverine inputs into the Monterey Submarine Canyon System and sources of the continental material. Osmium isotopes in the crusts are compared to the Cenozoic Os seawater curve to develop an age model for the samples that show the crusts range in age of initiation of crust growth from approximately 20 to 6 Myr. Lead and neodymium isotopes measured in select Fe-Mn crusts show that large amounts of terrestrial material entered the CCM via the Monterey Canyon from prior to 6.8+/-0.5 until 4.5 +/-0.5 Myr ago. These data combined with reconstructions of the paleo-coastline indicate that incision of the modern Monterey Canyon started around 7 Myr ago. Isotope plots of potential source regions indicate that the source of the material is the border of the southern Sierra Nevada and western Basin and Range. This answers a long-standing and fundamental question about the timing and formation of the Monterey Canyon, the dominant feature of the Monterey Bay. The third study presented here uses the differences in lead and neodymium isotopic values in CCM Fe-Mn crusts over time compared to open-ocean Pacific, North Pacific, and Arctic Ocean Fe-Mn crusts to identify regional time-series trends and sources for these important oceanographic tracers. I found that sediment fluxes and inputs of terrestrial material from North American rivers effects the lead and neodymium isotope composition of regional seawater.

Hawaiian hot spot dynamics as inferred from the Hf and Pb isotope evolution of Mauna Kea volcano

NASA Astrophysics Data System (ADS)

Blichert-Toft, Janne; Weis, Dominique; Maerschalk, Claude; Agranier, Arnaud; Albarède, Francis

2003-02-01

The present work reports multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements of the isotopic compositions of Hf and Pb in the first 3 km of the deep core retrieved by the Hawaii Scientific Drilling Project. The measurements cover all the samples from the standard geochemical reference set, glasses from the deep hole, and replicates from the pilot hole. Both Hf and Pb are less radiogenic in Mauna Loa compared to Mauna Kea. The transition between Mauna Kea and Mauna Loa lavas in the deep core is progressive for ɛHf and 208Pb/204Pb, but a sharp discontinuity is observed for 208Pb*/206Pb*. There is no correlation between the alkalinity of the samples and isotopic composition. In detail, the Hf isotope compositions of samples from the pilot hole are not all identical to those of the HSDP-2 core for samples retrieved from a similar depth, suggesting that steep topography existed at the time of emplacement or that a different eruptive sequence was recorded. The strong correlation between 208Pb*/206Pb* and 3He/4He (He data from M. D. Kurz et al. (Rapid helium isotopic variability in Mauna Kea shield lavas from the Hawaiian Scientific Drilling Project, submitted to Geochemistry Geophysics Geosystems, 2002)) requires the episodic incorporation of a component that resembles the basalts erupted by either Kilauea or the Loihi eruptive centers (this component is referred to as K/L). The data suggest that some 500 kyr ago, Mauna Kea was tapping a mantle source similar to that tapped by Kilauea today. Isotopic variability of Pb and He cannot be accounted for by radiogenic ingrowth in a closed system, but requires the mixing of mantle source components with distinct outgassing histories. The time series of isotopic and concentration data in Mauna Kea samples spanning about 350,000 years of age indicate the recurrence of geochemical patterns in the melting column. Ignoring the most recent alkalic samples, we find that the dominant fluctuations of ɛHf and 207Pb/204Pb correspond to a period of 50,000 years. For La/Yb, Zr/Nb, 87Sr/86Sr, 206Pb/204Pb, 207Pb/206Pb, and 208Pb/206Pb, a dominant period of ca. 18,000 years is obtained. Once provision is made for the existence of harmonics, the consistency between the isotopic spectrum of the pilot hole and the HDSP-2 core is very good. The input of the K/L component does not seem to be periodic. We use these recurrence intervals in conjunction with the upwelling rate deduced from buoyancy flux and seismic evidence of the maximum dimension of scatterers to constrain the radius of the Hawaiian plume conduit to be in the range of 10-50 km and the upwelling velocity to be in the range of 0.13-3 m/yr. Plausible vertical length scales of heterogeneities in the conduit are 6.5-160 km.

Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

USGS Publications Warehouse

Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

2009-01-01

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

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

DOE PAGES

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

2016-05-02

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

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

High-precision isotopic characterization of USGS reference materials by TIMS and MC-ICP-MS

NASA Astrophysics Data System (ADS)

Weis, Dominique; Kieffer, Bruno; Maerschalk, Claude; Barling, Jane; de Jong, Jeroen; Williams, Gwen A.; Hanano, Diane; Pretorius, Wilma; Mattielli, Nadine; Scoates, James S.; Goolaerts, Arnaud; Friedman, Richard M.; Mahoney, J. Brian

2006-08-01

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

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

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

Zn isotopes in hydrothermal sulfides and their oxidation products along the south mid-Atlantic ridge: evidence of hydrothermal fluid deposition

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Wang, Jianqiang; Chu, Fengyou; Lei, Jijiang; Wang, Hao; Li, Zhenggang

2018-04-01

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13-15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from -0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ ( n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=-0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ ( n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

The early bird gets the shrimp: Confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population

USGS Publications Warehouse

Wunder, Michael B.; Jehl, Joseph R.; Stricker, Craig A.

2012-01-01

1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ13C, δ15N, δ2H and δ18O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally, it demonstrates the utility of studying variance structures and questioning assumptions implicit in the interpretation of stable isotope data from wild animals.

Benthic Foraminifera Clumped Isotope Calibration

NASA Astrophysics Data System (ADS)

Piasecki, A.; Marchitto, T. M., Jr.; Bernasconi, S. M.; Grauel, A. L.; Tisserand, A. A.; Meckler, N.

2017-12-01

Due to the widespread spatial and temporal distribution of benthic foraminifera within ocean sediments, they are a commonly used for reconstructing past ocean temperatures and environmental conditions. Many foraminifera-based proxies, however, require calibration schemes that are species specific, which becomes complicated in deep time due to extinct species. Furthermore, calibrations often depend on seawater chemistry being stable and/or constrained, which is not always the case over significant climate state changes like the Eocene Oligocene Transition. Here we study the effect of varying benthic foraminifera species using the clumped isotope proxy for temperature. The benefit of this proxy is that it is independent of seawater chemistry, whereas the downside is that it requires a relatively large sample amounts. Due to recent advancements in sample processing that reduce the sample weight by a factor of 10, clumped isotopes can now be applied to a range paleoceanographic questions. First however, we need to prove that, unlike for other proxies, there are no interspecies differences with clumped isotopes, as is predicted by first principles modeling. We used a range of surface sediment samples covering a temperature range of 1-20°C from the Pacific, Mediterranean, Bahamas, and the Atlantic, and measured the clumped isotope composition of 11 different species of benthic foraminifera. We find that there are indeed no discernible species-specific differences within the sample set. In addition, the samples have the same temperature response to the proxy as inorganic carbonate samples over the same temperature range. As a result, we can now apply this proxy to a wide range of samples and foraminifera species from different ocean basins with different ocean chemistry and be confident that observed signals reflect variations in temperature.

Stable carbon and nitrogen isotope values of dorsal spine age rings indicate temporal variation in the diet of striped marlin (Kajikia audax) in waters around Cabo San Lucas, Mexico.

PubMed

Acosta-Pachón, Tatiana A; Ortega-García, Sofia; Graham, Brittany

2015-09-30

Billfishes, such as marlin, are top pelagic predators that play an important role in maintaining the stability of marine food webs. Notwithstanding the importance of these species, there remain gaps in our knowledge on their movements, foraging, and trophic status in the early stage of life. We measured the δ(13)C and δ(15)N values in each annual growth band deposited in the dorsal spine from striped marlin caught off Cabo San Lucas, Mexico, to produce retrospective isotopic profiles that would enable us to detect any significant isotopic changes across development. The samples were analyzed using an elemental analyzer coupled to an isotope ratio mass spectrometer. There was no relationship between the size of striped marlin and the δ(15) N values. Differences in δ(15)N mean values across different age classes were not significant and the variation in δ(15)N values through the marlins' life cycle was less than 2‰. However, the mean δ(15)N values between individuals varied by up to 6‰. The δ(13)C values increased as a function of age, and the mean δ(13)C values varied significantly between age classes. Fin spines can be used to construct retrospective isotopic histories for the investigation of trophic dynamics and migratory histories in billfishes, for which population dynamics are often poorly known. Copyright © 2015 John Wiley & Sons, Ltd.

Isotopic Recorders of Pollution in Heterogeneous Urban Areas

NASA Astrophysics Data System (ADS)

Pataki, D. E.; Cobley, L.; Smith, R. M.; Ehleringer, J. R.; Chritz, K.

2017-12-01

A significant difficulty in quantifying urban pollution lies in the extreme spatial and temporal heterogeneity of cities. Dense sources of both point and non-point source pollution as well as the dynamic role of human activities, which vary over very short time scales and small spatial scales, complicate efforts to establish long-term urban monitoring networks that are relevant at neighborhood, municipal, and regional scales. Fortunately, the natural abundance of isotopes of carbon, nitrogen, and other elements provides a wealth of information about the sources and fate of urban atmospheric pollution. In particular, soils and plant material integrate pollution sources and cycling over space and time, and have the potential to provide long-term records of pollution dynamics that extend back before atmospheric monitoring data are available. Similarly, sampling organic material at high spatial resolution can provide "isoscapes" that shed light on the spatial heterogeneity of pollutants in different urban parcels and neighborhoods, along roads of varying traffic density, and across neighborhoods of varying affluence and sociodemographic composition. We have compiled numerous datasets of the isotopic composition of urban organic matter that illustrate the potential for isotopic monitoring of urban areas as a means of understanding hot spots and hot moments in urban atmospheric biogeochemistry. Findings to date already reveal the critical role of affluence, economic activity, demographic change, and land management practices in influencing urban pollution sources and sinks, and suggest an important role of stable isotope and radioisotope measurements in urban atmospheric and biogeochemical monitoring.

Carbon-Isotopic Dynamics of Streams, Taylor Valley, Antarctica: Biological Effects

NASA Technical Reports Server (NTRS)

Neumann, K.; DesMarais, D. J.

