Isotopic fingerprint of the middle Olt River basin, Romania.

PubMed

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

2014-01-01

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

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.

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.

Review: Current applications and challenges for liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS).

PubMed

Godin, Jean-Philippe; McCullagh, James S O

2011-10-30

High-precision isotope analysis is recognized as an essential research tool in many fields of study. Until recently, continuous flow isotope ratio mass spectrometry (CF-IRMS) was available via an elemental analyzer or a gas chromatography inlet system for compound-specific analysis of light stable isotopes. In 2004, however, an interface that coupled liquid chromatography with IRMS (LC/IRMS) became commercially available for the first time. This brought the capability for new areas of application, in particular enabling compound-specific δ(13)C analysis of non-volatile, aqueous soluble, compounds from complex mixtures. The interface design brought with it several analytical constraints, however, in particular a lack of compatibility with certain types of chromatography as well as limited flow rates and mobile phase compositions. Routine LC/IRMS methods have, however, been established for measuring the δ(13)C isotopic ratios of underivatized individual compounds for application in archeology, nutrition and physiology, geochemistry, hydrology, soil science and food authenticity. Seven years after its introduction, we review the technical advances and constraints, methodological developments and new applications of liquid chromatography coupled to isotope ratio mass spectrometry. Copyright © 2011 John Wiley & Sons, Ltd.

Process for recovering evolved hydrogen enriched with at least one heavy hydrogen isotope

DOEpatents

Tanaka, John; Reilly, Jr., James J.

1978-01-01

This invention relates to a separation means and method for enriching a hydrogen atmosphere with at least one heavy hydrogen isotope by using a solid titaniun alloy hydride. To this end, the titanium alloy hydride containing at least one metal selected from the group consisting of vanadium, chromium, manganese, molybdenum, iron, cobalt and nickel is contacted with a circulating gaseous flow of hydrogen containing at least one heavy hydrogen isotope at a temperature in the range of -20.degree. to +40.degree. C and at a pressure above the dissociation pressure of the hydrided alloy selectively to concentrate at least one of the isotopes of hydrogen in the hydrided metal alloy. The contacting is continued until equilibrium is reached, and then the gaseous flow is isolated while the temperature and pressure of the enriched hydride remain undisturbed selectively to isolate the hydride. Thereafter, the enriched hydrogen is selectively recovered in accordance with the separation factor (S.F.) of the alloy hydride employed.

Measurement of isotope ratios on transient signals by MC-ICP-MS.

PubMed

Günther-Leopold, Ines; Wernli, Beat; Kopajtic, Zlatko; Günther, Detlef

2004-01-01

Precise and accurate isotope ratio measurements are an important task in many applications such as isotope-dilution mass spectrometry, bioavailability studies, or the determination of isotope variations in geological or nuclear samples. The technique of MC-ICP-MS has attracted much attention because it permits the precise measurement of isotope compositions for a wide range of elements combined with excellent detection limits due to high ionisation efficiencies. However, the results are based mainly on measurements using continuous sample introduction. In the present study the determination of isotope ratios on various transient signals with a time duration of 30 to 60 s has been achieved by coupling high-performance liquid chromatography to a multicollector inductively coupled plasma mass spectrometer. In order to investigate the origin of ratio drifts across the transient signals for this hyphenated technique, measurements with the same standard solutions were also carried out using a flow-injection device for sample introduction. As a result of this application it could be concluded that the main source of the bias in the measured isotope ratios is within the ICP-MS instead of fractionation effects on the chromatographic column material. Preliminary studies on short transient signals of gaseous samples (dry plasma) showed a reverse fractionation effect compared with wet plasma conditions (flow injection and HPLC).

Separation of isotopes by cyclical processes

DOEpatents

Hamrin, Jr., Charles E.; Weaver, Kenny

1976-11-02

Various isotopes of hydrogen are separated by a cyclic sorption process in which a gas stream containing the isotopes is periodically passed through a high pressure column containing a palladium sorbent. A portion of the product from the high pressure column is passed through a second column at lower pressure to act as a purge. Before the sorbent in the high pressure column becomes saturated, the sequence is reversed with the stream flowing through the former low-pressure column now at high pressure, and a portion of the product purging the former high pressure column now at low pressure. The sequence is continued in cyclic manner with the product being enriched in a particular isotope.

Nicotine, acetanilide and urea multi-level 2H-, 13C- and 15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry.

PubMed

Schimmelmann, Arndt; Albertino, Andrea; Sauer, Peter E; Qi, Haiping; Molinie, Roland; Mesnard, François

2009-11-01

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 delta values of these reference materials should bracket the isotopic range of samples with unknown delta 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 delta13C and delta15N, 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: delta2H(nicotine) -162 to -45 per thousand, delta13C(nicotine) -30.05 to +7.72 per thousand, delta15N(nicotine) -6.03 to +33.62 per thousand; delta15N(acetanilide) +1.18 to +40.57 per thousand; delta13C(urea) -34.13 to +11.71 per thousand, delta15N(urea) +0.26 to +40.61 per thousand (recommended delta 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 delta15N values. Comparative delta13C and delta15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials. Copyright 2009 John Wiley & Sons, Ltd.

High-precision determination of 18O/16O ratios of silver phosphate by EA-pyrolysis-IRMS continuous flow technique.

PubMed

Lécuyer, Christophe; Fourel, François; Martineau, François; Amiot, Romain; Bernard, Aurélien; Daux, Valérie; Escarguel, Gilles; Morrison, John

2007-01-01

A high-precision, and rapid on-line method for oxygen isotope analysis of silver phosphate is presented. The technique uses high-temperature elemental analyzer (EA)-pyrolysis interfaced in continuous flow (CF) mode to an isotopic ratio mass spectrometer (IRMS). Calibration curves were generated by synthesizing silver phosphate with a 13 per thousand spread in delta(18)O values. Calibration materials were obtained by reacting dissolved potassium dihydrogen phosphate (KH(2)PO(4)) with water samples of various oxygen isotope compositions at 373 K. Validity of the method was tested by comparing the on-line results with those obtained by classical off-line sample preparation and dual inlet isotope measurement. In addition, silver phosphate precipitates were prepared from a collection of biogenic apatites with known delta(18)O values ranging from 12.8 to 29.9 per thousand (V-SMOW). Reproducibility of +/- 0.2 per thousand was obtained by the EA-Py-CF-IRMS method for sample sizes in the range 400-500 microg. Both natural and synthetic samples are remarkably well correlated with conventional (18)O/(16)O determinations. Silver phosphate is a very stable material and easy to degas and, thus, could be considered as a good candidate to become a reference material for the determination of (18)O/(16)O ratios of phosphate by high-temperature pyrolysis. Copyright 2006 John Wiley & Sons, Ltd.

D and 18O enrichment measurements in biological fluids in a continuous-flow elemental analyser with an isotope-ratio mass spectrometer using two configurations.

PubMed

Ripoche, N; Ferchaud-Roucher, V; Krempf, M; Ritz, P

2006-09-01

In doubly labelled water studies, biological sample enrichments are mainly measured using off-line techniques (equilibration followed by dual-inlet introduction) or high-temperature elemental analysis (HT-EA), coupled with an isotope-ratio mass spectrometer (IRMS). Here another continuous-flow method, (CF-EA/IRMS), initially dedicated to water, is tested for plasma and urine analyses. The elemental analyser configuration is adapted for each stable isotope: chromium tube for deuterium reduction and glassy carbon reactor for 18O pyrolysis. Before on-line conversion of water into gas, each matrix is submitted to a short and easy treatment, which is the same for the analysis of the two isotopes. Plasma is passed through centrifugal filters. Urine is cleaned with black carbon and filtered (0.45 microm diameter). Tested between 150 and 300 ppm in these fluids, the D/H ratio response is linear with good repeatability (SD<0.2 ppm) and reproducibility (SD<0.5 ppm). For 18O/16O ratios (from 2000 to 2200 ppm), the same repeatability is obtained with a between-day precision lower than 1.4 ppm. The accuracy on biological samples is validated by comparison to classical dual-inlet methods: 18O analyses give more accurate results. The data show that enriched physiological fluids can be successfully analysed in CF-EA/IRMS. Copyright (c) 2006 John Wiley & Sons, Ltd.

Following Carbon Isotopes from Methane to Molecules

NASA Astrophysics Data System (ADS)

Freeman, K. H.

2017-12-01

Continuous-flow methods introduced by Hayes (Matthews and Hayes, 1978; Freeman et al., 1990; Hayes et al., 1990) for compound-specific isotope analyses (CSIA) transformed how we study the origins and fates of organic compounds. This analytical revolution launched several decades of research in which researchers connect individual molecular structures to diverse environmental and climate processes affecting their isotopic profiles. Among the first applications, and one of the more dramatic isotopically, was tracing the flow of natural methane into cellular carbon and cellular biochemical constituents. Microbial oxidation of methane can be tracked by strongly 13C-depleted organic carbon in early Earth sedimentary environments, in marine and lake-derived biomarkers in oils, and in modern organisms and their environments. These signatures constrain microbial carbon cycling and inform our understanding of ocean redox. The measurement of molecular isotopes has jumped forward once again, and it is now possible to determine isotope abundances at specific positions within increasingly complex organic structures. In addition, recent analytical developments have lowered sample sensitivity limits of CSIA to picomole levels. These new tools have opened new ways to measure methane carbon in the natural environment and within biochemical pathways. This talk will highlight how molecular isotope methods enable us to follow the fate of methane carbon in complex environments and along diverse metabolic pathways, from trace fluids to specific carbon positions within microbial biomarkers.

A continuous stream flash evaporator for the calibration of an IR cavity ring-down spectrometer for the isotopic analysis of water.

PubMed

Gkinis, Vasileios; Popp, Trevor J; Johnsen, Sigfus J; Blunier, Thomas

2010-12-01

A new technique for high-resolution simultaneous isotopic analysis of δ¹⁸O and δD in liquid water is presented. A continuous stream flash evaporator has been designed that is able to vapourise a stream of liquid water in a continuous mode and deliver a stable and finely controlled water vapour sample to a commercially available infrared cavity ring-down spectrometer. Injection of sub-microlitre amounts of the liquid water is achieved by pumping liquid water sample through a fused silica capillary and instantaneously vapourising it with 100% efficiency in a home-made oven at a temperature of 170 °C. The system's simplicity, low power consumption and low dead volume together with the possibility for automated unattended operation provides a solution for the calibration of laser instruments performing isotopic analysis of water vapour. Our work is mainly driven by the possibility to perform high-resolution online water isotopic analysis on continuous-flow analysis (CFA) systems typically used to analyse the chemical composition of ice cores drilled in polar regions. In the following, we describe the system's precision and stability and sensitivity to varying levels of sample size and we assess the observed memory effects. A test run with standard waters of different isotopic compositions is presented, demonstrating the ability to calibrate the spectrometer's measurements on a VSMOW scale with a relatively simple and fast procedure.

Continuous production of tritium in an isotope-production reactor with a separate circulation system

DOEpatents

Cawley, W.E.; Omberg, R.P.

1982-08-19

A method is described for producing tritium in a fast breeder reactor cooled with liquid metal. Lithium is allowed to flow through the reactor in separate loops in order to facilitate the production and removal of tritium.

High-resolution continuous-flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

NASA Astrophysics Data System (ADS)

Emanuelsson, B. D.; Baisden, W. T.; Bertler, N. A. N.; Keller, E. D.; Gkinis, V.

2015-07-01

Here we present an experimental setup for water stable isotope (δ18O and δD) continuous-flow measurements and provide metrics defining the performance of the setup during a major ice core measurement campaign (Roosevelt Island Climate Evolution; RICE). We also use the metrics to compare alternate systems. Our setup is the first continuous-flow laser spectroscopy system that is using off-axis integrated cavity output spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research, LGR) in combination with an evaporation unit to continuously analyze water samples from an ice core. A Water Vapor Isotope Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to (1) enable measurements on several water standards, (2) increase the temporal resolution by reducing the response time and (3) reduce the influence from memory effects. While this setup was designed for the continuous-flow analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. The custom setups provide a shorter response time (~ 54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~ 62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the custom setups have a reduced memory effect. Stability tests comparing the custom and WVISS setups were performed and Allan deviations (σAllan) were calculated to determine precision at different averaging times. For the custom 2013 setup the precision after integration times of 103 s is 0.060 and 0.070 ‰ for δ18O and δD, respectively. The corresponding σAllan values for the custom 2014 setup are 0.030, 0.060 and 0.043 ‰ for δ18O, δD and δ17O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042 ‰ after 103 s for δ18O, δD and δ17O, respectively. Both the custom setups and WVISS setup are influenced by instrumental drift with δ18O being more drift sensitive than δD. The σAllan values for δ18O are 0.30 and 0.18 ‰ for the custom 2013 and WVISS setup, respectively, after averaging times of 104 s (2.78 h). Using response time tests and stability tests, we show that the custom setups are more responsive (shorter response time), whereas the University of Copenhagen (UC) setup is more stable. More broadly, comparisons of different setups address the challenge of integrating vaporizer/spectrometer isotope measurement systems into a CFA campaign with many other analytical instruments.

Lifetime Stable isotopes profiles in whale earplug: assessment of foraging and migrations in the Northern Hemisphere

NASA Astrophysics Data System (ADS)

Mansouri, F.; Crain, D.; Winfield, Z.; Trumble, S.; Usenko, S.

2017-12-01

Whale earplugs, historically used for aging, were used to reconstruct lifetime stable isotope profiles for carbon (δ13C) and nitrogen (δ15N) for individual whales by delaminating lamina within the earplug. These stable isotope profile, which provide Continuous lifetime records of feeding, foraging ecology, and migration, were determined for 20 individuals from 4 baleen species including fin, minke, humpback, and blue whales spanning more than a century (1869 - 2014) using stable isotope analysis. Approximately 1 mg tissue from each lamina (n=1200) was analyzed for carbon and nitrogen stable isotope using continuous flow isotope ratio mass spectrometer (CF-IRMS). This research using whale earplugs have combined age estimates with stable isotope measurements to reconstruct lifetime foraging profiles with a 6-month resolution, providing an unprecedented opportunity to assess periods and trends in dietary fluctuations as well as migration between different foraging area which have distinct isotope values. Trends with these profiles suggest long-term changing in migration, while annual variability highlights seasonal fasting and feeding. Isotopic ratios were also used to identify subpopulations of Atlantic fin whales, which enabled us to assign unidentified humpback and minke whales to the Atlantic or Pacific Oceans. This historical archive of data provides us an unprecedented tool to assess long term marine ecosystem and subsequently marine organism transition to alternate foraging area and shed light on the whale's population status in the Northern hemisphere.

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.

Delta13C and delta18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite.

PubMed

Révész, Kinga M; Landwehr, Jurate M

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 +/- 20 micro g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H(3)PO(4)/CaCO(3)) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H(3)PO(4)/CaCO(3) reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 degrees C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was

MONITORING POLYCHLORINATED BIPHENYLS (PCBS) BIODEGRADATION USING CONTINUOUS-FLOW ISOTOPE RATIO MASS SPECTROMETRY

EPA Science Inventory

Research has shown that polychlorinated biphenyls (PCBs) in some cases can be removed from the environment by biodegradation. Aerobic and anaerobic biological processes have been determined in previous research to be capable of degrading PCBs. During the aerobic and anaerobic d...

An economical method for the continuous production of iodine-123

NASA Technical Reports Server (NTRS)

Blue, J. W.; Smith, W. R.; Sodd, V. J.

1968-01-01

Simple and inexpensive method produces iodine 123, in a conventional cyclotron. Tellurium 122, a stable isotope available in enrichments exceeding 95 percent, is held on a porous metal plate by a flowing stream of helium and bombarded with either alpha particles or helium 3.

Combined use of isotopic and hydrometric data to conceptualize ecohydrological processes in a high-elevation tropical ecosystem

USGS Publications Warehouse

Mosquera, Giovanny M; Celleri, Rolando; Lazo, Patricio X; Vache, Kellie B; Perakis, Steven; Crespo, Patricio

2016-01-01

Few high-elevation tropical catchments worldwide are gauged and even fewer are studied using combined hydrometric and isotopic data. Consequently, we lack information needed to understand processes governing rainfall-runoff dynamics and to predict their influence on downstream ecosystem functioning. To address this need, we present a combination of hydrometric and water stable isotopic observations in the wet Andean páramo ecosystem of the Zhurucay Ecohydrological Observatory (7.53 km2). The catchment is located in the Andes of south Ecuador between 3400 and 3900 m a.s.l. Water samples for stable isotopic analysis were collected during 2 years (May 2011 – May 2013), while rainfall and runoff measurements were continuously recorded since late 2010. The isotopic data reveal that Andosol soils predominantly situated on hillslopes drain laterally to Histosols (Andean páramo wetlands) mainly located at the valley bottom. Histosols, in turn, feed water to creeks and small rivers throughout the year, establishing hydrologic connectivity between wetlands and the drainage network. Runoff is primarily comprised of pre-event water stored in the Histosols, which is replenished by rainfall that infiltrates through the Andosols. Contributions from the mineral horizon and the top of the fractured bedrock are small and only seem to influence discharge in small catchments during low flow generation (non-exceedance flows < Q35). Variations in source contributions are controlled by antecedent soil moisture, rainfall intensity, and duration of rainy periods. Saturated hydraulic conductivity of the soils, higher than the year-round low precipitation intensity, indicates that Hortonian overland flow rarely occurs during high intensity precipitation events. Deep groundwater contributions to discharge seem to be minimal. These results suggest that, in this high-elevation tropical ecosystem: 1) subsurface flow is a dominant hydrological process and 2) (Histosols) wetlands are the major source of stream runoff. Our study highlights that detailed isotopic characterization during short time periods provides valuable information about ecohydrological processes in regions where very few basins are gauged.

Temporal variation in stable isotopes ( 18O and 2H) and major ion concentrations within the Darling River between Bourke and Wilcannia due to variable flows, saline groundwater influx and evaporation

NASA Astrophysics Data System (ADS)

Meredith, K. T.; Hollins, S. E.; Hughes, C. E.; Cendón, D. I.; Hankin, S.; Stone, D. J. M.

2009-11-01

SummaryThe Darling River faces environmental pressures from both climate change and anthropogenic influences leading to a reduction in fresh water availability for the river system. This study uses temporal hydrochemical and stable isotope data ( 18O and 2H) that has been collected over a five-year period (2002 to 2007), as part of the Global Network for Isotopes in Rivers (GNIR) programme, which is aimed at monitoring hydrological processes in large river systems throughout the world. Daily stream flow, monthly stable isotope and major ion chemistry data is presented for sampling locations along the Darling River at Bourke, Louth and Wilcannia, as well as additional more detailed data from locations near Glen Villa. The hydrochemical data is used to partition groundwater influx that is not readily separable by using only the available isotopic data. Individual flow events in the river were found to be isotopically distinct but the Local Evaporation Lines (LELs) that develop after these events have a similar slope indicating similar climatic conditions across this region. After a storm event, fresh waters that are isotopically depleted are introduced to the system and d-excess ( d) values return towards meteoric values. During low flow, the Cl -, Na +, Mg 2+, SO 42-, δ 18O and δ 2H values all increase systematically, and d values become more negative. Hydrochemical and isotopic tracers in conjunction with high resolution sampling strategies have been used to quantify the contribution of evaporation, bank storage release and saline groundwater influx to the evolution of the river waters. Fractional contributions (% of volume) of groundwater to the river water were calculated for different reaches using Cl - concentrations, δ 18O and d values and it was found that river waters comprised of approximately 60-99% saline groundwater during zero flow. The reduced water levels in the river during the drought conditions experienced in the period of this study had detrimental impacts on the surface water system by providing a pathway for saline groundwaters to discharge into the river system. Persistent drought and continued over-abstraction of surface waters will lead to further saline groundwater intrusion along this reach of the river. This work shows that a suite of hydrochemical and isotopic tracers are needed on spatially and temporally significant scales to unravel the hydrological complexities of dryland river systems such as the Darling River.

Improved methodologies for continuous-flow analysis of stable water isotopes in ice cores

NASA Astrophysics Data System (ADS)

Jones, Tyler R.; White, James W. C.; Steig, Eric J.; Vaughn, Bruce H.; Morris, Valerie; Gkinis, Vasileios; Markle, Bradley R.; Schoenemann, Spruce W.

2017-02-01

Water isotopes in ice cores are used as a climate proxy for local temperature and regional atmospheric circulation as well as evaporative conditions in moisture source regions. Traditional measurements of water isotopes have been achieved using magnetic sector isotope ratio mass spectrometry (IRMS). However, a number of recent studies have shown that laser absorption spectrometry (LAS) performs as well or better than IRMS. The new LAS technology has been combined with continuous-flow analysis (CFA) to improve data density and sample throughput in numerous prior ice coring projects. Here, we present a comparable semi-automated LAS-CFA system for measuring high-resolution water isotopes of ice cores. We outline new methods for partitioning both system precision and mixing length into liquid and vapor components - useful measures for defining and improving the overall performance of the system. Critically, these methods take into account the uncertainty of depth registration that is not present in IRMS nor fully accounted for in other CFA studies. These analyses are achieved using samples from a South Pole firn core, a Greenland ice core, and the West Antarctic Ice Sheet (WAIS) Divide ice core. The measurement system utilizes a 16-position carousel contained in a freezer to consecutively deliver ˜ 1 m × 1.3 cm2 ice sticks to a temperature-controlled melt head, where the ice is converted to a continuous liquid stream and eventually vaporized using a concentric nebulizer for isotopic analysis. An integrated delivery system for water isotope standards is used for calibration to the Vienna Standard Mean Ocean Water (VSMOW) scale, and depth registration is achieved using a precise overhead laser distance device with an uncertainty of ±0.2 mm. As an added check on the system, we perform inter-lab LAS comparisons using WAIS Divide ice samples, a corroboratory step not taken in prior CFA studies. The overall results are important for substantiating data obtained from LAS-CFA systems, including optimizing liquid and vapor mixing lengths, determining melt rates for ice cores with different accumulation and thinning histories, and removing system-wide mixing effects that are convolved with the natural diffusional signal that results primarily from water molecule diffusion in the firn column.

Mathematical modeling of filling of gas centrifuge cascade for nickel isotope separation by various feed flow rate

NASA Astrophysics Data System (ADS)

Ushakov, Anton; Orlov, Alexey; Sovach, Victor P.