1998-01-01

We have investigated the role of biological processes in the C-isotopic dynamics of the aquatic ecosystems in Taylor Valley, Antarctica. This cold desert ecosystem is characterized by the complete lack of vascular plants, and the presence of algal mats in ephemeral streams and perennially ice covered lakes. Streams having abundant algal mats and mosses have very low sigma CO2 concentrations, as well as the most depleted delta C-13 values (-4%). Previous work has shown that algal mats in these streams have delta C-13 values averaging -7.01%. These values are similar to those observed in the algal mats in shallow areas of the lakes in Taylor Valley, where CO2 is thought to be colimiting to growth. These low Sigma CO2 concentrations, and delta C(13) signatures heavier than the algal mats, suggest that CO2 may be colimiting in the streams, as well. Streams with little algal growth, especially the longer ones in Fryxell Basin, have higher Sigma CO2 concentrations and much more enriched isotopic signatures (as high as +8%). In these streams, the dissolution of isotopically enriched, cryogenic CaCO3 is probably the major source of dissolved carbonate. The delta C(13) geochemistry of Antarctic streams is radically different from the geochemistry of more temperate streams, as it is not affected by terrestrially produced, isotopically depleted Sigma CO2. These results have important implications for the understanding of "biogenic" carbonate that might have been produced from aquatic ecosystems in the past on Mars.

Isotope effects associated with tunneling and double proton transfer in the hydrogen bonds of benzoic acid

NASA Astrophysics Data System (ADS)

Xue, Q.; Horsewill, A. J.; Johnson, M. R.; Trommsdorff, H. P.

2004-06-01

The isotope effects associated with double proton transfer in the hydrogen bonds of benzoic acid (BA) dimers have been measured using field-cycling 1H NMR relaxometry and quasielastic neutron scattering. By studying mixed isotope (hydrogen and deuterium) samples, the dynamics of three isotopologues, BA-HH, BA-HD, and BA-DD, have been investigated. Low temperature measurements provide accurate measurements of the incoherent tunneling rate, k0. This parameter scales accurately with the mass number, m, according to the formula k0=(E/m)e-F√m providing conclusive evidence that the proton transfer process is a strongly correlated motion of two hydrons. Furthermore, we conclude that the tunneling pathway is the same for the three isotopologue species. Measurements at higher temperatures illuminate the through barrier processes that are mediated via intermediate or excited vibrational states. In parallel with the investigation of proton transfer dynamics, the theoretical and experimental aspects of studying spin-lattice relaxation in single crystals of mixed isotope samples are investigated in depth. Heteronuclear dipolar interactions between 1H and 2H isotopes contribute significantly to the overall proton spin-lattice relaxation and it is shown that these must be modeled correctly to obtain accurate values for the proton transfer rates. Since the sample used in the NMR measurements was a single crystal, full account of the orientation dependence of the spin-lattice relaxation with respect to the applied B field was incorporated into the data analysis.

Clumped isotope thermometry in deeply buried sedimentary carbonates: The effects of C-O bond reordering and recrystallization

NASA Astrophysics Data System (ADS)

Passey, B. H.; Shenton, B.; Grossman, E. L.; Henkes, G. A.; Laya, J. C.; Perez-Huerta, A.

2014-12-01

Constraining the thermal histories of sedimentary basins is fundamental to a range of geologic applications including tectonics, petroleum system analysis, and the genesis of ore deposits. Carbonate rocks can serve as archives of basin thermal histories through solid-state reordering of their 13C-18O, or 'clumped isotope', bonds at elevated burial temperatures. Here we present one of the first applied studies of carbonate clumped isotope reordering to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Permian Palmarito Formation, Venezuela and the Carboniferous Bird Spring Formation, Nevada, USA. Carbonate components in the Palmarito Formation, buried to ~4 km depth, yield statistically indistinguishable clumped isotope temperatures (T(Δ47)) ranging from 86 to 122 °C. Clumped isotope temperatures of components in the more deeply buried Bird Spring Formation (>5 km), range from ~100 to 165 °C and differ by component type, with brachiopods and pore-filling cements yielding the highest T(Δ47) (mean = 153 and 141 °C, respectively) and crinoids and host rock yielding significantly cooler T(Δ47) (mean = 103 and 114 °C). New high-resolution thermal histories are coupled with kinetic models to predict the extent of solid-state C-O bond reordering during burial and exhumation for both sites. Application of these models suggests that brachiopods in the Palmarito Formation experienced partial bond reordering without complete equilibration of clumped isotopes at maximum burial temperature. In contrast, clumped isotope bonds of brachiopods from the Bird Spring Formation appear to have completely equilibrated at maximum burial temperature, and now reflect blocking temperatures 'locked-in' during cooling. The 40-50 °C cooler clumped isotope temperatures measured in Bird Spring Formation crinoids and host rock can be explained by both recrystallization and cementation during shallow burial and a greater inherent resistance to solid-state reordering than brachiopods.

Stable carbon and nitrogen isotope analysis of avian uric acid.

PubMed

Bird, Michael I; Tait, Elaine; Wurster, Christopher M; Furness, Robert W

2008-11-01

We report results obtained using a new technique developed to measure the stable-isotope composition of uric acid isolated from bird excreta (guano). Results from a diet-switch feeding trial using zebra finches suggest that the delta(13)C of uric acid in the guano equilibrates with the diet of the bird within 3 days of a change in diet, while the equilibration time for delta(15)N may be longer. The average carbon isotope discrimination between uric acid and food before the diet switch was +0.34 +/- 1 per thousand (1sigma) while after the diet switch this increased slightly to +0.83 +/- 0.7 per thousand (1sigma). Nitrogen isotope discrimination was +1.3 +/- 0.3 per thousand (1sigma) and +0.3 +/- 0.3 per thousand (1sigma) before and after the diet switch; however, it is possible that the nitrogen isotope values did not fully equilibrate with diet switch over the course of the experiment. Analyses of other chemical fractions of the guano (organic residue after uric acid extraction and non-uric acid organics solubilised during extraction) suggest a total range of up to 3 per thousand for both delta(13)C and delta(15)N values in individual components of a single bulk guano sample. The analysis of natural samples from a range of terrestrial and marine species demonstrates that the technique yields isotopic compositions consistent with the known diets of the birds. The results from natural samples further demonstrate that multiple samples from the same species collected from the same location yield similar results, while different species from the same location exhibit a range of isotopic compositions indicative of different dietary preferences. Given that many samples of guano can be rapidly collected without any requirement to capture specimens for invasive sampling, the stable-isotope analysis of uric acid offers a new, simple and potentially powerful tool for studying avian ecology and metabolism.

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.

Compound-Specific Isotope Analyses to Assess TCE Biodegradation in a Fractured Dolomitic Aquifer.

PubMed

Clark, Justin A; Stotler, Randy L; Frape, Shaun K; Illman, Walter A

2017-01-01

The potential for trichloroethene (TCE) biodegradation in a fractured dolomite aquifer at a former chemical disposal site in Smithville, Ontario, Canada, is assessed using chemical analysis and TCE and cis-DCE compound-specific isotope analysis of carbon and chlorine collected over a 16-month period. Groundwater redox conditions change from suboxic to much more reducing environments within and around the plume, indicating that oxidation of organic contaminants and degradation products is occurring at the study site. TCE and cis-DCE were observed in 13 of 14 wells sampled. VC, ethene, and/or ethane were also observed in ten wells, indicating that partial/full dechlorination has occurred. Chlorine isotopic values (δ 37 Cl) range between 1.39 to 4.69‰ SMOC for TCE, and 3.57 to 13.86‰ SMOC for cis-DCE. Carbon isotopic values range between -28.9 and -20.7‰ VPDB for TCE, and -26.5 and -11.8‰ VPDB for cis-DCE. In most wells, isotopic values remained steady over the 15-month study. Isotopic enrichment from TCE to cis-DCE varied between 0 and 13‰ for carbon and 1 and 4‰ for chlorine. Calculated chlorine-carbon isotopic enrichment ratios (ϵ Cl /ϵ C ) were 0.18 for TCE and 0.69 for cis-DCE. Combined, isotopic and chemical data indicate very little dechlorination is occurring near the source zone, but suggest bacterially mediated degradation is occurring closer to the edges of the plume. © 2016, National Ground Water Association.

Ca, Sr and Ba stable isotopes reveal the fate of soil nutrients along a tropical climosequence

USGS Publications Warehouse

Bullen, Thomas D.; Chadwick, Oliver A.

2016-01-01

Nutrient biolifting is an important pedogenic process in which plant roots obtain inorganic nutrients such as phosphorus (P) and calcium (Ca) from minerals at depth and concentrate those nutrients at the surface. Here we use soil chemistry and stable isotopes of the alkaline earth elements Ca, strontium (Sr) and barium (Ba) to test the hypothesis that biolifting of P has been an important pedogenic process across a soil climosequence developed on volcanic deposits at Kohala Mountain, Hawaii. The geochemical linkage between these elements is revealed as generally positive site-specific relationships in soil mass gains and losses, particularly for P, Ba and Ca, using the ratio of immobile elements titanium and niobium (Ti/Nb) to link individual soil samples to a restricted compositional range of the chemically and isotopically diverse volcanic parent materials. At sites where P is enriched in surface soils relative to abundances in deeper soils, the isotope compositions of exchangeable Ca, Sr and Ba in the shallowest soil horizons (< 10 cm depth) are lighter than those of the volcanic parent materials and trend toward those of plants growing on fresh volcanic deposits. In contrast the isotope composition of exchangeable Ba in deeper soil horizons (> 10 cm depth) at those sites is consistently heavier than the volcanic parent materials. The isotope compositions of exchangeable Ca and Sr trend toward heavier compositions with depth more gradually, reflecting increasing leakiness from these soils in the order Ba < Sr < Ca and downward transfer of light biocycled Ca and Sr to deeper exchange sites. Given the long-term stability of ecosystem properties at the sites where P is enriched in surface soils, a simple box model demonstrates that persistence of isotopically light exchangeable Ca, Sr and Ba in the shallowest soil horizons requires that the uptake flux to plants from those near-surface layers is less than the recycling flux returned to the surface as litterfall. This observation implicates an uptake flux from an additional source which we attribute to biolifting. We view the heavy exchangeable Ba relative to soil parent values in deeper soils at sites where P is enriched in surface soils, and indeed at all but the wettest site across the climosequence, to represent the complement of an isotopically light Ba fraction removed from these soils by plant roots consistent with the biolifting hypothesis. We further suggest that decreasing heaviness of depth-integrated exchangeable Ba in deeper soils with increasing median annual precipitation across the climosequence reflects greater reliance on shallow nutrient sources as site water balance increases. While the Ca, Sr and Ba isotopes considered together were useful in confirming an important role for nutrient biolifting across the climosequence, the Ba isotopes provided the most robust tracer of biolifting and have the greatest potential to find application as an isotopic proxy for P dynamics in soils.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