2018-03-01

This article presents the results of research filling of gas centrifuge cascade for separation of the multicomponent isotope mixture with process gas by various feed flow rate. It has been used mathematical model of the nonstationary hydraulic and separation processes occurring in the gas centrifuge cascade. The research object is definition of the regularity transient of nickel isotopes into cascade during filling of the cascade. It is shown that isotope concentrations into cascade stages after its filling depend on variable parameters and are not equal to its concentration on initial isotope mixture (or feed flow of cascade). This assumption is used earlier any researchers for modeling such nonstationary process as set of steady-state concentration of isotopes into cascade. Article shows physical laws of isotope distribution into cascade stage after its filling. It's shown that varying each parameters of cascade (feed flow rate, feed stage number or cascade stage number) it is possible to change isotope concentration on output cascade flows (light or heavy fraction) for reduction of duration of further process to set of steady-state concentration of isotopes into cascade.

δ13C and δ18O isotopic composition of CaCO3 measured by continuous flow isotope ratio mass spectrometry: statistical evaluation and verification by application to Devils Hole core DH-11 calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate M.

2002-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ± 20 µg) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26 °C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ≤0.1 and ≤0.2 per mill or ‰, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for δ18O to achieve this level of precision. Aliquot screening methods were shown to further minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings. 

Catalytic recombination of dissociation products with Pt/SnO2 for rare and common isotope long-life, closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Brown, Kenneth G.; Sidney, B. D.; Schryer, D. R.; Upchurch, B. T.; Miller, I. M.

1986-01-01

This paper reports results on recombination of pulsed CO2 laser dissociation products with Pt/SnO2 catalysts, and supporting studies in a surrogate laboratory catalyst reactor. The closed-cycle, pulsed CO2 laser has been continuously operated for one million pulses with an overall power degradation of less than 5 percent by flowing the laser gas mixture through a 2-percent Pt/SnO2 catalyst bed. In the surrogate laboratory reactor, experiments have been conducted to determine isotopic exchange with the catalyst when using rare-isotope gases. The effects of catalyst pretreatment, sample weight, composition, and temperature on catalyst efficiency have also been determined.

Comparison of secondary ion mass spectrometry and micromilling/continuous flow isotope ratio mass spectrometry techniques used to acquire intra-otolith delta18O values of wild Atlantic salmon (Salmo salar).

PubMed

Hanson, N N; Wurster, C M; Todd, C D

2010-09-15

The chemical signals in the sequential layers of fish otoliths have the potential to provide fisheries biologists with temporal and spatial details of migration which are difficult to obtain without expensive tracking methods. Signal resolution depends, however, on the extraction technique used. We compared the use of mechanical micromilling and continuous flow isotope ratio mass spectrometry (CF-IRMS) methods with secondary ion mass spectrometry (SIMS) to obtain delta(18)O profiles from otoliths of wild Atlantic salmon (Salmo salar) and used these to corroborate the time of freshwater emigration of the juvenile with macroscopic patterns within the otolith. Both techniques showed the transition occurring at the same visible feature on the otolith, allowing future analyses to easily identify the juvenile (freshwater) versus adult (marine) life-stages. However, SIMS showed a rapid and abrupt transition whereas micromilling provided a less distinct signal. The number of samples that could be obtained per unit area sampled using SIMS was 2 to 3 times greater than that when using micromilling/CF-IRMS although the delta(18)O values and analytical precisions (approximately 0.2 per thousand) of the two methods were comparable. In addition, SIMS delta(18)O results were used to compare otolith aragonite values with predicted values calculated using various isotope fractionation equations. Copyright 2010 John Wiley & Sons, Ltd.

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

Silylated Derivatives Retain Carbon and Alter Expected 13C-Tracer Enrichments Using Continuous Flow-Combustion-Isotope Ratio Mass Spectrometry

PubMed Central

Shinebarger, Steven R.; Haisch, Michael; Matthews, Dwight E.

2008-01-01

Continuous-flow inlets from oxidation reactors are commonly used systems for biological sample introduction into isotope ratio mass spectrometers (IRMS) to measure 13C enrichment above natural abundance. Because the samples must be volatile enough to pass through a gas chromatograph, silylated derivatization reactions are commonly used to modify biological molecules to add the necessary volatility. Addition of a t-butyldimethylsilyl (TBDMS) group is a common derivatization approach. However, we have found that samples do not produce the expected increment in measured 13C abundance as the TBDMS derivatives. We have made measurements of 13C enrichment of leucine and glutamate standards of known 13C enrichment using derivatives without silicon (N-acetyl n-propyl ester), with silicon (TBDMS), and an intermediate case. The measurements of 13C in amino acids derivatized without silicon were as expected. The 13C enrichment measurements using the TBDMS derivative were higher than expected, but could be corrected to produce the expected 13C enrichment measurement by IRMS if one carbon was removed per silicon. We postulate that the silicon in the derivative forms silicon carbide compounds in the heated cupric oxide reactor, rather than forming silicon dioxide. Doing so reduces the amount of CO2 formed from the carbon in the sample. Silylated derivatives retain carbon with the silicon and must be used carefully and with correction factors to measure 13C enrichments by continuous-flow IRMS. PMID:12510745

Spatially resolved δ13C analysis using laser ablation isotope ratio mass spectrometry

NASA Astrophysics Data System (ADS)

Moran, J.; Riha, K. M.; Nims, M. K.; Linley, T. J.; Hess, N. J.; Nico, P. S.

2014-12-01

Inherent geochemical, organic matter, and microbial heterogeneity over small spatial scales can complicate studies of carbon dynamics through soils. Stable isotope analysis has a strong history of helping track substrate turnover, delineate rhizosphere activity zones, and identifying transitions in vegetation cover, but most traditional isotope approaches are limited in spatial resolution by a combination of physical separation techniques (manual dissection) and IRMS instrument sensitivity. We coupled laser ablation sampling with isotope measurement via IRMS to enable spatially resolved analysis over solid surfaces. Once a targeted sample region is ablated the resulting particulates are entrained in a helium carrier gas and passed through a combustion reactor where carbon is converted to CO2. Cyrotrapping of the resulting CO2 enables a reduction in carrier gas flow which improves overall measurement sensitivity versus traditional, high flow sample introduction. Currently we are performing sample analysis at 50 μm resolution, require 65 ng C per analysis, and achieve measurement precision consistent with other continuous flow techniques. We will discuss applications of the laser ablation IRMS (LA-IRMS) system to microbial communities and fish ecology studies to demonstrate the merits of this technique and how similar analytical approaches can be transitioned to soil systems. Preliminary efforts at analyzing soil samples will be used to highlight strengths and limitations of the LA-IRMS approach, paying particular attention to sample preparation requirements, spatial resolution, sample analysis time, and the types of questions most conducive to analysis via LA-IRMS.

Partitioning evapotranspiration via continuous sampling of water vapor isotopes over common row crops and candidate biofuel crops.

NASA Astrophysics Data System (ADS)

Miller, J. N.; Black, C. K.; Bernacchi, C.

2014-12-01

Global demand for renewable energy is accelerating land conversion from common row crops such as maize and soybean to cellulosic biofuel crops such as miscanthus and switchgrass. This land conversion is expected to alter ecohydrology via changes in evapotranspiration (ET). However, the direction in which evapotranspiration will shift, either partitioning more moisture through soil evaporation (E) or through plant transpiration (T) is uncertain. To investigate how land conversion from maize to miscanthus affects ET partitioning we measured the isotopic composition of water vapor via continuous air sampling. We obtained continuous diurnal measurements of δ2H and δ18O for miscanthus and maize on multiple days over the course of the growing season. Water vapor isotopes drawn from two heights were measured at 2 Hz using a cavity ringdown spectrometer and partitioned into components of E and T using a simple mixing equation. A second approach to partitioning was accomplished by subtracting transpiration measurements, obtained through sap flow sensors, from total ET, measured via eddy covariance. Preliminary results reveal that both methods compare favorably and that transpiration dominates variations in ET in miscanthus fields more so than in fields of maize.

Tracking ENSO with tropical trees: Progress in stable isotope dendroclimatology

NASA Astrophysics Data System (ADS)

Evans, M. N.; Poussart, P. F.; Saleska, S. R.; Schrag, D. P.

2002-12-01

The terrestrial tropics remain an important gap in the growing proxy network used to characterize past ENSO behavior. Here we describe a strategy for development of proxy estimates of paleo-ENSO, via proxy rainfall estimates derived from stable isotope (δ18O) measurements made on tropical trees. The approach applies a new model of oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brand, 1996) to develop proxy chronological, rainfall and growth rate estimates from tropical trees, even those lacking annual rings. The promise and pitfalls of the approach are illustrated in pilot datasets from the US, Costa Rica, Brazil, and Peru, which show isotopic cycles of 4-6 per mil, and interannual anomalies of up to 8 per mil. Together with the mature ENSO proxies (corals, extratropical tree-rings, varved sediments, and ice cores), replicated and well-dated stable isotope chronologies from tropical trees may eventually improve our understanding of ENSO history over the past several hundred years.

Flow-through SIP - A novel stable isotope probing approach limiting cross-feeding

NASA Astrophysics Data System (ADS)

Mooshammer, Maria; Kitzinger, Katharina; Schintlmeister, Arno; Kjedal, Henrik; Nielsen, Jeppe Lund; Nielsen, Per; Wagner, Michael

2017-04-01

Stable isotope probing (SIP) is a widely applied tool to link specific microbial populations to metabolic processes in the environment without the prerequisite of cultivation, which has greatly advanced our understanding of the role of microorganisms in biogeochemical cycling. SIP relies on tracing specific isotopically labeled substrates (e.g., 13C, 15N, 18O) into cellular biomarkers, such as DNA, RNA or phospholipid fatty acids, and is considered to be a robust technique to identify microbial populations that assimilate the labeled substrate. However, cross-feeding can occur when labeled metabolites are released from a primary consumer and then used by other microorganisms. This leads to erroneous identification of organisms that are not directly responsible for the process of interest, but are rather connected to primary consumers via a microbial food web. Here, we introduce a new approach that has the potential to eliminate the effect of cross-feeding in SIP studies and can thus also be used to distinguish primary consumers from other members of microbial food webs. In this approach, a monolayer of microbial cells are placed on a filter membrane, and labeled substrates are supplied by a continuous flow. By means of flow-through, labeled metabolites and degradation products are constantly removed, preventing secondary consumption of the substrate. We present results from a proof-of-concept experiment using nitrifiers from activated sludge as model system, in which we used fluorescence in situ hybridization (FISH) with rRNA-targeted oligonucleotide probes for identification of nitrifiers in combination with nanoscale secondary ion mass spectrometry (NanoSIMS) for visualization of isotope incorporation at the single-cell level. Our results show that flow-through SIP is a promising approach to significantly reduce cross-feeding and secondary substrate consumption in SIP experiments.

Understanding of changes in river flow using recently collected field and observational data from Russian Arctic

NASA Astrophysics Data System (ADS)

Shiklomanov, A. I.; Tokarev, I. V.; Davydov, S. P.; Davydova, A.; Streletskiy, D. A.

2017-12-01

There is substantial evidence supporting increasing river runoff in the Eurasian pan-Arctic, but the causes of these changes are not well understood. To determine the contributions of various water sources to river runoff generation in small streams and large rivers located in the continuous permafrost zone, an extensive field campaign was carried out near the town of Cherskii, Russia. Measurements of hydrometeorological characteristics, as well as stable isotope composition and hydrochemistry of precipitation, river flow and ground ice, were obtained during the 2013-2016 period. When combined with older data (2005-2009), the isotopic composition of atmospheric precipitation showed a general trend towards heavier winter precipitation, attributed mainly to observed increases in winter air temperature. Samples of water and ground ice from several boreholes showed that isotopic compositions of water from the active layer, transient layer and permafrost are significantly different. Thus, stable isotopes can be used to assess contributions of different soil layers to stream flow generation. Increases in streamflow of small test watersheds were observed during dry periods in August-September. These increases were associated with considerable stable isotope depletion in streamflow samples, which is likely caused by thawing of the transient- and possibly upper permafrost layers. The absence of correlation between water and air temperature during these periods (R2 = 0.22 in August-September and R2 = 0.8 in June-July) also suggests an increasing contribution of thawing ground ice to the streamflow. To quantitatively assess the contribution of various water sources to the river runoff of Kolyma River, we used stable isotope data along with a physically based hydrological model developed at the University of New Hampshire. Preliminary results suggest that thawing permafrost increased August-September discharge in Kolyma near Cherskii by 8% in 2013, 11% in 2014 and 4% in 2015, even though none of these years was extremely warm or wet. We estimate that 5cm of permafrost thaw (with 30% ice content) over the entire Kolyma basin can contribute about 10 km3/year (or 10%) to annual discharge and significantly change the water regime during low-flow periods (fall-winter).

Correction algorithm for online continuous flow δ13C and δ18O carbonate and cellulose stable isotope analyses

NASA Astrophysics Data System (ADS)

Evans, M. N.; Selmer, K. J.; Breeden, B. T.; Lopatka, A. S.; Plummer, R. E.

2016-09-01

We describe an algorithm to correct for scale compression, runtime drift, and amplitude effects in carbonate and cellulose oxygen and carbon isotopic analyses made on two online continuous flow isotope ratio mass spectrometry (CF-IRMS) systems using gas chromatographic (GC) separation. We validate the algorithm by correcting measurements of samples of known isotopic composition which are not used to estimate the corrections. For carbonate δ13C (δ18O) data, median precision of validation estimates for two reference materials and two calibrated working standards is 0.05‰ (0.07‰); median bias is 0.04‰ (0.02‰) over a range of 49.2‰ (24.3‰). For α-cellulose δ13C (δ18O) data, median precision of validation estimates for one reference material and five working standards is 0.11‰ (0.27‰); median bias is 0.13‰ (-0.10‰) over a range of 16.1‰ (19.1‰). These results are within the 5th-95th percentile range of subsequent routine runtime validation exercises in which one working standard is used to calibrate the other. Analysis of the relative importance of correction steps suggests that drift and scale-compression corrections are most reliable and valuable. If validation precisions are not already small, routine cross-validated precision estimates are improved by up to 50% (80%). The results suggest that correction for systematic error may enable these particular CF-IRMS systems to produce δ13C and δ18O carbonate and cellulose isotopic analyses with higher validated precision, accuracy, and throughput than is typically reported for these systems. The correction scheme may be used in support of replication-intensive research projects in paleoclimatology and other data-intensive applications within the geosciences.

Preferential flow pathways revealed by field based stable isotope analysis of CO2 by mid-infrared laser spectroscopy

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Nowak, Martin; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A. C.; Jost, Hj

2016-04-01

A newly developed and commercially available isotope ratio laser spectrometer for CO2 analyses has been tested during a 10-day field monitoring campaign at the Ketzin pilot site for CO2 storage in northern Germany. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10-day carbon stable isotope data set with 30 minutes resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within 2σ analytical precision (<0.3 ‰). This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time table isotope data directly in the field. The injected CO2 tracer had a distinct δ13C value that was largely different from the reservoir background value. The laser spectroscopy data revealed a prior to this study unknown, intensive dynamic with fast changing δ13C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The new technique might contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

A Geochemical Mass-Balance Method for Base-Flow Separation, Upper Hillsborough River Watershed, West-Central Florida, 2003-2005 and 2009

USGS Publications Warehouse

Kish, G.R.; Stringer, C.E.; Stewart, M.T.; Rains, M.C.; Torres, A.E.

2010-01-01

Geochemical mass-balance (GMB) and conductivity mass-balance (CMB) methods for hydrograph separation were used to determine the contribution of base flow to total stormflow at two sites in the upper Hillsborough River watershed in west-central Florida from 2003-2005 and at one site in 2009. The chemical and isotopic composition of streamflow and precipitation was measured during selected local and frontal low- and high-intensity storm events and compared to the geochemical and isotopic composition of groundwater. Input for the GMB method included cation, anion, and stable isotope concentrations of surface water and groundwater, whereas input for the CMB method included continuous or point-sample measurement of specific conductance. The surface water is a calcium-bicarbonate type water, which closely resembles groundwater geochemically, indicating that much of the surface water in the upper Hillsborough River basin is derived from local groundwater discharge. This discharge into the Hillsborough River at State Road 39 and at Hillsborough River State Park becomes diluted by precipitation and runoff during the wet season, but retains the calcium-bicarbonate characteristics of Upper Floridan aquifer water. Field conditions limited the application of the GMB method to low-intensity storms but the CMB method was applied to both low-intensity and high-intensity storms. The average contribution of base flow to total discharge for all storms ranged from 31 to 100 percent, whereas the contribution of base flow to total discharge during peak discharge periods ranged from less than 10 percent to 100 percent. Although calcium, magnesium, and silica were consistent markers of Upper Floridan aquifer chemistry, their use in calculating base flow by the GMB method was limited because the frequency of point data collected in this study was not sufficient to capture the complete hydrograph from pre-event base-flow to post-event base-flow concentrations. In this study, pre-event water represented somewhat diluted groundwater. Streamflow conductivity integrates the concentrations of the major ions, and the logistics of acquiring specific conductance at frequent time intervals are less complicated than data collection, sample processing, shipment, and analysis of water samples in a laboratory. The acquisition of continuous specific conductance data reduces uncertainty associated with less-frequently collected geochemical point data.

Regional hydrogeology and hydrochemistry of deep formation waters in the Williston Basin (Canada-USA): implications for fluid migration in the basin

NASA Astrophysics Data System (ADS)

Rostron, B. J.

2010-12-01

The regional groundwater flow-system in the Williston Basin (Canada-USA) is one of the best examples of a mega-scale confined aquifer-system in the world. With its well-defined recharge and discharge areas separated by approximately 1000 km horizontal and 1 km vertical distance, the basin is an ideal natural laboratory to study regional groundwater flow and hydrochemistry. Springs and shallow water wells in the recharge and discharge areas, along with deeper oil and gas wells, allow for detailed mapping of formation-pressures. Further, these wells provide access for sampling and geochemical analyses of formation waters along flow paths. Basin-scale hydrogeological and hydrochemical mapping combined with newly obtained geochemical and isotopic data from more than 2000 wells across the basin provide new insights into the present and paleohydrogeology of the basin. Results indicate: 1) the hydrogeology and hydrochemistry of the basin must be mapped on hydrogeological (not political) boundaries; 2) many aquifers have similar water chemistries, yet unique isotopic fingerprints; 3) stable isotope distributions provide insight(s) into regional fluid flow patterns; 4) analysis of bromine concentrations and stable isotopic compositions provide evidence that at least some of the brine in the basin owes its origin to evaporated seawater and not just dissolved evaporites as previously thought; 5) regional patterns of stable isotopes and halogens can be used to trace different flow "events" in the basin's history; 6) calcium-rich brines in the center of the basin may be associated with relict calcium-rich seawaters; 7) hydrocarbon migration pathways have been variably impacted by evolving hydrodynamic conditions; and 8) there is strong evidence of past glacially-driven recharge in the current discharge area of the basin. These observations show that the hydrogeology and hydrochemistry of the basin is more complex than previously thought. Portions of the basin appear to respond rapidly to changes in boundary conditions including: the recharge areas; midline areas that have experienced extensive salt dissolution; and present discharge areas that appear to show evidence of glacially-driven recharge. Other portions of the basin appear to have had little to no fluid-flow despite being continuous and highly-permeable. Mixing, and not depth, appears to control water compositions. Insights gained from regional hydrogeology and hydrochemical provide an improved understanding the present and past mega-scale fluid migration in the Williston Basin.

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

PubMed

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

2012-04-15

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

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

Measurement of delta13C and delta18O Isotopic Ratios of CaCO3 by a Thermoquest Finnigan GasBench II Delta Plus XL Continous Flow Isotope Ratio Mass Spectrometer with Application to Devils Hole Core DH-11 Calcite

USGS Publications Warehouse

Revesz, Kinga M.; Landwehr, Jurate Maciunas; Keybl, Jaroslav Edward

2001-01-01

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400?20 ?g) of calcium carbonate. This new method streamlines the classical phosphoric acid - calcium carbonate (H3PO4 - CaCO3) reaction method by making use of a Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. To obtain reproducible and accurate results, optimal conditions for the H3PO4 - CaCO3 reaction had to be determined. At the acid-carbonate reaction temperature suggested by the equipment manufacturer, the oxygen isotope ratio results were unsatisfactory (standard deviation () greater than 1.5 per mill), probably because of a secondary reaction. When the acid-carbonate reaction temperature was lowered to 26?C and the reaction time was increased to 24 hours, the precision of the carbon and oxygen isotope ratios for duplicate analyses improved to 0.1 and 0.2 per mill, respectively. The method was tested by analyzing calcite from Devils Hole, Nevada, which was formed by precipitation from ground water onto the walls of a sub-aqueous cavern during the last 500,000 years. Isotope-ratio values previously had been obtained by the classical method for Devils Hole core DH-11. The DH-11 core had been recently re-sampled, and isotope-ratio values were obtained using this new method. The results were comparable to those obtained by the classical method. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, a cutting error that was then independently confirmed. The reproducibility of the isotopic values is demonstrated by a correlation of approximately 0.96 for both isotopes, after correcting for an alignment offset. This result indicates that the new method is a viable alternative to the classical method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable timesavings.

A temporal stable isotopic (d18O, dD, d-excess) comparison in glacier meltwater streams, Taylor Valley, Antarctica

USDA-ARS?s Scientific Manuscript database

In this paper, we describe the importance of hyporheic dynamics within Andersen Creek and Von Guerard Stream, Taylor Valley, Antarctica, from the 2010-11 melt season using natural tracers. Water collection started at flow onset and continued, with weekly hyporheic zone sampling. The water d18O and d...

Coal fly ash interaction with environmental fluids: Geochemical and strontium isotope results from combined column and batch leaching experiments

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

Brubaker, Tonya M; Stewart, Brian W; Capo, Rosemary C

2013-05-01

The major element and Sr isotope systematics and geochemistry of coal fly ash and its interactions with environmental waters were investigated using laboratory flow-through column leaching experiments (sodium carbonate, acetic acid, nitric acid) and sequential batch leaching experiments (water, acetic acid, hydrochloric acid). Column leaching of Class F fly ash samples shows rapid release of most major elements early in the leaching procedure, suggesting an association of these elements with soluble and surface bound phases. Delayed release of certain elements (e.g., Al, Fe, Si) signals gradual dissolution of more resistant silicate or glass phases as leaching continues. Strontium isotope resultsmore » from both column and batch leaching experiments show a marked increase in {sup 87}Sr/{sup 86}Sr ratio with continued leaching, yielding a total range of values from 0.7107 to 0.7138. For comparison, the isotopic composition of fluid output from a fly ash impoundment in West Virginia falls in a narrow range around 0.7124. The experimental data suggest the presence of a more resistant, highly radiogenic silicate phase that survives the combustion process and is leached after the more soluble minerals are removed. Strontium isotopic homogenization of minerals in coal does not always occur during the combustion process, despite the high temperatures encountered in the boiler. Early-released Sr tends to be isotopically uniform; thus the Sr isotopic composition of fly ash could be distinguishable from other sources and is a useful tool for quantifying the possible contribution of fly ash leaching to the total dissolved load in natural surface and ground waters.« less

A stable isotope-based approach to tropical dendroclimatology

NASA Astrophysics Data System (ADS)

Evans, Michael N.; Schrag, Daniel P.