Monitoring CO2 concentration and δ13C in an underground cavity using a commercial isotope ratio infrared spectrometer

NASA Astrophysics Data System (ADS)

Guillon, Sophie; Agrinier, Pierre; Pili, Éric

2015-04-01

CO2 stable carbon isotopes are very attractive in environmental research to investigate both natural and anthropogenic carbon sources. Laser-based isotope ratio infrared spectrometers (IRIS) allow in situ continuous monitoring of CO2 isotopes, and therefore they have a potential for unprecedented understanding of carbon sources and dynamics with a high temporal resolution. Here we present the performance assessment of a commercial IRIS analyzer, including the measurement setup and the data processing scheme that we used. Even if the analyzer performs 1-Hz measurements, an integration time of the order of 1 h is commonly needed to obtain acceptable precision for δ13C. The main sources of uncertainty on δ13C come from the concentration dependence and from the temporal instability of the analyzer. The method is applied to the in situ monitoring of the CO2 carbon isotopes in an underground cavity (Roselend Natural Laboratory, France) during several months. On a weekly timescale, the temporal variability of CO2 is dominated by transient contamination by human breath. Discarding these anthropogenic contaminations, CO2 and δ13C backgrounds do not show diurnal or seasonal fluctuations. A CO2 flux released into the tunnel by the surrounding rocks is measured. The carbon isotope composition of this CO2, identified with a Keeling plot, is consistent with a main production by microbial respiration and a minor production from weathering of carbonate minerals. The presented instrument and application study are relevant to cave monitoring, whether to understand CO2 dynamics in visited and/or painted caves for preservation purposes or to understand paleoclimate recording in speleothems.

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.

Using stable isotopes and models to explore estuarine linkages at multiple scales

EPA Science Inventory

Estuarine managers need tools to respond to dynamic stressors that occur in three linked environments – coastal ocean, estuaries and watersheds. Models have been the tool of choice for examining these dynamic systems because they simplify processes and integrate over multiple sc...

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet been applied to estimate the labile pool of mercury in contaminated soils. We performed a series of soil incubations spiked with 196Hg2+aiming at measuring and modelling the progressive assimilation of Hg ions into less labile forms. Soils with a wide range of characteristics are taken for our research purpose, inclusive of Hg concentrations ranging from 0.1 to 390 mg kg-1, pH between 3.5 - 7.5 and total organic carbon (TOC) between 2.5 - 8 %. In parallel, the labile pool of Hg estimated using ID will be compared with that determined using conventional extraction methods, e.g. sequential extraction procedures. These altogether allows us to answer (1) how the E-value of Hg in soils is comparable to those estimated based on selective extraction methods, (2) how the labile Hg correlates with the total soil Hg, soil pH and TOC, and (3) how the solubility of added Hg (e.g. via rainfall) decreased in soils of different properties during aging. The obtained results fills the knowledge gap concerning Hg biogeochemistry in the terrestrial environment and serves as a basis for estimating (and predicting) the risk of soil Hg diffusion from a point source to the adjacent environments.

Carbon allocation and carbon isotope fluxes in the plant-soil-atmosphere continuum: a review

NASA Astrophysics Data System (ADS)

Brüggemann, N.; Gessler, A.; Kayler, Z.; Keel, S. G.; Badeck, F.; Barthel, M.; Boeckx, P.; Buchmann, N.; Brugnoli, E.; Esperschütz, J.; Gavrichkova, O.; Ghashghaie, J.; Gomez-Casanovas, N.; Keitel, C.; Knohl, A.; Kuptz, D.; Palacio, S.; Salmon, Y.; Uchida, Y.; Bahn, M.

2011-04-01

The terrestrial carbon (C) cycle has received increasing interest over the past few decades, however, there is still a lack of understanding of the fate of newly assimilated C allocated within plants and to the soil, stored within ecosystems and lost to the atmosphere. Stable carbon isotope studies can give novel insights into these issues. In this review we provide an overview of an emerging picture of plant-soil-atmosphere C fluxes, as based on C isotope studies, and identify processes determining related C isotope signatures. The first part of the review focuses on isotopic fractionation processes within plants during and after photosynthesis. The second major part elaborates on plant-internal and plant-rhizosphere C allocation patterns at different time scales (diel, seasonal, interannual), including the speed of C transfer and time lags in the coupling of assimilation and respiration, as well as the magnitude and controls of plant-soil C allocation and respiratory fluxes. Plant responses to changing environmental conditions, the functional relationship between the physiological and phenological status of plants and C transfer, and interactions between C, water and nutrient dynamics are discussed. The role of the C counterflow from the rhizosphere to the aboveground parts of the plants, e.g. via CO2 dissolved in the xylem water or as xylem-transported sugars, is highlighted. The third part is centered around belowground C turnover, focusing especially on above- and belowground litter inputs, soil organic matter formation and turnover, production and loss of dissolved organic C, soil respiration and CO2 fixation by soil microbes. Furthermore, plant controls on microbial communities and activity via exudates and litter production as well as microbial community effects on C mineralization are reviewed. The last part of the paper is dedicated to physical interactions between soil CO2 and the soil matrix, such as CO2 diffusion and dissolution processes within the soil profile. From the presented evidence we conclude that there exists a tight coupling of physical, chemical and biological processes involved in C cycling and C isotope fluxes in the plant-soil-atmosphere system. Generally, research using information from C isotopes allows an integrated view of the different processes involved. However, complex interactions among the range of processes complicate or impede the interpretation of isotopic signals in CO2 or organic compounds at the plant and ecosystem level. This is where new research approaches should be aimed at.

Equilibrium fractionation of H and O isotopes in water from path integral molecular dynamics

NASA Astrophysics Data System (ADS)

Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Ferlat, Guillaume; Vuilleumier, Rodolphe; Mauri, Francesco

2014-06-01

The equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. Although thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. For crystals, the fractionation factor α can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. These calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. In the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics (MD) runs. It is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. In this work we present a systematic study of the calculation of the D/H and 18O/16O equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. Namely, we use a thermodynamic integration approach based on Path Integral MD calculations (PIMD) and an empirical potential model of water. Compared with standard MD, PIMD takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. We compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. The results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. In addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in the investigated system.

Complete Measurement of Stable Isotopes in N2O (δ15N, δ15Nα, δ15Nβ, δ18O, δ17O) Using Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS)

NASA Astrophysics Data System (ADS)

Leen, J. B.; Gupta, M.

2014-12-01

Nitrate contamination in water is a worldwide environmental problem and source apportionment is critical to managing nitrate pollution. Fractionation caused by physical, chemical and biological processes alters the isotope ratios of nitrates (15N/14N, 18O/16O and 17O/16O) and biochemical nitrification and denitrification impart different intramolecular site preference (15N14NO vs. 14N15NO). Additionally, atmospheric nitrate is anomalously enriched in 17O compared to other nitrate sources. The anomaly (Δ17O) is conserved during fractionation processes, providing a tracer of atmospheric nitrate. All of these effects can be used to apportion nitrate in soil. Current technology for measuring nitrate isotopes is complicated and costly - it involves conversion of nitrate to nitrous oxide (N2O), purification, preconcentration and measurement by isotope ratio mass spectrometer (IRMS). Site specific measurements require a custom IRMS. There is a pressing need to make this measurement simpler and more accessible. Los Gatos Research has developed a next generation mid-infrared Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) analyzer to quantify all stable isotope ratios of N2O (δ15N, δ15Nα, δ15Nβ, δ18O, δ17O). We present the latest performance data demonstrating the precision and accuracy of the OA-ICOS based measurement. At an N2O concentration of 322 ppb, the analyzer quantifies [N2O], δ15N, δ15Na, δ15Nb, and δ18O with a precision of ±0.05 ppb, ±0.4 ‰, ±0.45 ‰, and ±0.6 ‰, and ±0.8 ‰ respectively (1σ, 100s; 1σ, 1000s for δ18O). Measurements of gas standards demonstrate accuracy better than ±1 ‰ for isotope ratios over a wide dynamic range (200 - 100,000 ppb). The measurement of δ17O requires a higher concentration (1 - 50 ppm), easily obtainable through conversion of nitrates in water. For 10 ppm of N2O, the instrument achieves a δ17O precision of ±0.05 ‰ (1σ, 1000s). This performance is sufficient to quantify atmospheric nitrate in soil and groundwater and may be used to differentiate other sources of nitrate for which the range of Δ17O values is much smaller. By measuring δ15N, δ15Nα, δ15Nβ, δ18O and δ17O, our instrument will help researchers unravel the complicated nitrate mixing problem to determine the sources and sinks of nitrate pollution.

You are not always what we think you eat. Selective assimilation across multiple whole-stream isotopic tracer studies

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

Dodds, W. K.; Collins, S. M.; Hamilton, S. K.

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N available in sampled food sources such as decomposing leaves, epilithon, and fine particulate detritus over feeding periods of weeks or more. Thus, common methods of sampling food sources consumed by animals in streams do not sufficiently reflect the pool of N they assimilate. Lastly, Isotope tracer studies, combined with modeling andmore » food separation techniques, can improve estimation of N pools in food sources that are assimilated by consumers.« less

You are not always what we think you eat. Selective assimilation across multiple whole-stream isotopic tracer studies

DOE PAGES

Dodds, W. K.; Collins, S. M.; Hamilton, S. K.; ...