2004-08-01

We describe a strategy for development of chronological control in tropical trees lacking demonstrably annual ring formation, using high resolution δ 18O measurements in tropical wood. The approach applies existing models of the oxygen isotopic composition of alpha-cellulose (Roden et al., 2000), a rapid method for cellulose extraction from raw wood (Brendel et al., 2000), and continuous flow isotope ratio mass spectrometry (Brenna et al., 1998) to develop proxy chronological, rainfall and growth rate estimates from tropical trees lacking visible annual ring structure. Consistent with model predictions, pilot datasets from the temperate US and Costa Rica having independent chronological control suggest that observed cyclic isotopic signatures of several permil (SMOW) represent the annual cycle of local rainfall and relative humidity. Additional data from a plantation tree of known age from ENSO-sensitive northwestern coastal Peru suggests that the 1997-8 ENSO warm phase event was recorded as an 8‰ anomaly in the δ 18O of α-cellulose. The results demonstrate reproducibility of the stable isotopic chronometer over decades, two different climatic zones, and three tropical tree genera, and point to future applications in paleoclimatology.

Eddy Covariance measurements of stable isotopes (δD and δ18O) in water vapor

NASA Astrophysics Data System (ADS)

Braden-Behrens, J.; Knohl, A.

2016-12-01

Stable isotopes are a promising tool to enhance our understanding of ecosystem gas exchanges. Studying 18O and 2H (D) in water vapour (H2Ov) can e.g. help partitioning evapotranspiration into its components. With recent developments in laser spectroscopy direct Eddy Covariance (EC) measurements to investigate fluxes of stable isotopologues became feasible. But so far only very few case studies applying the EC method to stable isotopes in water vapor have been carried out worldwide At our micrometeorological EC tower in a managed beech forest in Thuringia, Germany, we continuously measure fluxes of water vapor isotopologues using EC since autumn 2015. The set-up is based on an off-axis cavity output water vapor isotope analyzer (WVIA, Los Gatos Research. Inc, USA) that measures the water vapour concentration and its isotopic composition (δD and δ18O). The instrument is optimized for high flow rates (app. 4slpm) to generate high frequent (2Hz) measurements. The HF-optimized WVIA showed sufficient precision with a minimal Allan Deviation of 0.023 ‰ for δD and 0.02 ‰ for δ18O for averaging periods of app. 700 s and 400 s resp. The instrument is 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 large 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. We evaluate the calibration approach, present specific aspects of the set-up such as the HF optimization and compare the measured and averaged spectra and cospectra of the isotopologue analyzer with those of the longterm EC installation (using a LI-6262 as well as a LI-7200 infrared gas analyzer at 10 Hz). Furthermore, we show results for the isotopologue fluxes before and after leaf unfolding in spring/summer 2016. This novel instrument for EC measurements of water vapor isotopologues provides a new exciting opportunity for studying the hydrological cycle in long-term observation networks like Ameriflux and ICOS.

The Roles of the Yellowstone Hotspot and Crustal Assimilation in Generating Pleistocene-Holocene Basalts on the Eastern Snake River Plain

NASA Astrophysics Data System (ADS)

Mintz, H.; Chadwick, J.

2017-12-01

The southwest motion of the North American plate across the Yellowstone hotspot created a chain of age-progressive rhyolitic calderas over the past 16 myr. in southern Idaho, U.S. The focus of Yellowstone activity now resides in northwest Wyoming, but basaltic volcanism has continued in its wake in southern Idaho on the eastern Snake River Plain (ESRP). These younger basaltic lavas are not age progressive and have buried the Yellowstone rhyolites on the ESRP. The ultimate source of the basalts is commonly ascribed to the passage or presence of the hotspot. However, the mechanisms involved, and the relative roles of the hotspot, other mantle sources, and the North American crust in generating the ESRP basalts remain unclear and have been the subject of recent geochemical and isotopic studies. In this study, the role of crustal assimilation is addressed by analyzing the chemical and isotopic characteristics of some of the youngest Pleistocene-Holocene tholeiitic volcanic fields on the ESRP, which were erupted through varying thicknesses of continental crust. Samples were analyzed from the Hell's Half Acre flow (5,200 years old; all dates Kuntz et al., 1986, 1994), Cerro Grande flow (13,380 years), and Black Butte Crater (a.k.a. Shoshone) flow (10,130 years), which were erupted at distances from between about 200 to 300 km from the current location of the hotspot. The crust of the ESRP thins from northeast to southwest, from about 47 km at the Hells Half Acre flow to 40 km at the Black Butte Crater flow, a thickness difference of about 15%. The apparently similar tectonic and magmatic environments of the three sampled flows suggest the crustal thickness variation may be a primary influence on the magnitude of assimilation and therefore the isotopic characteristics of the lavas. The goal of this work is to constrain the relative role of assimilation and to understand the source(s) of the magmas and the Yellowstone hotspot contribution. Major elements, trace elements, and Pb-Sr-Nd isotopic data for the flows and crustal xenoliths, in conjunction with mixing modeling with MELTS software, constrain potential differences in fractional crystallization, residence times in the crust, and crustal assimilation for the flows.

Isotopic decoupling during porous melt flow: A case-study in the Lherz peridotite

NASA Astrophysics Data System (ADS)

Le Roux, V.; Bodinier, J.-L.; Alard, O.; O'Reilly, S. Y.; Griffin, W. L.

2009-03-01

Most peridotite massifs and mantle xenoliths show a wide range of isotopic variations, often involving significant decoupling between Hf, Nd and Sr isotopes. These variations are generally ascribed either to mingling of individual components of contrasted isotopic compositions or to time integration of parent-element enrichment by percolating melts/fluids, superimposed onto previous depletion event(s). However, strong isotopic decoupling may also arise during porous flow as a result of daughter-elements fractionation during solid-liquid interaction. Although porous flow is recognized as an important process in mantle rocks, its effects on mantle isotopic variability have been barely investigated so far. The peridotites of the Lherz massif (French Pyrenees) display a frozen melt percolation front separating highly refractory harzburgites from refertilized lherzolites. Isotopic signatures observed at the melt percolation front show a strong decoupling of Hf from Nd and Sr isotopes that cannot be accounted for by simple mixing involving the harzburgite protolith and the percolating melt. Using one dimensional percolation-diffusion and percolation-reaction modeling, we show that these signatures represent transient isotopic compositions generated by porous flow. These signatures are governed by a few critical parameters such as daughter element concentrations in melt and peridotite, element diffusivity, and efficiency of isotopic homogenization rather than by the chromatographic effect of melt transport and the refertilization reaction. Subtle variations in these parameters may generate significant inter-isotopic decoupling and wide isotopic variations in mantle rocks.

Effects of Sea Level Rise on Groundwater Flow Paths in a Coastal Aquifer System

NASA Astrophysics Data System (ADS)

Morrissey, S. K.; Clark, J. F.; Bennett, M. W.; Richardson, E.; Stute, M.

2008-05-01

Changes in groundwater flow in the Floridan aquifer system, South Florida, from the rise in sea level at the end of the last glacial period may be indicative of changes coastal aquifers will experience with continued sea level rise. As sea level rises, the hydraulic head near the coast increases. Coastal aquifers can therefore experience decreased groundwater gradients (increased residence times) and seawater intrusion. Stable isotopes of water, dissolved noble gas temperatures, radiocarbon and He concentrations were analyzed in water collected from 68 wells in the Floridan aquifer system throughout South Florida. Near the recharge area, geochemical data along groundwater flow paths in the Upper Floridan aquifer show a transition from recently recharged groundwater to glacial-aged water. Down gradient from this transition, little variation is apparent in the stable isotopes and noble gas recharge temperatures, indicating that most of the Upper Floridan aquifer contains groundwater recharged during the last glacial period. The rapid 120-meter rise in sea level marking the end of the last glacial period increased the hydraulic head in the Floridan aquifer system near the coast, slowing the flow of groundwater from the recharge area to the ocean and trapping glacial-aged groundwater. The raised sea level also flooded half of the Florida platform and caused seawater to intrude into the Lower Floridan. This circulation of seawater in the Lower Floridan continues today as our data indicate that the groundwater is similar to modern seawater with a freshwater component entering vertically from the recharge area to the Upper Floridan.

A New Method of Obtaining High-Resolution Paleoclimate Records from Speleothem Fluid Inclusions

NASA Astrophysics Data System (ADS)

Logan, A. J.; Horton, T. W.

2010-12-01

We present a new method for stable hydrogen and oxygen isotope analysis of ancient drip water trapped within cave speleothems. Our method improves on existing fluid inclusion isotopic analytical techniques in that it decreases the sample size by a factor of ten or more, dramatically improving the spatial and temporal precision of fluid inclusion-based paleoclimatology. Published thermal extraction methods require large samples (c. 150 mg) and temperatures high enough (c. 500-900°C) to cause calcite decomposition, which is also associated with isotopic fractionation of the trapped fluids. Extraction by crushing faces similar challenges, where the failure to extract all the trapped fluid can result in isotopic fractionation, and samples in excess of 500 mg are required. Our new method combines the strengths of these published thermal and crushing methods using continuous-flow isotope ratio analytical techniques. Our method combines relatively low-temperature (~250°C) thermal decrepitation with cryogenic trapping across a switching valve sample loop. In brief, ~20 mg carbonate samples are dried (75°C for >1 hour) and heated (250°C for >1 hour) in a quartz sample chamber under a continuously flowing stream of ultra-high purity helium. Heating of the sample chamber is achieved by use of a tube furnace. Fluids released during the heating step are trapped in a coiled stainless steel cold trap (~ -98°C) serving as the sample loop in a 6-way switching valve. Trapped fluids are subsequently injected into a high-temperature conversion elemental analyzer by switching the valve and rapidly thawing the trap. This approach yielded accurate and precise measurements of injected liquid water IAEA reference materials (GISP; SMOW2; SLAP2) for both hydrogen and oxygen isotopic compositions. Blanking tests performed on the extraction line demonstrate extremely low line-blank peak heights (<50mv). Our tests also demonstrate that complete recovery of liquid water is possible and that a minimum quantity of ~100nL water was required. In contrast to liquid water analyses, carbonate inclusion waters gave highly variable results. As plenty of signal was produced from relatively small sample sizes (~20 mg), the observed isotopic variation most likely reflects fractionation during fluid extraction, or natural isotopic variability. Additional tests and modifications to the extraction procedure are in progress, using a recently collected New Zealand stalagmite from a West Coast cave (DOC collection permit WC-27462-GEO). U-Th age data will accompany a paleoclimate record from this stalagmite obtained using standard carbonate analytical techniques, and compared to the results from our new fluid inclusion analyses.

Controls on the distribution and isotopic composition of helium in deep ground-water flows

USGS Publications Warehouse

Zhao, X.; Fritzel, T.L.B.; Quinodoz, H.A.M.; Bethke, C.M.; Torgersen, T.

1998-01-01

The distribution and isotopic composition of helium in sedimentary basins can be used to interpret the ages of very old ground waters. The piston-flow model commonly used in such interpretation, how ever, does not account for several important factors and as such works well only in very simple flow regimes. In this study of helium transport in a hypothetical sedimentary basin, we develop a numerical model that accounts for the magnitude and distribution of the basal helium flux, hydrodynamic dispersion, and complexities in flow regimes such as subregional flow cells. The modeling shows that these factors exert strong controls on the helium distribution and isotopic composition. The simulations may provide a basis for more accurate interpretations of observed helium concentrations and isotopic ratios in sedimentary basins.

Magma mixing and the generation of isotopically juvenile silicic magma at Yellowstone caldera inferred from coupling 238U–230Th ages with trace elements and Hf and O isotopes in zircon and Pb isotopes in sanidine

USGS Publications Warehouse

Stelten, Mark E.; Cooper, Kari M.; Vazquez, Jorge A.; Reid, Mary R.; Barfod, Gry H.; Wimpenny, Josh; Yin, Qing-Zhu

2013-01-01

The nature of compositional heterogeneity within large silicic magma bodies has important implications for how silicic reservoirs are assembled and evolve through time. We examine compositional heterogeneity in the youngest (~170 to 70 ka) post-caldera volcanism at Yellowstone caldera, the Central Plateau Member (CPM) rhyolites, as a case study. We compare 238U–230Th age, trace-element, and Hf isotopic data from zircons, and major-element, Ba, and Pb isotopic data from sanidines hosted in two CPM rhyolites (Hayden Valley and Solfatara Plateau flows) and one extracaldera rhyolite (Gibbon River flow), all of which erupted near the caldera margin ca. 100 ka. The Hayden Valley flow hosts two zircon populations and one sanidine population that are consistent with residence in the CPM reservoir. The Gibbon River flow hosts one zircon population that is compositionally distinct from Hayden Valley flow zircons. The Solfatara Plateau flow contains multiple sanidine populations and all three zircon populations found in the Hayden Valley and Gibbon River flows, demonstrating that the Solfatara Plateau flow formed by mixing extracaldera magma with the margin of the CPM reservoir. This process highlights the dynamic nature of magmatic interactions at the margins of large silicic reservoirs. More generally, Hf isotopic data from the CPM zircons provide the first direct evidence for isotopically juvenile magmas contributing mass to the youngest post-caldera magmatic system and demonstrate that the sources contributing magma to the CPM reservoir were heterogeneous in 176Hf/177Hf at ca. 100 ka. Thus, the limited compositional variability of CPM glasses reflects homogenization occurring within the CPM reservoir, not a homogeneous source.

Estimating ground-water exchange with lakes using water-budget and chemical mass-balance approaches for ten lakes in ridge areas of Polk and Highlands counties, Florida

USGS Publications Warehouse

Sacks, L.A.; Swancar, Amy; Lee, T.M.

1998-01-01

Water budget and chemical mass-balance approaches were used to estimate ground-water exchange with 10 lakes in ridge areas of Polk and Highlands Counties, Florida. At each lake, heads were monitored in the surficial aquifer system and deeper Upper Floridan aquifer, lake stage and rainfall were measured continuously, and lakes and wells were sampled three times between October 1995 and December 1996. The water-budget approach computes net ground-water flow (ground-water inflow minus outflow) as the residual of the monthly waterbudget equation. Net ground-water flow varied seasonally at each of the 10 lakes, and was notably different between lakes, illustrating short-term differences in ground-water fluxes. Monthly patterns in net ground-water flow were related to monthly patterns of other hydrologic variables such as rainfall, ground-water flow patterns, and head differences between the lake and the Upper Floridan aquifer. The chemical mass-balance approach combines the water budget and solute or isotope mass-balance equations, and assumes steady-state conditions. Naturally occurring tracers that were analyzed for include calcium, magnesium, sodium, potassium, chloride, and bromide, the isotopes deuterium and oxygen-18. Chloride and sodium were the most successful solute tracers; however, their concentrations in ground water typically varied spatially, and in places were similar to that in lake water, limiting their sensitivity as tracers. In contrast, the isotopes were more robust tracers because the isotopic composition of ground water was relatively uniform and was distinctly different from the lake water. Groundwater inflow computed using the chemical massbalance method varied significantly between lakes, and ranged from less than 10 to more than 150 inches per year. Both water-budget and chemical mass-balance approaches had limitations, but the multiple lines of evidence gained using both approaches improved the understanding of the role of ground water in the water budget of the lakes.

Field-based stable isotope analysis of carbon dioxide by mid-infrared laser spectroscopy for carbon capture and storage monitoring.

PubMed

van Geldern, Robert; Nowak, Martin E; Zimmer, Martin; Szizybalski, Alexandra; Myrttinen, Anssi; Barth, Johannes A C; Jost, Hans-Jürg

2014-12-16

A newly developed isotope ratio laser spectrometer for CO2 analyses has been tested during a tracer experiment at the Ketzin pilot site (northern Germany) for CO2 storage. For the experiment, 500 tons of CO2 from a natural CO2 reservoir was injected in supercritical state into the reservoir. The carbon stable isotope value (δ(13)C) of injected CO2 was significantly different from background values. In order to observe the breakthrough of the isotope tracer continuously, the new instruments were connected to a stainless steel riser tube that was installed in an observation well. The laser instrument is based on tunable laser direct absorption in the mid-infrared. The instrument recorded a continuous 10 day carbon stable isotope data set with 30 min resolution directly on-site in a field-based laboratory container during a tracer experiment. To test the instruments performance and accuracy the monitoring campaign was accompanied by daily CO2 sampling for laboratory analyses with isotope ratio mass spectrometry (IRMS). The carbon stable isotope ratios measured by conventional IRMS technique and by the new mid-infrared laser spectrometer agree remarkably well within analytical precision. This proves the capability of the new mid-infrared direct absorption technique to measure high precision and accurate real-time stable isotope data directly in the field. The laser spectroscopy data revealed for the first time a prior to this experiment unknown, intensive dynamic with fast changing δ(13)C values. The arrival pattern of the tracer suggest that the observed fluctuations were probably caused by migration along separate and distinct preferential flow paths between injection well and observation well. The short-term variances as observed in this study might have been missed during previous works that applied laboratory-based IRMS analysis. The new technique could contribute to a better tracing of the migration of the underground CO2 plume and help to ensure the long-term integrity of the reservoir.

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

NASA Astrophysics Data System (ADS)

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

2007-11-01

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

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.

Water storages and fluxes within the small watershed in continuous permafrost zone

NASA Astrophysics Data System (ADS)

Lebedeva, Liudmila; Makarieva, Olga; Nesterova, Nataliya; Meyer, Hanno; Efremov, Vladimir; Ogonerov, Vasiliy

2017-04-01

It is widely accepted that the main source of river runoff in continuous permafrost zone is surface flow and the flow in the seasonally thawing layer. Although the existence of taliks (a layer of year-round unfrozen ground that can be found in permafrost areas) is acknowledged they are usually not considered in the analysis of streamwater sources and in hydrological modelling approaches. The study aims at assessing the possible river sources in small permafrost basin and their contribution to streamflow with special attention to hydrological role of taliks. The study is based on field surveys in 2015 and 2016, the analysis for stable isotopes (δD and δ18O) and the application of a simple mixing model. The Shestakovka River (basin area 170 km2) is a left tributary of the Lena River in the vicinity of Yakutsk city, Eastern Siberia. The climate is dry and continental. Mean air temperature is -9.5°C, precipitation is 240 mm/year, annual runoff depth - 24 mm. Dominant landscapes are pine forest (47% of the watershed area), larch-birch forest (38%) and bogs (14%). Suprapermafrost talik with an area of 58 000 m2 was found on the slope covered by the pine forest in 1980s. Field studies showed that the summer flow depth in talik is 60 mm. In 2015 and 2016 264 water samples from river streams, lakes, snow, rain, suprapermafrost groundwater and ground ice were taken in the Shestakovka River watershed and analyzed for stable isotopes composition. Snow has the lightest isotopic composition that varies between -230 and -275‰ in δD and between -30 and - 37‰ in δ18O. Rain water is on average most enriched in δD (-70…-150‰) and in δ18O (-6…-19‰). River water and surface flow in bogs are depleted during snowmelt (April - May) and enriched at the end of the summer. δ18O and δD concentrations in lake water vary from -20‰ and -185‰ in snowmelt period to -10‰ and -110‰ in July and August respectively. Suprapermafrost groundwater in two taliks has δ18O values between -19‰ and -24‰, δD values between -150‰ and -175‰. Isotopic concentrations of groundwater are stable through the year. Field surveys and the analysis of isotopic concentrations showed that some surface flow occurs only in bogs. Subsurface flow forms in larch forests in seasonally thawing layer in July and August. Dry sandy deposits at some slopes in pine forests do not produce surface or shallow subsurface flow but could contain deeper groundwater in taliks. The results of simple two-component mixing model application has shown that in 2015 snowmelt water contributed only 54-70% of streamflow while 30-46% of freshet was supplied by pre-event water. In our opinion suprapermafrost talik water is the most feasible source of the pre-event water. The presence of groundwater in streamflow is indirectly confirmed by the fact that the correlation of total river runoff with last-year precipitation is stronger than with this-year precipitation. It suggests that large and slow water storages in the basins are important chain of hydrological cycle. Taliks could potentially be a significant source for the small rivers in permafrost environments that is not reflected in current process understanding and modelling approaches. The study is partially supported by Russian foundation of basic research, projects No 15-05-08144 and No 16-35-50151.

Monitoring Subsurface Fluid Flow Using Perfluorocarbon Tracers: Another Tool Potentially Available for Subsurface Fluid Flow Assessments

EPA Pesticide Factsheets

Perfluorocarbon Tracers (PFTs) Complement stable Isotopes and Geochemistry for Verifying, Assessing or Modeling Fluid Flow. Geochemistry, Isotopes and PFT’s complement Geophysics to monitor and verify plume movement, leakage to shallow aquifers or surface

Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

PubMed

Cretnik, Stefan; Bernstein, Anat; Shouakar-Stash, Orfan; Löffler, Frank; Elsner, Martin

2014-05-20

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms.

Carbon isotope analysis of dissolved organic carbon in fresh and saline (NaCl) water via continuous flow cavity ring-down spectroscopy following wet chemical oxidation

USGS Publications Warehouse

Conaway, Christopher; Thomas, Randal B.; Saad, Nabil; Thordsen, James J.; Kharaka, Yousif K.

2015-01-01

This work examines the performance and limitations of a wet chemical oxidation carbon analyser interfaced with a cavity ring-down spectrometer (WCO-CRDS) in a continuous flow (CF) configuration for measuring δ13C of dissolved organic carbon (δ13C-DOC) in natural water samples. Low-chloride matrix (<5 g Cl/L) DOC solutions were analysed with as little as 2.5 mg C/L in a 9 mL aliquot with a precision of 0.5 ‰. In high-chloride matrix (10–100 g Cl/L) DOC solutions, bias towards lighter δ13C-DOC was observed because of incomplete oxidation despite using high-concentration oxidant, extended reaction time, or post-wet chemical oxidation gas-phase combustion. However, through a combination of dilution, chloride removal, and increasing the oxidant:sample ratio, high-salinity samples with sufficient DOC (>22.5 µg C/aliquot) may be analysed. The WCO-CRDS approach requires more total carbon (µg C/aliquot) than conventional CF-isotope ratio mass spectrometer, but is nonetheless applicable to a wide range of DOC concentration and water types, including brackish water, produced water, and basinal brines.

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

Hepatoblastoma Biology Using Isotope Ratio Mass Spectrometry: Utility of a Unique Technique for the Analysis of Oncological Specimens.