2014-10-01

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N available in sampled food sources such as decomposing leaves, epilithon, and fine particulate detritus over feeding periods of weeks or more. Thus, common methods of sampling food sources consumed by animals in streams do not sufficiently reflect the pool of N they assimilate. Lastly, Isotope tracer studies, combined with modeling andmore » food separation techniques, can improve estimation of N pools in food sources that are assimilated by consumers.« less

Kinetic control on Zn isotope signatures recorded in marine diatoms

NASA Astrophysics Data System (ADS)

Köbberich, Michael; Vance, Derek

2017-08-01

Marine diatoms dominate the oceanic cycle of the essential micronutrient zinc (Zn). The stable isotopes of zinc and other metals are increasingly used to understand trace metal micronutrient cycling in the oceans. One clear feature of the early isotope data is the heavy Zn isotope signature of the average oceanic dissolved pool relative to the inputs, potentially driven by uptake of light isotopes into phytoplankton cells and export to sediments. However, despite the fact that diatoms strip Zn from surface waters across the Antarctic polar front in the Southern Ocean, the local upper ocean is not isotopically heavy. Here we use culturing experiments to quantify the extent of Zn isotope fractionation by diatoms and to elucidate the mechanisms driving it. We have cultured two different open-ocean diatom species (T. oceanica and Chaetoceros sp.) in a series of experiments at constant medium Zn concentration but at bioavailable medium Fe ranging from limiting to replete. We find that T. oceanica can maintain high growth rates and Zn uptake rates over the full range of bioavailable iron (Fe) investigated, and that the Zn taken up has a δ66Zn that is unfractionated relative to that of the bioavailable free Zn in the medium. The studied representative of the genus Chaetoceros, on the other hand, shows more significantly reduced Zn uptake rates at low Fe and records more variable biomass δ66Zn signatures, of up to 0.85‰ heavier than the medium. We interpret the preferential uptake of heavy isotopes at extremely low Zn uptake rates as potentially due to either of the following two mechanisms. First, the release of extracellular polymeric substances (EPS), at low Fe levels, may preferentially scavenge heavy Zn isotopes. Second, the Zn uptake rate may be slow enough to establish pseudo-equilibrium conditions at the transporter site, with heavy Zn isotopes forming more stable surface complexes. Thus we find that, in our experiments, Fe-limitation exerts a key control that not only limits diatom growth, but also affects the Zn uptake physiology of diatoms. Uptake of heavy isotopes occurs under Fe-limiting conditions that drive extremely low Zn uptake rates. On the other hand, more rapid Zn uptake rates result in biomass that is indistinguishable from the external bioavailable free Zn pool. These experimental results can, in principle, explain the range of Zn isotopic compositions found in the real surface ocean, given the geographically variable interplay between Fe-limitation, Zn uptake rates, and the degree of organic complexation of oceanic Zn.

The Geologic and Geochemical Setting of Lago Fagnano, Tierra del Fuego, Argentina

NASA Astrophysics Data System (ADS)

Tingle, D.; Odle, K.; Knettel, P.; Redding, S.; Perry, E.; Ellins, K.; Ormiston, C.; Dovzak, N.; Anderson, S.

2005-12-01

Lago Fagnano, Tierra del Fuego, Argentina is the largest and southernmost ice-free lake on Earth. The isolated lake is unique because the geographic and geologic context provides information relating to the westerly wind patterns, interaction of multiple water sources (hot springs, glacial meltwater, precipitation, groundwater), and tectonic dynamics along a major transform fault. In March, 2005, four students and three teachers from Boerne High School, south-central Texas joined scientists from the United States, Argentina and Switzerland engaged in a geophysical survey of this lake. Lago Fagnano potentially contains within its sediments an undisturbed record of the geotectonic and global climate variability of past 20,000 years. The science team imaged the lake floor with a boat specially equipped to collect both high resolution data (high frequency), imaging the upper 10-15 meters of the sediment, and long range data (low frequency), penetrating 100 or more meters into the sediment. The group conducted field research of existing tectonic features at the eastern end of Tierra del Fuego, an activity directly tied to the research objectives of the science team. They also collected water and soil samples to assess chemical and isotopic trends in the Lago Fagnano region. The research performed can help to characterize the modern geochemical setting of the lake. Analyses of dissolved oxygen, NH4+, PO42-, pH (water) and N, P, and pH (soils) demonstrate a link between low nutrient levels and low biodiversity (which was confirmed by observation) in Tierra del Fuego. Water and soil data are incorporated into a database to facilitate comparisons to North American samples collected and analyzed during the Boerne High School summer field courses. Twenty-three ^18O and ^D analyses yielded a south-north isotopic trend across the Lago Fagnano region. ^18O and ^D transition from -11.92 to -3.53% and -87.81 to -40.26%, respectively, moving south to the Beagle Channel. These isotopic data, in addition to the soil and water physical and chemical data, provide a snapshot of the geochemical dynamics of the Lago Fagnano watershed. They are valuable because interpretations of paleoclimate will be based on the geochemical history preserved within the lake sediment record. Identification of modern isotopic trends in the Lago Fagnano watershed is helpful for accurate interpretations of the sediment record.

Towards a Better Understanding of the Oxygen Isotope Signature of Atmospheric CO2: Determining the 18O-Exchange Between CO2 and H2O in Leaves and Soil On-line with Laser-Based Spectroscopy

NASA Astrophysics Data System (ADS)

Gangi, L.; Rothfuss, Y.; Vereecken, H.; Brueggemann, N.

2013-12-01

The oxygen isotope signature of carbon dioxide (δ18O-CO2) is a powerful tool to disentangle CO2 fluxes in terrestrial ecosystems, as CO2 attains a contrasting 18O signature by the interaction with isotopically different soil and leaf water pools during soil respiration and photosynthesis, respectively. However, using the δ18O-CO2 signal to quantify plant-soil-atmosphere CO2 fluxes is still challenging due to a lack of knowledge concerning the magnitude and effect of individual fractionation processes during CO2 and H2O diffusion and during CO2-H2O isotopic exchange in soils and leaves, especially related to short-term changes in environmental conditions (non-steady state). This study addresses this research gap by combined on-line monitoring of the oxygen isotopic signature of CO2 and water vapor during gas exchange in soil and plant leaves with laser-based spectroscopy, using soil columns and plant chambers. In both experimental setups, the measured δ18O of water vapor was used to infer the δ18O of liquid water, and, together with the δ18O-CO2, the degree of oxygen isotopic equilibrium between the two species (θ). Gas exchange experiments with different functional plant types (C3 coniferous, C3 monocotyledonous, C3 dicotyledonous, C4) revealed that θ and the influence of the plant on the ambient δ18O-CO2 (CO18O-isoforcing) not only varied on a diurnal timescale but also when plants were exposed to limited water availability, elevated air temperature, and abrupt changes in light intensity (sunflecks). Maximum θ before treatments ranged between 0.7 and 0.8 for the C3 dicotyledonous (poplar) and C3 monocotyledonous (wheat) plants, and between 0.5 and 0.6 for the conifer (spruce) and C4 plant (maize) while maximum CO18O-isoforcing was highest in wheat (0.03 m s-1 ‰), similar in poplar and maize (0.02 m s-1 ‰), and lowest in spruce (0.01 m s-1 ‰). Multiple regression analysis showed that up to 97 % of temporal dynamics in CO18O-isoforcing could be explained by variations in stomatal conductance, θ, and δ18O of H2O at the evaporation site. The determined maximum in vivo activity of carbonic anhydrase, the enzyme which catalyzes the CO2-H2O oxygen isotope exchange inside leaves, varied between the different plant species and was, as observed for θ, higher in poplar and wheat, and lower in maize and spruce. Preliminary experiments with soil columns filled with sand demonstrated that gas-permeable microporous polypropylene tubing, which was installed at different depths in the soil columns, was appropriate for determining δ18O-H2O and δ18O-CO2 simultaneously without fractionation. Hence, this new methodology is promising for further studies on the oxygen isotopic exchange between CO2 and H2O in soils. Altogether, this study highlights that the δ18O-CO2 exchange in the soil-plant-atmosphere continuum is highly dynamic in response to short-term variations in environmental conditions, and emphasizes the need for an improved parameterization of models simulating δ18O-CO2.

The Marine Biogeochemistry of Zinc Isotopes

DTIC Science & Technology

2007-06-01

hydrothermal fluids and minerals, cultured marine phytoplankton, natural plankton, and seawater. By measuring Zn isotopes in a diverse array of...variations were discovered in hydrothermal fluids and minerals, with hydrothermal fluids ranging in 6 66Zn from 0.02 %o to +0.93 %o, and chimney minerals...drives much of the Zn isotope fractionation in hydrothermal systems. In cultured diatoms, a relationship was discovered between Zn transport by

Isotopic studies of the late Archean plutonic rocks of the Wind River Range, Wyoming.

USGS Publications Warehouse

Stuckless, J.S.; Hedge, C.E.; Worl, R.G.; Simmons, K.R.; Nkomo, I.T.; Wenner, D.B.

1985-01-01

Two late Archaean intrusive events were documented in the Wind River Range by isotopic studies of the Rb-Sr and U-Th-Pb systems in whole-rock samples and the U-Pb systematics for zircon. An age of approx 2630(20) m.y. for the Louis Lake batholith and apparent ages of 2504(40) to 2575(50) m.y. for the Bear Ears pluton were obtained. Post-magmatic hydrothermal events approximately Tertiary in age, lowered delta 18O values and disturbed parent-daughter relationships in most of the isotopic systems investigated. The two intrusive units apparently were derived from different protoliths. Initial isotopic ratios and petrochemistry for the Louis Lake batholith are consistent with an early Archaean trondhjemitic to tonalitic source. The protolith for the Bear Ears pluton must have been subjected to high-grade metamorphism that caused loss of Rb and U prior to magma generation. -L.C.H.

The oxygen isotope composition of Almahata Sitta

NASA Astrophysics Data System (ADS)

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

2010-10-01

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

Application of computational fluid dynamics for the simulation of cryogenic molecular sieve bed absorber of hydrogen isotopes recovery system for Indian LLCB-TBM

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

Gayathri Devi, V.; Sircar, A.; Sarkar, B.

One of the most challenging tasks in the design of the fuel cycle system lies in the effective design of Tritium Extraction System (TES) which involves proper extraction and purification of tritium in the fuel cycle of the fusion reactor. Indian Lead Lithium cooled Ceramic Breeder Test Blanket Module (LLCB-TBM) would extract hydrogen isotopes through Cryogenic Molecular Sieve Bed (CMSB) adsorber system. A prototype Hydrogen Isotopes Recovery System (HIRS) is being developed to validate the concepts for tritium extraction by adsorption mass transfer mechanism. In this study, a design model has been developed and analyzed to simulate the adsorption massmore » transfer kinetics in a fixed bed adsorption column. The simulation leads primarily to effective design of HIRS, which is a state-of-the-art technology. The paper describes the process simulation approach and the results of Computational Fluid Dynamics (CFD) analysis. The effects of different operating conditions are studied to investigate their influence on the hydrogen isotopes adsorption capacity. The results of the present simulation study would be used to understand the best optimized transport phenomenon before realizing the TES as a system for LLCB-TBM. (authors)« less

Modeling calcification periods of Cytheridella ilosvayi from Florida based on isotopic signatures and hydrological data

NASA Astrophysics Data System (ADS)

Meyer, Juliane; Wrozyna, Claudia; Leis, Albrecht; Piller, Werner E.

2017-11-01

The isotopic signatures of ostracod shells are the result of the temperature and composition of their host water and the phenology and ecology of the target species. Investigations addressing the influence of site-specific environmental variations on the isotopic ranges of ostracod shells are still rare but can provide important information on habitat-dependent variations and may signify a seasonally restricted timing of calcification periods. Here we present isotopic signatures (δ18Oostr, δ13Costr) of living Cytheridella ilosvayi (Ostracoda) and physical, chemical, and isotopic (δD, δ18Owater, δ13CDIC) compositions of 14 freshwater habitats (rivers, lakes, canals, marshes, sinkholes) in South Florida from winter 2013 and summer 2014. We also present instrumental data of river temperatures and δ18O of precipitation (δ18Oprec) from this region. The physicochemical and isotopic compositions of the selected sites characterize the different habitats and show the influence of the source water, biological activity, and duration of exposure to the surface. Mean δ18Oostr and δ13Costr signatures of C. ilosvayi shells correlate well with the isotopic composition of their host waters. Within-sample variabilities in repeated isotopic measurements of single ostracod shells reflect habitat-dependent ranges. The similarly high range of ostracod δ18O in rivers and one marsh sample indicates that both temperature and δ18Oprec are responsible for their variation in the whole study area. Rivers and canals, which are predominantly influenced by the input and mixing of inorganic carbon from the catchment, show smaller δ13Costr ranges than the marsh dominated by local fluctuations in biological activities. Based on these observations, background data of water temperatures and δ18Oprec were used to calculate monthly δ18O variations in a theoretical calcite formed in rivers in Florida assuming a direct reaction on precipitation changes. The calculated values showed a high variation coupled with low mean values during the summer wet season, while during the winter dry season the variation remains small and mean values increased. Inferred configurations were used to approximate possible calcification periods of C. ilosvayi. For a plausible calcification period, mean values and ranges of δ18Oostr had to be equal to the theoretical calcite with a slight positive offset (vital effect). The applied model suggests a seasonal calcification period of C. ilosvayi in early spring that is probably coupled to the hydrologic cycle of Florida.

Comparison of TIMS and MC-ICP-MS Analyses of Pb Isotopic Compositions on Prehistoric Mauna Loa Basalts: Implications for Plume Source Components

NASA Astrophysics Data System (ADS)

De Jong, J.; Weis, D.; Maerschalk, C.; Rhodes, J. M.

2001-12-01

Recent isotopic studies on Hawaiian lavas have shown the necessity of constraining fractionation for Pb isotopes. This isotopic system presents systematic variations reflecting the presence of different plume components in the source of Hawaiian basalts. We have analyzed a series of 23 tholeiitic Mauna Loa basalts ranging in age from 36,780 to 140 y for their Pb isotopic compositions by TIMS (Micromass Sector 54) and MC-ICP-MS (Nu Plasma) to directly compare results from the same, carefully leached, samples. These analyses indicate an internal precision better than 120 ppm for the MC-ICP-MS Pb ratios, while for the TIMS ratios, it is in the per mil range. This results in a more coherent dataset for the MC-ICP-MS analyses, with the range of 207Pb/204Pb variations decreasing by a factor of 3 and of 208Pb/204Pb ratios by a factor of 1.5. The co-variations between the Pb isotopic data and other geochemical parameters for the Hawaiian lavas are now much stronger and better defined. There are clearly two groups amongst the prehistoric Mauna Loa basalts: one group with higher 87Sr/86Sr (>0.7038) and low 206Pb/204Pb (<18.15) that covers the entire range of Nb/Y (0.31 to 0.51) observed in this volcano, and the other group with low 87Sr/86Sr (<0.7038) and higher 206Pb/204Pb with Nb/Y<0.4. The second group is only present in basalts younger than 3,000 y or older than 24,000 y. The high 87Sr/86Sr group was not sampled in the HSDP I drill core, which covers an age range of 100,000 y. This either reflects a sampling bias, as the upper flow units (<10,000 y) were not sampled for geochemistry, or variations in magma supply. Altogether, Mauna Loa lava flows that are younger than 20,000 y show much more isotopic variation than older flows and there is a nearly continuous transition away from the Kilauea component. This may indicate that the transition between the Mauna Loa and Mauna Kea trends is not as sharp as previously documented. This study shows the importance of reducing the error associated with mass fractionation by measuring Pb isotopes by MC-ICP-MS to constrain plume components in the mantle source of oceanic basalts.

Eddy Covariance measurements of stable isotopes (δD and δ18O) in water vapor

NASA Astrophysics Data System (ADS)

Braden-Behrens, Jelka; Knohl, Alexander

2017-04-01

Stable isotopes are a promising tool to enhance our understanding of ecosystem gas exchanges. Studying 18O and 2H in water vapour (H2Ov) can e.g. help partitioning evapotranspiration into its components. With recent developments in laser spectroscopy direct Eddy Covariance (EC) measurements for investigating fluxes of stable isotopologues became feasible. So far very few case studies have applied the EC method to measure stable isotopes in water vapor. We continuously measure fluxes of water vapor isotopologues with the EC method in a managed beech forest in Thuringia, Germany, since autumn 2015 using the following setup: An off-axis integrated cavity output water vapor isotope analyzer (WVIA, Los Gatos Research. Inc, USA) measures the water vapour concentration and its isotopic composition (δD and δ18O). The instrument, that was optimized for high flow rates (app. 4slpm) to generate high frequency (2Hz) measurements, showed sufficient precision with Allan Deviations of app. 0.12 ‰ for δD and 0.06 ‰ for δ18O for averaging periods of 100s. The instrument was calibrated hourly using a high-flow optimized version of the water vapor isotope standard source (WVISS, Los Gatos Research. Inc, USA) that provides water vapor with known isotopic composition for a large range of different concentrations. Our calibration scheme includes a near continuous concentration range calibration instead of a simple 2 or 3-point calibration to face the analyzers strong concentration dependency within a range of app. 6 000 to 16 000 ppm in winter and app. 8 000 to 23 000 ppm in summer. In the used setup, the high-flow and high-frequency optimized water vapor isotope analyzer (WVIA) showed suitable characteristics (Allan deviation and spectral energy distribution) to perform Eddy covariance measurements of stable isotopes in H2Ov. Thus, this novel instrument for EC measurements of water vapor isotopologues provides a new opportunity for studying the hydrological cycle in long-term observation networks like Fluxnet and ICOS.

The IRHUM database - bioavailable strontium isotope ratios of France for geochemical fingerprinting

NASA Astrophysics Data System (ADS)

Willmes, Malte; Moffat, Ian; Grün, Rainer; Armstrong, Richard; Kinsley, Les; McMorrow, Linda

2013-04-01

Strontium isotope ratios (87Sr/86Sr) are used as a geochemical tracer in a wide range of fields including archaeology, ecology, soil, food and forensic sciences. These applications are based on the principle that strontium isotopic ratios of materials reflect the geological sources of the strontium, which were available during its formation. Geologic regions with distinct strontium isotope ranges, which depend on their age and composition, can be differentiated. A major constraint for current studies is the lack of robust reference maps to evaluate the strontium isotope ratios measured in the samples. The aim of the IRHUM (isotopic reconstruction of human migration) database is to provide a reference map of bioavailable strontium isotope ratios for continental France. The current dataset contains 400 sample locations covering the major geologic units of the Paris and Aquitaine Basin, the Massif Central, and the Pyrenees. At each site soil and plant samples have been collected to cover the whole range of strontium ratios at a specific location. The database is available online at www.rses.anu.edu.au/research-areas/archaeogeochemistry and contains the bioavailable strontium isotope data as well as major and trace element concentrations for soil and plant samples. Strontium isotopes were analysed using a Neptune multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) and elemental concentrations with a Varian Vista Pro Axial ICP-AES (inductively-coupled plasma atomic emission spectrometer). In addition, IRHUM provides spatial context for each sample, including background geology, field observations and soil descriptions. This metadata allows users to evaluate the suitability of a specific data point for their study. The IRHUM database fills an important gap between high resolution studies from specific sites (e.g. archaeological sites), to the very broad geochemical mapping of Europe. Thus it provides an excellent tool to evaluate the regional context of a sample and complement more closed spaced studies. New results will be added to the database continuously with the aim of covering all major geologic units of France within the next year.

O and H Isotope Ratios of Syenite Blocks in the El Abrigo Ignimbrite, Tenerife, Canary Islands: A Hydrothermal Fingerprint for Assimilation

NASA Astrophysics Data System (ADS)

Larson, P. B.; Nichols, H. J.; Wolff, J. A.; Marti, J.