PubMed

Taran, Katarzyna; Frączek, Tomasz; Sitkiewicz, Anna; Sikora-Szubert, Anita; Kobos, Józef; Paneth, Piotr

2016-07-07

Hepatoblastoma is the most common primary liver tumor in children. However, it occurs rarely, with an incidence of 0.5-1.5 cases per million children. There is no clear explanation of the relationship between clinicopathologic features, therapy, and outcome in hepatoblastoma cases, so far. One of the most widely accepted prognostic factors in hepatoblastoma is histology of the tumor. The aim of the study was to determine the potential differences in biology of hepatoblastoma histological subtypes at the atomic level using the unique method of isotope ratio mass spectrometry, which is especially valuable in examination of small groups of biological samples. Twenty-four measurements of nitrogen stable isotope ratio, carbon stable isotope ratio and total carbon to nitrogen mass ratio in fetal and embryonal hepatoblastoma tissue were performed using a Sercon 20-22 Continuous Flow Isotope Ratio Mass Spectrometer (CF-IRMS) coupled with a Sercon SL elemental analyzer for simultaneous carbon-nitrogen-sulfur (NCS) analysis. A difference of about 1.781‰ in stable nitrogen isotope 15N/14N ratio was found between examined hepatoblastoma histological subtypes. The prognosis in liver tumors cases in children may be challenging particularly because of the lack of versatile methods of its evaluation. Isotope ratio mass spectrometry allows one to determine the difference between hepatoblastoma histological subtypes and clearly indicates the cases with the best outcome.

Toothpaste lava from the Barren Island volcano (Andaman Sea)

NASA Astrophysics Data System (ADS)

Sheth, Hetu C.; Ray, Jyotiranjan S.; Kumar, Alok; Bhutani, Rajneesh; Awasthi, Neeraj

2011-04-01

Toothpaste lava is a basaltic lava flow type transitional between pahoehoe and aa and has been described from Paricutin, Kilauea and Etna volcanoes. Here we describe a spectacular example of toothpaste lava, forming part of a recent (possibly 1994-95) aa flow on the active volcano of Barren Island (Andaman Sea). This flow of subalkalic basalt shows abundant squeeze-ups of viscous toothpasate lava near its entry into the sea. The squeeze-ups are sheets and slabs, up to several meters across and tens of centimeters thick, extruded from boccas. They are often prominently curved, have striated upper surfaces with close-spaced, en echelon linear ridges and grooves, broad wave-like undulations perpendicular to the striations, and sometimes, clefts. Textural, geochemical, and Sr-Nd isotopic data on the squeeze-ups and the exposed aa flow core indicate very crystal-rich, viscous, and isotopically very homogeneous lava. We envisage that a greatly reduced speed of this viscous flow at the coastline, possibly aided by a shallowing of the basal slope, led to lateral spreading of the flow, which caused tension in its upper parts. This, with continued (albeit dwindling) lava supply at the back, led to widespread tearing of the flow surface and extrusion of the squeeze-ups. The larger slabs, while extruding in a plastic condition, curved under their own weight, whereas their surfaces experienced brittle deformation, forming the en echelon grooves. The extruded, detached, and rotated sheets and slabs were carried forward for some distance atop the very slowly advancing aa core, before the flow solidified.

Ca, Sr, O and D isotope approach to defining the chemical evolution of hydrothermal fluids: example from Long Valley, CA, USA

USGS Publications Warehouse

Brown, Shaun T.; Kennedy, B. Mack; DePaolo, Donald J.; Hurwitz, Shaul; Evans, William C.

2013-01-01

We present chemical and isotopic data for fluids, minerals and rocks from the Long Valley meteoric-hydrothermal system. The samples encompass the presumed hydrothermal upwelling zone in the west moat of the caldera, the Casa Diablo geothermal field, and a series of wells defining a nearly linear, ∼16 km long, west-to-east trend along the likely fluid flow path. Fluid samples were analyzed for the isotopes of water, Sr, and Ca, the concentrations of major cations and anions, alkalinity, and total CO2. Water isotope data conform to trends documented in earlier studies, interpreted as indicating a single hydrothermal fluid mixing with local groundwater. Sr isotopes show subtle changes along the flow path, which requires rapid fluid flow and minimal reaction between the channelized fluids and the wallrocks. Sr and O isotopes are used to calculate fracture spacing using a dual porosity model. Calculated fracture spacing and temperature data for hydrothermal fluids indicate the system is (approximately) at steady-state. Correlated variations among total CO2, and the concentration and isotopic composition of Ca suggest progressive fluid degassing (loss of CO2), which drives calcite precipitation as the fluid flows west-to-east and cools. The shifts in Ca isotopes require that calcite precipitated at temperatures of 150–180 °C is fractionated by ca. −0.3‰ to −0.5‰ relative to aqueous species. Our data are the first evidence that Ca isotopes undergo kinetic fractionation at high temperatures (>100 °C) and can be used to trace calcite precipitation along hydrothermal fluid flow paths.

Rate dependent fractionation of sulfur isotopes in through-flowing systems

NASA Astrophysics Data System (ADS)

Giannetta, M.; Sanford, R. A.; Druhan, J. L.

2017-12-01

The fidelity of reactive transport models in quantifying microbial activity in the subsurface is often improved through the use stable isotopes. However, the accuracy of current predictions for microbially mediated isotope fractionations within open through-flowing systems typically depends on nutrient availability. This disparity arises from the common application of a single `effective' fractionation factor assigned to a given system, despite extensive evidence for variability in the fractionation factor between eutrophic environments and many naturally occurring, nutrient-limited environments. Here, we demonstrate a reactive transport model with the capacity to simulate a variable fractionation factor over a range of microbially mediated reduction rates and constrain the model with experimental data for nutrient limited conditions. Two coupled isotope-specific Monod rate laws for 32S and 34S, constructed to quantify microbial sulfate reduction and predict associated S isotope partitioning, were parameterized using a series of batch reactor experiments designed to minimize microbial growth. In the current study, we implement these parameterized isotope-specific rate laws within an open, through-flowing system to predict variable fractionation with distance as a function of sulfate reduction rate. These predictions are tested through a supporting laboratory experiment consisting of a flow-through column packed with homogenous porous media inoculated with the same species of sulfate reducing bacteria used in the previous batch reactors, Desulfovibrio vulgaris. The collective results of batch reactor and flow-through column experiments support a significant improvement for S isotope predictions in isotope-sensitive multi-component reactive transport models through treatment of rate-dependent fractionation. Such an update to the model will better equip reactive transport software for isotope informed characterization of microbial activity within energy and nutrient limited environments.

Continuous flow stable isotope methods for study of δ13C fractionation during halomethane production and degradation

USGS Publications Warehouse

Kalin, Robert M.; Hamilton, John T.G.; Harper, David B.; Miller, Laurence G.; Lamb, Clare; Kennedy, James T.; Downey, Angela; McCauley, Sean; Goldstein, Allen H.

2001-01-01

Gas chromatography/mass spectrometry/isotope ratio mass spectrometry (GC/MS/IRMS) methods for δ13C measurement of the halomethanes CH3Cl, CH3Br, CH3I and methanethiol (CH3SH) during studies of their biological production, biological degradation, and abiotic reactions are presented. Optimisation of gas chromatographic parameters allowed the identification and quantification of CO2, O2, CH3Cl, CH3Br, CH3I and CH3SH from a single sample, and also the concurrent measurement of δ13C for each of the halomethanes and methanethiol. Precision of δ13C measurements for halomethane standards decreased (±0.3, ±0.5 and ±1.3‰) with increasing mass (CH3Cl, CH3Br, CH3I, respectively). Given that carbon isotope effects during biological production, biological degradation and some chemical (abiotic) reactions can be as much as 100‰, stable isotope analysis offers a precise method to study the global sources and sinks of these halogenated compounds that are of considerable importance to our understanding of stratospheric ozone destruction. 

High Resolution Continuous Flow Analysis System for Polar Ice Cores

NASA Astrophysics Data System (ADS)

Dallmayr, Remi; Azuma, Kumiko; Yamada, Hironobu; Kjær, Helle Astrid; Vallelonga, Paul; Azuma, Nobuhiko; Takata, Morimasa

2014-05-01

In the last decades, Continuous Flow Analysis (CFA) technology for ice core analyses has been developed to reconstruct the past changes of the climate system 1), 2). Compared with traditional analyses of discrete samples, a CFA system offers much faster and higher depth resolution analyses. It also generates a decontaminated sample stream without time-consuming sample processing procedure by using the inner area of an ice-core sample.. The CFA system that we have been developing is currently able to continuously measure stable water isotopes 3) and electrolytic conductivity, as well as to collect discrete samples for the both inner and outer areas with variable depth resolutions. Chemistry analyses4) and methane-gas analysis 5) are planned to be added using the continuous water stream system 5). In order to optimize the resolution of the current system with minimal sample volumes necessary for different analyses, our CFA system typically melts an ice core at 1.6 cm/min. Instead of using a wire position encoder with typical 1mm positioning resolution 6), we decided to use a high-accuracy CCD Laser displacement sensor (LKG-G505, Keyence). At the 1.6 cm/min melt rate, the positioning resolution was increased to 0.27mm. Also, the mixing volume that occurs in our open split debubbler is regulated using its weight. The overflow pumping rate is smoothly PID controlled to maintain the weight as low as possible, while keeping a safety buffer of water to avoid air bubbles downstream. To evaluate the system's depth-resolution, we will present the preliminary data of electrolytic conductivity obtained by melting 12 bags of the North Greenland Eemian Ice Drilling (NEEM) ice core. The samples correspond to different climate intervals (Greenland Stadial 21, 22, Greenland Stadial 5, Greenland Interstadial 5, Greenland Interstadial 7, Greenland Stadial 8). We will present results for the Greenland Stadial -8, whose depths and ages are between 1723.7 and 1724.8 meters, and 35.520 to 35.636 kyr b2k 7), respectively. The results show the conductivity measured upstream and downstream of the debubbler. We will calculate the depth resolution of our system and compare it with earlier studies. 1) Bigler at al, "Optimization of High-Resolution Continuous Flow Analysis For Transient Climate Signals in Ice Cores". Environ. Sci. Technol. 2011, 45, 4483-4489 2) Kaufmann et al, "An Improved Continuous Flow Analysis System for High Resolution Field Measurements on Ice Cores". Environmental Environ. Sci. Technol. 2008, 42, 8044-8050 3) Gkinis, V., T. J. Popp, S. J. Johnsen and T, Blunier, 2010: A continuous stream flash evaporator for the calibration of an IR cavity ring down spectrometer for the isotopic analysis of water. Isotopes in Environmental and Health Studies, 46(4), 463-475. 4) McConnell et al, "Continuous ice-core chemical analyses using inductively coupled plasma mass spectrometry. Environ. Sci. Technol. 2002, 36, 7-11 5) Rhodes et al, "Continuous methane measurements from a late Holocene Greenland ice core : Atmospheric and in-situ signals" Earth and Planetary Science Letters. 2013, 368, 9-19 6) Breton et al, "Quantifying Signal Dispersion in a Hybrid Ice Core Melting System". Environ. Sci. Technol. 2012, 46, 11922-11928 7) Rasmussen et al, " A first chronology for the NEEM ice core". Climate of the Past. 2013, 9, 2967--3013

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.

Calibration strategies for the determination of stable carbon absolute isotope ratios in a glycine candidate reference material by elemental analyser-isotope ratio mass spectrometry.