2001-12-01

As part of an ongoing project investigating assimilation in ocean island magmas, we are measuring stable isotope ratios of hydrothermally altered lithic fragments in phonolitic pyroclastic deposits from Tenerife, Canary Islands. Nepheline syenite blocks occur in the 0.196 Ma El Abrigo ignimbrite of the Diego Hernandez Formation (DHF). The DHF is the most recent of at least three caldera-forming magmatic cycles on Tenerife. The blocks are fragments of evolved plutons that are chemically similar to phonolites but extend to more strongly differentiated compositions. Distinct major and trace element concentrations suggest that the blocks derive from two intrusions, here referred to as A and B. The B syenites have chemical affinities with the El Abrigo phonolite, and some blocks contain small pockets of residual glass, suggesting that the B pluton may have been coeval with the El Abrigo magma. O isotope ratios of the B syenites lie within the range 4.8 to 7.0 per mil. The B samples are mostly fresh, and their higher O isotope ratios are near pristine magmatic values. Lower values occur in rocks with mild hydrothermal mineralogic alteration, and their values reflect limited high-temperature water-rock isotope exchange. O isotope ratios for A blocks are lower (0.1 to 6.3 per mil, most less than 2.0 per mil), and some samples show extensive mineral alteration. Near-ubiquitous alteration among the A samples, distinct major and trace element compositions, and lack of glass show that this syenite was older than, and unrelated to, the El Abrigo magma. Syenite D/H ratios range from -90 to -120 per mil. O vs H isotope relations indicate that an 18O-depleted meteoric water was the most important reservoir for the high-temperature hydrothermal fluid. Assimilation of altered syenite should provide a distinct stable isotope fingerprint that would be inherited by the product magma. DHF phonolites yield O ratios in the range 5.5 to 7.0 per mil, which may be this fingerprint. Assimilation of variably altered syenites, with accompanying fractionation, is a viable mechanism for producing this stable isotope variability in the magmas.

Ethane C-C clumping in natural gas : a proxy for cracking processes ?

NASA Astrophysics Data System (ADS)

Clog, M. D.; Ferreira, A. A.; Santos Neto, E. V.; Eiler, J. M.

2014-12-01

Ethane (C2H6) is the second-most abundant alkane in most natural gas reservoirs, and is used to produce ethylene for petrochemical industries. It is arguably the simplest molecule that can manifest multiple 13C substitutions. There are several plausible controls on Δ13C2H6in natural gas: thermodynamically controlled homogeneous isotope exchange reactions analogous to those behind carbonate clumped isotope thermometry; inheritance from larger biomolecules that undergo thermal degradation to produce natural gas; mixing of natural gases that differ markedly in bulk isotopic composition; diffusive fractionation; or combinations of these and/or other, less expected fractionations. There is little basis for predicting which of these will control isotopic variations among natural ethanes, but we think it likely that addition of this new isotopic proxy will reveal new insights into the natural chemistry of ethane. We have developed a method to measure the abundance of 13C2H6 in natural samples, using high-resolution mass spectrometry. We define Δ13C2H6 as 1000 . ((13C2H6/12C2H6)measured/(13C2H6/12C2H6)stochastic -1). We studied several suites of natural gas samples and experimentally produced or modified ethane. Natural ethanes, including closely related samples from a single natural gas field, exhibit surprisingly large ranges in Δ13C2H6 (4 ‰ overall; up to 3 ‰ in one gas field). Such ranges cannot be explained by thermodynamic equilibrium at a range of different temperatures, or by diffusive fractionation. Kinetic isotope effects associated with 'cracking' reactions, and/or inheritance of non-equilibrium carbon isotope structures from source organics are more likely causes. We observe a correlation between Δ13C2H6 and the concentration of alkanes other than methane in several suites of natural gases, suggesting the causes of clumped isotope variations are tied to the controls on gas wetness. An experiment examining ethane residual to high-temperature pyrolysis confirms this trend could be an isotopic fingerprint for ethane destruction.

Isotope labeling to determine the dynamics of metabolic response in CHO cell perfusion bioreactors using MALDI-TOF-MS.

PubMed

Karst, Daniel J; Steinhoff, Robert F; Kopp, Marie R G; Soos, Miroslav; Zenobi, Renato; Morbidelli, Massimo

2017-11-01

The steady-state operation of Chinese hamster ovary (CHO) cells in perfusion bioreactors requires the equilibration of reactor dynamics and cell metabolism. Accordingly, in this work we investigate the transient cellular response to changes in its environment and their interactions with the bioreactor hydrodynamics. This is done in a benchtop perfusion bioreactor using MALDI-TOF MS through isotope labeling of complex intracellular nucleotides (ATP, UTP) and nucleotide sugars (UDP-Hex, UDP-HexNAc). By switching to a 13 C 6 glucose containing feed media during constant operation at 20 × 10 6 cells and a perfusion rate of 1 reactor volume per day, isotopic steady state was studied. A step change to the 13 C 6 glucose medium in spin tubes allowed the determination of characteristic times for the intracellular turnover of unlabeled metabolites pools, τST (≤0.56 days), which were confirmed in the bioreactor. On the other hand, it is shown that the reactor residence time τR (1 day) and characteristic time for glucose uptake τGlc (0.33 days), representative of the bioreactor dynamics, delayed the consumption of 13 C 6 glucose in the bioreactor and thus the intracellular 13 C enrichment. The proposed experimental approach allowed the decoupling of bioreactor hydrodynamics and intrinsic dynamics of cell metabolism in response to a change in the cell culture environment. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:1630-1639, 2017. © 2017 American Institute of Chemical Engineers.

The influence of lithology on surface water sources | Science ...

EPA Pesticide Factsheets

Understanding the temporal and spatial variability of surface water sources within a basin is vital to our ability to manage the impacts of climate variability and land cover change. Water stable isotopes can be used as a tool to determine geographic and seasonal sources of water at the basin scale. Previous studies in the Coastal Range of Oregon reported that the variation in the isotopic signatures of surface water does not conform to the commonly observed “rainout effect”, which exhibits a trend of increasing isotopic depletion with rising elevation. The primary purpose of this research is to investigate the mechanisms governing seasonal and spatial variations in the isotopic signature of surface waters within the Marys River Basin, located in the leeward side of the Oregon Coastal Range. Surface water and precipitation samples were collected every 2-3 weeks for isotopic analysis of δ18O and δ2H for one year. Results indicate a significant difference in isotopic signature between watersheds underlain by basalt and sandstone. The degree of separation was the most distinct during the summer when low flows reflect deeper groundwater sources, whereas isotopic signatures during the rainy season (fall and winter) showed a greater degree of similarity between the two lithologies. This indicates that baseflow within streams drained by sandstone versus basalt is being supplied from two distinctly separate water sources. In addition, Marys River flow at the outle

Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction.

PubMed

Chapman, Elizabeth C; Capo, Rosemary C; Stewart, Brian W; Kirby, Carl S; Hammack, Richard W; Schroeder, Karl T; Edenborn, Harry M

2012-03-20

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Transformation of Upland Water and Carbon Dynamics by Thawing Permafrost in the Alaskan Interior

NASA Astrophysics Data System (ADS)

Ewing, S. A.; Paces, J. B.; O'Donnell, J. A.; Kanevskiy, M. Z.; Shur, Y.; Jorgenson, M. T.; Harden, J.; Aiken, G. R.; Striegl, R.

2009-05-01

Large arctic rivers can provide an integrated signal of regional permafrost thaw and associated carbon dynamics. A long-term (30-y) decrease in dissolved organic carbon (DOC) and increase in dissolved inorganic carbon in the Yukon River Basin (YRB) suggest increased flow through mineral soils as a result of permafrost thaw. We used U series isotopes to test for the influence of thaw on soil and surface waters in small upland catchments at two sites within the YRB. In natural waters, 234U/238U activity ratios exceed 1.00 (secular equilibrium) as a function of water-rock contact time. Previous work has shown that in major YRB rivers, seasonally and spatially variable 234U/238U ratios could indicate both groundwater inputs and permafrost thaw, with ratios ranging from 1.1 to 2.6. We show that 234U/238U ratios in soil and surface water from these small catchments span the range of values observed in the major rivers, and indicate greater influence of older water where the mineral soil and underlying sediment facilitate drainage and permafrost degradation. Analysis of deep, ice-rich loess permafrost cores (2-10 m) reveals that thaw of Pleistocene ice can release high concentrations of DOC (>1000 ppm) and ammonium in thaw waters. The age and chemical composition of these waters allows for improved prediction of downstream carbon dynamics upon thaw. Field observation of hillslope soil sequences indicates that both topography and mineral substrate influence the effects of thaw on water and carbon dynamics in small catchments.

Overview of the ISOL facility for the RISP

NASA Astrophysics Data System (ADS)

Woo, H. J.; Kang, B. H.; Tshoo, K.; Seo, C. S.; Hwang, W.; Park, Y.-H.; Yoon, J. W.; Yoo, S. H.; Kim, Y. K.; Jang, D. Y.

2015-02-01

The key feature of the Isotope Separation On-Line (ISOL) facility is its ability to provide high-intensity and high-quality beams of neutron-rich isotopes with masses in the range of 80-160 by means of a 70-MeV proton beam directly impinging on uranium-carbide thin-disc targets to perform forefront research in nuclear structure, nuclear astrophysics, reaction dynamics and interdisciplinary fields like medical, biological and material sciences. The technical design of the 10-kW and the 35-kW direct fission targets with in-target fission rates of up to 1014 fissions/s has been finished, and for the development of the ISOL fission-target chemistry an initial effort has been made to produce porous lanthanum-carbide (LaCx) discs as a benchmark for the final production of porous UCx discs. For the production of various beams, three classes of ion sources are under development at RISP (Rare Isotope Science Project), the surface ion source, the plasma ion source (FEBIAD), the laser ion source, and the engineering design of the FEBIAD is in progress for prototype fabrication. The engineering design of the ISOL target/ion source front-end system is also in progress, and a prototype will be used for an off-line test facility in front of the pre-separator. The technical designs of other basic elements at the ISOL facility, such as the RF-cooler, the high-resolution mass separator, and the A/q separator, have been finished, and the results, along with the future plans, are introduced.

Negligible fractionation of Kr and Xe isotopes by molecular diffusion in water

NASA Astrophysics Data System (ADS)

Tyroller, Lina; Brennwald, Matthias S.; Busemann, Henner; Maden, Colin; Baur, Heinrich; Kipfer, Rolf

2018-06-01

Molecular diffusion is a key transport process for noble gases in water. Such diffusive transport is often thought to cause a mass-dependent fractionation of noble gas isotopes that is inversely proportional to the square root of the ratio of their atomic mass, referred to as the square root relation. Previous studies, challenged the commonly held assumption that the square root relation adequately describes the behaviour of noble gas isotopes diffusing through water. However, the effect of diffusion on noble gas isotopes has only been determined experimentally for He, Ne and Ar to date, whereas the extent of fractionation of Kr and Xe has not been measured. In the present study the fractionation of Kr and Xe isotopes diffusing through water immobilised by adding agar was quantified through measuring the respective isotope ratio after diffusing through the immobilised water. No fractionation of Kr and Xe isotopes was observed, even using high-precision noble gas analytics. These results complement our current understanding on isotopic fractionation of noble gases diffusing through water. Therefore this complete data set builds a robust basis to describe molecular diffusion of noble gases in water in a physical sound manner which is fundamental to assess the physical aspects of gas dynamics in aquatic systems.

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

PubMed

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

2014-08-19

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

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.

Mapping the Spatial and Temporal Distribution of N and O Isotopes in Precipitation Nitrate Across the Northeastern and Mid-Atlantic United States

NASA Astrophysics Data System (ADS)

Elliott, E. M.; Kendall, C.; Harlin, K.; Butler, T.; Carlton, R.; Wankel, S.

2004-12-01

Atmospheric deposition of N is a universally important pathway by which ecosystems receive fixed, bioavailable N. Since the 1880s, atmospheric deposition of N has become increasingly important, as NOx emissions from fossil fuel combustion have steadily increased. In particular, the Northeastern and Mid-Atlantic U.S. receive some of the highest rates of nitrate wet deposition in the country, causing a cascade of detrimental effects. In order to effectively mediate the impacts of nitrate deposition, it is critical to understand the dynamics among NOx sources, atmospheric chemical transformations and transport, and the characteristics of the nitrate that is ultimately deposited. To address this need, this research takes advantage of recent methodological improvements, coupled with national networks (NADP, AIRMoN) of archived precipitation, to characterize N and O isotopic composition of nitrate in precipitation across the Northeastern and Mid-Atlantic U.S. We investigate the critical question of whether variations in \\delta15N and \\delta18O of nitrate wet deposition are mainly a function of atmospheric processes (e.g., seasonal variations in reaction pathways) or variable NOx source contributions (e.g., power plant emissions, vehicle exhaust). Spatial and seasonal variability of \\delta15N and \\delta18O is investigated using bimonthly archived samples from 2000. Furthermore, a high resolution record of daily precipitation from a single site is used to highlight within-season isotopic variability. Potential correlations between isotopic values and major NOx sources are explored using EPA datasets for monthly county-level emissions from two major NOx sources, electric generating units and on-road vehicles. Analysis of samples for \\Delta17O is in progress. A key concern regarding analysis of archived samples is nitrate preservation. We tested the stability of nitrate concentrations, and hence potential isotopic fractionations, by reanalyzing filtered, refrigerated, archived NADP samples with a range of nitrate and ammonium concentrations. We found highly significant correlations (R2=0.9995, p<0.001, n=28) between nitrate concentrations measured in 2000 and 2003, indicating that no major alterations had occurred. With regard to spatial patterns, preliminary isotopic analyses indicate that \\delta15N of precipitation nitrate varies considerably among states. Moreover, initial data corroborate previously reported seasonal trends in both \\delta15N and \\delta18O, with higher values in the colder months. Seasonal trends in \\delta15N are remarkably consistent, with up to an 8 \\permil difference between winter and summer months. \\delta18O values of nitrate are generally higher and have a smaller range than previously reported for precipitation, with values ranging from +60 to +90 \\permil. In addition, archived daily precipitation collected during 2000 from a single AIRMoN site give insight into the seasonal and within-season variability of \\delta15N and \\delta18O of precipitation nitrate. Back-trajectory analyses are used to examine the geographic source of air masses for individual events, and seasonal frontal patterns are discussed.

Two water worlds: Isotope evidence shows that trees and streams return different pools of water to the hydrosphere

EPA Science Inventory

Ecohydrological coupling at the watershed scale is poorly characterized. While soil-water storage is dynamic and strongly influenced by plants, few integrated tools exist for quantifying the spatial and temporal dynamics and interactions among the major components of the terrestr...

Isotope Brayton electric power system for the 500 to 2500 watt range

NASA Technical Reports Server (NTRS)

Macosko, R. P.; Barna, G. J.; Block, H. B.; Ingle, B. D.

1972-01-01

An extensive study was conducted at the Lewis Research Center to evaluate an isotope Brayton electric power system for use in the 500 to 2500 W power range. Overall system simplicity was emphasized in order to reduce parasitic power losses and improve system reliability. Detailed parametric cycle analysis, conceptual component designs, and evaluation of system packaging were included. A single-loop system (gas) with six major components including one rotating unit was selected. Calculated net system efficiency varies from 23 to 28 percent over the power range.

Sources and drains: Major controls of hydrothermal fluid flow in the Kokanee Range, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Beaudoin, Georges; Therrien, René

1999-10-01

Vein fields are fractured domains of the lithosphere that have been infiltrated by hydrothermal fluids, which deposited minerals in response to changing physico-chemical conditions. Because oxygen is a major component of the infiltrating fluid and the surrounding rock matrix, the oxygen isotope composition of minerals found in veins is used to decipher ancient fluid flow within the lithosphere. We use a numerical model to simulate oxygen isotope transport in the Kokanee Range silver-lead-zinc vein field. The model considers advective, dispersive, and reactive transport in a three-dimensional porous rock matrix intersected by high-permeability planes representing fracture zones. Here we show that it is the geometrical configuration of the sources and of the drains of hydrothermal fluids, combined with the fracture pattern, that exerts the main control on the oxygen isotope distribution. Other factors that affect, to a lesser extent, the values and positions of oxygen isopleths are the fluids and rock-matrix isotopic compositions, the isotopic fractionation, the reaction rate constant, and hydraulic conductivities of the rock matrix and fracture zones.

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

USGS Publications Warehouse

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

1969-01-01

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

Liquid chromatography coupled to isotope ratio mass spectrometry: a new perspective on honey adulteration detection.

PubMed

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2006-12-27

A new procedure to determine individual sugar (sucrose, glucose, and fructose) 13C isotope ratios, using liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS), has been developed to improve isotopic methods devoted to the study of honey authenticity. For this purpose 79 commercial honey samples from various origins were analyzed. Values of delta13Choney ranged from -14.2 to -27.2", and delta13Cprotein ranged from -23.6 to -26.9". A very strong correlation is observed between the individual sugar 13C ratios, which are altered in the event of sugar addition, even at low levels. The use of Deltadelta13C [fruct-glu], Deltadelta13C [fruct-suc], and Deltadelta13C [gluc-suc] systematic differences as an authenticity criterion permits the sugar addition [C3, beet sugar; or C4, cane sugar, cane syrup, isoglucose syrup, and high-fructose corn syrup (HFCS)] to be reliably detected (DL = 1-10%). The new procedure has advantages over existing methods in terms of analysis time and sensitivity. In addition, it is the first isotopic method developed that allows beet sugar addition detection.

Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

2017-10-01

Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

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.

Massive isotopic effect in vacuum UV photodissociation of N2 and implications for meteorite data

PubMed Central

Chakraborty, Subrata; Muskatel, B. H.; Jackson, Teresa L.; Ahmed, Musahid; Levine, R. D.; Thiemens, Mark H.

2014-01-01

Nitrogen isotopic distributions in the solar system extend across an enormous range, from −400‰, in the solar wind and Jovian atmosphere, to about 5,000‰ in organic matter in carbonaceous chondrites. Distributions such as these require complex processing of nitrogen reservoirs and extraordinary isotope effects. While theoretical models invoke ion-neutral exchange reactions outside the protoplanetary disk and photochemical self-shielding on the disk surface to explain the variations, there are no experiments to substantiate these models. Experimental results of N2 photolysis at vacuum UV wavelengths in the presence of hydrogen are presented here, which show a wide range of enriched δ15N values from 648‰ to 13,412‰ in product NH3, depending upon photodissociation wavelength. The measured enrichment range in photodissociation of N2, plausibly explains the range of δ15N in extraterrestrial materials. This study suggests the importance of photochemical processing of the nitrogen reservoirs within the solar nebula. PMID:25267643

Tin isotope fractionation during magmatic processes and the isotope composition of the bulk silicate Earth

NASA Astrophysics Data System (ADS)

Wang, Xueying; Amet, Quentin; Fitoussi, Caroline; Bourdon, Bernard

2018-05-01

Tin is a moderately volatile element whose isotope composition can be used to investigate Earth and planet differentiation and the early history of the Solar System. Although the Sn stable isotope composition of several geological and archaeological samples has been reported, there is currently scarce information about the effect of igneous processes on Sn isotopes. In this study, high-precision Sn isotope measurements of peridotites and basalts were obtained by MC-ICP-MS with a double-spike technique. The basalt samples display small variations in δ124/116Sn ranging from -0.01 ± 0.11 to 0.27 ± 0.11‰ (2 s.d.) relative to NIST SRM 3161a standard solution, while peridotites have more dispersed and more negative δ124Sn values ranging from -1.04 ± 0.11 to -0.07 ± 0.11‰ (2 s.d.). Overall, basalts are enriched in heavy Sn isotopes relative to peridotites. In addition, δ124Sn in peridotites become more negative with increasing degrees of melt depletion. These results can be explained by different partitioning behavior of Sn4+ and Sn2+ during partial melting. Sn4+ is overall more incompatible than Sn2+ during partial melting, resulting in Sn4+-rich silicate melt and Sn2+-rich residue. As Sn4+ has been shown experimentally to be enriched in heavy isotopes relative to Sn2+, the effect of melting is to enrich residual peridotites in relatively more compatible Sn2+, which results in isotopically lighter peridotites and isotopically heavier mantle-derived melts. This picture can be disturbed partly by the effect of refertilization. Similarly, the presence of enriched components such as recycled oceanic crust or sediments could explain part of the variations in Sn isotopes in oceanic basalts. The most primitive peridotite analyzed in this study was used for estimating the Sn isotope composition of the BSE, with δ124Sn = -0.08 ± 0.11‰ (2 s.d.) relative to the Sn NIST SRM 3161a standard solution. Altogether, this suggests that Sn isotopes may be a powerful probe of redox processes in the mantle.

Isotopic Analysis of Fingernails as a USGS Open House Demonstration of the Use of Stable Isotopes in Foodweb Studies

NASA Astrophysics Data System (ADS)

Silva, S. R.; Kendall, C.; Young, M. B.; Choy, D.

2011-12-01

The USGS Isotope Tracers Project uses stable isotopes and tritium to add a unique dimension of chemical information to a wide range of environmental investigations. The use and application of isotopes is usually an unfamiliar and even esoteric topic to the general public. Therefore during three USGS open house events, as a public outreach effort, we demonstrated the use of stable isotopes by analyzing nitrogen and carbon isotopes from very small fragments of fingernail from willing participants. We titled the exhibit "You Are What You Eat". The results from all participants were plotted on a graph indicating the general influence of different food groups on the composition of body tissues as represented by fingernails. All participants were assigned a number and no personal-identification information was collected. A subset of participants provided us with an estimate of the number of days a week various foods were eaten and if they were vegetarians, vegans or non-vegetarians. Volunteers from our research group were on hand to explain and discuss fundamental concepts such as how foods attain their isotopic composition, the difference between C3 and C4 plants, the effects of assimilation, trophic enrichment, and the various uses of stable isotopes in environmental studies. The results of the fingernail analyses showed the variation of the range of isotopic compositions among about 400 people at each event, the distinct influence of C4 plants (mainly corn and cane sugar) on our carbon isotopic composition, and the isotopic differences between vegetarians and non vegetarians among other details (http://wwwrcamnl.wr.usgs.gov/isoig/projects/fingernails/). A poll of visitors attending the open house event in 2006 indicated that "You Are What You Eat" was among the most popular exhibits. Following the first two open house events we were contacted by a group of researchers from Brazil who had completed a very similar study. Our collaboration resulted in a publication in the American Journal of Physical Anthropology (Nardoto et al., 2006). This study found that despite global trends toward dietary homogenization, regional differences in food resources and dietary preferences were recorded in the carbon and nitrogen isotopic compositions of fingernails.

Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird

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

Pearson, Scott, F.; Levey, Douglas, J.; Greenberg, Catheryn, H.

2003-02-28

Pearson, S.F., D.J. Levey, C.H. Greenberg, and C.M. del Rio. 2003. Effects of elemental composition on the incorporation of dietary nitrogen and carbon isotopic signatures in an omnivorous songbird. Oecologia. 135:516-523. The use of stable isotopes to infer diet requires quantifying the relationship between diet and tissues and, in particular, knowing of how quickly isotopes turnover in different tissues and how isotopic concentrations of different food components change (discriminate) when incorporated into consumer tissues. We used feeding trials with wild-caught yellow-rumped warblers (Dendroica coronata) to determine d15N and d13C turnover rates for blood, d15N and d13C diet-tissue discrimination factors, andmore » diet-tissue relationships for blood and feathers. After 3 weeks on a common diet, 36 warblers were assigned to one of four diets differing in the relative proportion of fruit and insects. Plasma half-life estimates ranged from 0.4 to 0.7 days for d13C and from 0.5 to 1.7 days for d15N. Half-life did not differ among diets. Whole blood half-life for d13C ranged from 3.9 to 6.1 days. Yellow-rumped warbler tissues were enriched relative to diet by 1.7.3.6% for nitrogen isotopes and by 1.2 to 4.3% for carbon isotopes, depending on tissue and diet. Consistent with previous studies, feathers were the most enriched and whole blood and plasma were the least enriched or, in the case of carbon, slightly depleted relative to diet. In general, tissues were more enriched relative to diet for birds with high percentages of insects. For all tissues, carbon and nitrogen isotope discrimination factors increased with carbon and nitrogen concentrations of diets. The isotopic signature of plasma increased linearly with the sum of the isotopic signature of the diet and the discrimination factor. Because the isotopic signature of tissues depends on both elemental concentration and isotopic signature of the diet, attempts to reconstruct diet from stable isotope signatures require mixing models that incorporate elemental concentration.« less

Oxygen isotope ranking of late Eocene and Oligocene planktonic foraminifers: Implications for Oligocene sea-surface temperatures and global ice-volume

USGS Publications Warehouse

Poore, R.Z.; Matthews, R.K.

1984-01-01

Oxygen isotope analyses of late Eocene and Oligocene planktonic foraminifers from low and middle latitude sites in the Atlantic Basin show that different species from the same samples can yield significantly different isotopic values. The range of isotopic values observed between species is greatest at low-latitudes and declines poleward. Many planktonic foraminifers exhibit a systematic isotopic ranking with respect to each other and can therefore be grouped on the basis of their isotopic ranking. The isotopic ranking of some taxa, however, appears to vary geographically and/or through time. Isotopic and paleontologic data from DSDP Site 522 indicate that commonly used isotopic temperature scales underestimate Oligocene sea surface temperatures. We suggest these temperature scales require revision to reflect the presence of Oligocene glaciation. Comparison of isotopic and paleontologic data from Sites 522, 511 and 277 suggests cold, low-salinity surface waters were present in high southern latitudes during the early Oligocene. Lowsalinity, high latitude surface waters could be caused by Eocene/Oligocene paleogeography or by the production of warm saline bottom water. ?? 1984.

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

USGS Publications Warehouse

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

2008-01-01

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

Controls over spatial and seasonal variations on isotopic composition of the precipitation along the central and eastern portion of Brazil.

PubMed

Gastmans, Didier; Santos, Vinícius; Galhardi, Juliana Aparecida; Gromboni, João Felipe; Batista, Ludmila Vianna; Miotlinski, Konrad; Chang, Hung Kiang; Govone, José Silvio

2017-10-01

Based on Global Network Isotopes in Precipitation (GNIP) isotopic data set, a review of the spatial and temporal variability of δ 18 O and δ 2 H in precipitation was conducted throughout central and eastern Brazil, indicating that dynamic interactions between Intertropical and South Atlantic Convergence Zones, Amazon rainforest, and Atlantic Ocean determine the variations on the isotopic composition of precipitation over this area. Despite the seasonality and latitude effects observed, a fair correlation with precipitation amount was found. In addition, Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) air mass back trajectories were used to quantify the factors controlling daily variability in stable isotopes in precipitation. Through a linear multiple regression analysis, it was observed that temporal variations were consistent with the meteorological parameters derived from HYSPLIT, particularly precipitation amount along the trajectory and mix depth, but are not dependent on vapour residence time in the atmosphere. These findings also indicate the importance of convective systems to control the isotopic composition of precipitation in tropical and subtropical regions.

Fabrication of 12% {sup 240}Pu calorimetry standards

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

Long, S.M.; Hildner, S.; Gutierrez, D.

1995-08-01

Throughout the DOE complex, laboratories are performing calorimetric assays on items containing high burnup plutonium. These materials contain higher isotopic range and higher wattages than materials previously encountered in vault holdings. Currently, measurement control standards have been limited to utilizing 6% {sup 240}Pu standards. The lower isotopic and wattage value standards do not complement the measurement of the higher burnup material. Participants of the Calorimetry Exchange (CALEX) Program have identified the need for new calorimetric assay standards with a higher wattage and isotopic range. This paper describes the fabrication and verification measurements of the new CALEX standard containing 12% {supmore » 240}Pu oxide with a wattage of about 6 to 8 watts.« less

Preservation of Fe Isotope Proxies in the Rock Record

NASA Astrophysics Data System (ADS)

Johnson, C.; Beard, B.; Valley, J.; Valaas, E.

2005-12-01

Iron isotope variations provide powerful constraints on redox conditions and pathways involved during biogeochemical cycling of Fe in surface and near-surface environments. The relative isotopic homogeneity of igneous rocks and most bulk weathering products contrasts with the significant isotopic variations (4 per mil in 56Fe/54Fe) that accompany oxidation of Fe(II)aq, precipitation of sulfides, and reduction by bacteria. These isotopic variations often reflect intrinsic (equilibrium) Fe isotope fractionations between minerals and aqueous species whose interactions may be directly or indirectly catalyzed by bacteria. In addition, Fe isotope exchange may be limited between reactive Fe pools in low-temperature aqueous-sediment environments, fundamentally reflecting disequilibrium effects. In the absence of significant sulfide, dissimilatory Fe(III) reduction by bacteria produces relatively low 56Fe/54Fe ratios for Fe(II)aq and associated biogenic minerals such as magnetite and siderite. In contrast, Fe(II)aq that exchanges with Fe sulfides (FeS and pyrite) is relatively enriched in 56Fe/54Fe ratios. In modern and ancient environments, anoxic diagenesis tends to produce products that have low 56Fe/54Fe ratios, whereas oxidation of Fe(II)aq from hydrothermal sources tends to produce ferric Fe products that have high 56Fe/54Fe ratios. Redox cycling by bacteria tends to produce reactive ferric Fe reservoirs that have low 56Fe/54Fe ratios. Application of Fe isotopes as a proxy for redox conditions in the ancient rock record depends upon the preservation potential during metamorphism, given the fact that most Archean sedimentary sequences have been subjected to regional greenschist- to granulite-facies metamorphism. The 1.9 Ga banded iron formations (BIFs) of the Lake Superior region that are intruded by large ~1 Ga intrusions (e.g., Duluth gabbro) provide a test of the preservation potential for primary, low-temperature Fe isotope variations in sedimentary rocks. 56Fe/54Fe ratios for re-crystallized magnetite from BIFs of the Biwabik iron formation that have apparent oxygen-isotope (quartz-magnetite) temperatures between 270 and 800 oC span a significant portion of the range measured in lower-grade BIFs from South Africa and Australia. d56Fe values for Biwabik magnetite vary from -0.2 to +0.7 per mil, whereas magnetite from the Dales Gorge member of the Brockman iron formation and the Kuruman iron formation has d56Fe values that lie between -1.2 and +1.3 per mil. Iron isotope fractionations between magnetite and Fe silicates (greenalite, hedenbergite, and fayalite) in the Biwabik iron formation regularly decrease with increasing oxygen-isotope temperatures, approaching the zero fractionation expected at igneous temperatures; apparent magnetite-Fe silicate fractionations range from +0.2 per mil at 650 oC to +0.5 per mil at 300 oC, lying close to those predicted using the revised beta factors of Polyakov et al. (2005, Goldschmidt). During closed-system Fe isotope exchange during metamorphism, the overall range in d56Fe values for magnetite will remain relatively constant, although it may shift to higher d56Fe values relative to primary (low-temperature) magnetite due to the non-zero magnetite-Fe silicate fractionation factor at moderate temperature ranges. If the mineral parageneis is known, and some assumptions regarding primary mineralogy can be made, these small corrections may be made to successfully infer the original Fe isotope compositions of sedimentary minerals and rocks that have been subjected to metamorphism.