PubMed

Dunn, Philip J H; Malinovsky, Dmitry; Goenaga-Infante, Heidi

2015-04-01

We report a methodology for the determination of the stable carbon absolute isotope ratio of a glycine candidate reference material with natural carbon isotopic composition using EA-IRMS. For the first time, stable carbon absolute isotope ratios have been reported using continuous flow rather than dual inlet isotope ratio mass spectrometry. Also for the first time, a calibration strategy based on the use of synthetic mixtures gravimetrically prepared from well characterised, highly (13)C-enriched and (13)C-depleted glycines was developed for EA-IRMS calibration and generation of absolute carbon isotope ratio values traceable to the SI through calibration standards of known purity. A second calibration strategy based on converting the more typically determined delta values on the Vienna PeeDee Belemnite (VPDB) scale using literature values for the absolute carbon isotope ratio of VPDB itself was used for comparison. Both calibration approaches provided results consistent with those previously reported for the same natural glycine using MC-ICP-MS; absolute carbon ratios of 10,649 × 10(-6) with an expanded uncertainty (k = 2) of 24 × 10(-6) and 10,646 × 10(-6) with an expanded uncertainty (k = 2) of 88 × 10(-6) were obtained, respectively. The absolute carbon isotope ratio of the VPDB standard was found to be 11,115 × 10(-6) with an expanded uncertainty (k = 2) of 27 × 10(-6), which is in excellent agreement with previously published values.

Water isotopic ratios from a continuously melted ice core sample

NASA Astrophysics Data System (ADS)

Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Johnsen, S. J.

2011-06-01

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We build an interface between an Infra Red Cavity Ring Down Spectrometer (IR-CRDS) and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100 % efficiency in a home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on humidity levels. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1 ‰ and 0.5 ‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the framework of the NEEM deep ice core drilling project in Greenland, during the 2010 field season.

Water isotopic ratios from a continuously melted ice core sample

NASA Astrophysics Data System (ADS)

Gkinis, V.; Popp, T. J.; Blunier, T.; Bigler, M.; Schüpbach, S.; Kettner, E.; Johnsen, S. J.

2011-11-01

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW-SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

Seasonal variability of oxygen and hydrogen isotopes in a wetland system of the Yunnan-Guizhou Plateau, southwest China: a quantitative assessment of groundwater inflow fluxes

NASA Astrophysics Data System (ADS)

Cao, Xingxing; Wu, Pan; Zhou, Shaoqi; Han, Zhiwei; Tu, Han; Zhang, Shui

2018-02-01

The Caohai Wetland serves as an important ecosystem on the Yunnan-Guizhou Plateau and as a nationally important nature reserve for migratory birds in China. In this study, surface water, groundwater and wetland water were collected for the measurement of environmental isotopes to reveal the seasonal variability of oxygen and hydrogen isotopes (δ18O, δD), sources of water, and groundwater inflow fluxes. Results showed that surface water and groundwater are of meteoric origin. The isotopes in samples of wetland water were well mixed vertically in seasons of both high-flow (September) and low-flow (April); however, marked seasonal and spatial variations were observed. During the high-flow season, the isotopic composition in surface wetland water varied from -97.13 to -41.73‰ for δD and from -13.17 to -4.70‰ for δ18O. The composition of stable isotopes in the eastern region of this wetland was lower than in the western region. These may have been influenced by uneven evaporation caused by the distribution of aquatic vegetation. During the low-flow season, δD and δ18O in the more open water with dead aquatic vegetation ranged from -37.11 to -11.77‰, and from -4.25 to -0.08‰, respectively. This may result from high evaporation rates in this season with the lowest atmospheric humidity. Groundwater fluxes were calculated by mass transfer and isotope mass balance approaches, suggesting that the water sources of the Caohai Wetland were mainly from groundwater in the high-flow season, while the groundwater has a smaller contribution to wetland water during the low-flow season.

Discrimination factors of carbon and nitrogen stable isotopes from diet to hair and scat in captive tigers (Panthera tigris) and snow leopards (Uncia uncia).

PubMed

Montanari, Shaena; Amato, George

2015-06-15

In order to use stable isotope ratio values obtained from wild animal tissues, we must accurately calculate the differences in isotope ratios between diet and consumer (δtissue - δdiet). These values, called trophic discrimination factors (TDFs, denoted with ∆), are necessary for stable isotope ecology studies and are best calculated in controlled environments. Scat, hair, and diet samples were collected from captive tigers (n = 8) and snow leopards (n = 10) at the Bronx Zoo. The isotope ratios of carbon and nitrogen, the two most commonly used in ecological studies, of the samples were measured by continuous-flow isotope ratio mass spectrometry. The trophic discrimination factors were calculated for both carbon (δ(13)C values) and nitrogen (δ(15)N values). It was found that the only significant TDFs in this study were diet-hair, ∆(13)CHair, for snow leopards (5.97 ± 1.25‰) and tigers (6.45 ± 0.54‰), and diet-scat, ∆(15)NScat, in snow leopards (2.49 ± 1.30‰). The other mean isotope ratios were not significantly different from that of the premixed feline diet. The ∆(15)NHair values for both species were unusually low, potentially due to the protein content and quality of the feline diet. The discrimination factors of the stable isotopes of carbon and nitrogen calculated in this study can be applied to ecological studies of wild, non-captive terrestrial mammals. The effect of protein quality in isotope discrimination is also worthy of further investigation to better understand variation in TDFs. Carnivore scat is shown to be a valuable material for isotopic analysis. Copyright © 2015 John Wiley & Sons, Ltd.

Comparison of ground-water flow model particle-tracking results and isotopic data in the Mojave River ground-water basin, southern California, USA

USGS Publications Warehouse

Izbicki, John A.; Stamos, Christina L.; Nishikawa, Tracy; Martin, Peter

2004-01-01

Flow-path and time-of-travel results for the Mojave River ground-water basin, southern California, calculated using the ground-water flow model MODFLOW and particle-tracking model MODPATH were similar to flow path and time-of-travel interpretations derived from delta-deuterium and carbon-14 data. Model and isotopic data both show short flow paths and young ground-water ages throughout the floodplain aquifer along most the Mojave River. Longer flow paths and older ground-water ages as great as 10,000 years before present were measured and simulated in the floodplain aquifer near the Mojave Valley. Model and isotopic data also show movement of water between the floodplain and regional aquifer and subsequent discharge of water from the river to dry lakes in some areas. It was not possible to simulate the isotopic composition of ground-water in the regional aquifer away from the front of the San Gabriel and San Bernardino Mountains - because recharge in these areas does not occur under the present-day climatic conditions used for calibration of the model.

Using water vapor isotopes to examine evapotranspiration dynamics in corn and miscanthus reveals challenges to the technique as well as seasonal differences between crops.

NASA Astrophysics Data System (ADS)

Miller, J. N.; Bernacchi, C.

2016-12-01

Second-generation biofuel crops are being planted at an increasing extent around the globe. Changing land use from common field crops to perennial biofuel crops such as miscanthus or switchgrass is expected to alter ecohydrology via changes in evapotranspiration (ET). However, the direction in which evapotranspiration will shift, either partitioning more moisture through soil evaporation (E) or through plant transpiration (T) is uncertain. To investigate how land conversion from maize to miscanthus affects ET partitioning we measured the isotopic composition of water vapor via continuous air sampling. We obtained continuous diurnal measurements of δ2H and δ18O for miscanthus and maize on multiple days over the course of the growing season. Water vapor isotopes drawn from two heights were measured at 2 Hz using a cavity ringdown spectrometer and partitioned into components of E and T using a simple mixing equation. Partitioning was also accomplished with a combination of sap flow sensors and soil lysimeters. Preliminary results reveal that while daily transpiration fraction can be strongly influenced by meteorological events, the whole season transpiration fraction dominates variations in ET in miscanthus fields more so than in fields of maize.

Carbon and Hydrogen Isotope Measurements of Alcohols and Organic Acids by Online Pyroprobe-GC-IRMS

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.

2012-01-01

The detection of methane in the atmosphere of Mars, combined with evidence showing widespread water-rock interaction during martian history, suggests that the production of methane on Mars may be the result of mineral surface-catalyzed CO2 and or CO reduction during Fisher-Tropsch Type (FTT) reactions. A better understanding of these reaction pathways and corresponding C and H isotope fractionations is critical to deciphering the synthesis of organic compounds produced under abiotic hydrothermal conditions. Described here is a technique for the extraction and analysis of both C and H isotopes from alcohols (C1-C4) and organic acids (C1-C6). This work is meant to provide a "proof of concept" for making meaningful isotope measurements on complex mixtures of solid-phase hydrocarbons and other intermediary products produced during high-temperature and high-pressure synthesis on mineral-catalyzed surfaces. These analyses are conducted entirely "on-line" utilizing a CDS model 5000 Pyroprobe connected to a Thermo Trace GC Ultra that is interfaced with a Thermo MAT 253 isotope ratio mass spectrometer operating in continuous flow mode. Also, this technique is designed to carry a split of the GC-separated product to a DSQ II quadrupole mass spectrometer as a means of making semi-quantitative compositional measurements. Therefore, both chemical and isotopic measurements can be carried out on the same sample.

Progress in tropical isotope dendroclimatology

NASA Astrophysics Data System (ADS)

Evans, M. N.; Schrag, D. P.; Poussart, P. F.; Anchukaitis, K. J.

2005-12-01

The terrestrial tropics remain an important gap in the growing high resolution proxy network used to characterize the mean state and variability of the hydrological cycle. Here we review early efforts to develop a new class of proxy paleorainfall/humidity indicators using intraseasonal to interannual-resolution stable isotope data from tropical trees. The approach invokes a recently published model of oxygen isotopic composition of alpha-cellulose, rapid methods for cellulose extraction from raw wood, and continuous flow isotope ratio mass spectrometry to develop proxy chronological, rainfall and growth rate estimates from tropical trees, even those lacking annual rings. Isotopically-derived age models may be confirmed for modern intervals using trees of known age, radiocarbon measurements, direct measurements of tree diameter, and time series replication. Studies are now underway at a number of laboratories on samples from Costa Rica, northwestern coastal Peru, Indonesia, Thailand, New Guinea, Paraguay, Brazil, India, and the South American Altiplano. Improved sample extraction chemistry and online pyrolysis techniques should increase sample throughput, precision, and time series replication. Statistical calibration together with simple forward modeling based on the well-observed modern period can provide for objective interpretation of the data. Ultimately, replicated data series with well-defined uncertainties can be entered into multiproxy efforts to define aspects of tropical hydrological variability associated with ENSO, the meridional overturning circulation, and the monsoon systems.

High power gas laser - Applications and future developments

NASA Technical Reports Server (NTRS)

Hertzberg, A.

1977-01-01

Fast flow can be used to create the population inversion required for lasing action, or can be used to improve laser operation, for example by the removal of waste heat. It is pointed out that at the present time all lasers which are capable of continuous high-average power employ flow as an indispensable aspect of operation. High power laser systems are discussed, taking into account the gasdynamic laser, the HF supersonic diffusion laser, and electric discharge lasers. Aerodynamics and high power lasers are considered, giving attention to flow effects in high-power gas lasers, aerodynamic windows and beam manipulation, and the Venus machine. Applications of high-power laser technology reported are related to laser material working, the employment of the laser in controlled fusion machines, laser isotope separation and photochemistry, and laser power transmission.

Fluid flow in deforming media: interpreting stable isotope signatures of marbles

NASA Astrophysics Data System (ADS)

Bond, C. E.

2016-12-01

Fluid flow in the crust is controlled by permeable networks. These networks can be created and destroyed dynamically during rock deformation. Rock deformation is therefore critical in controlling fluid pathways in the crust and hence the location of mineral and other resources. Here, evidence for deformation-enhanced fluid infiltration shows that a range of deformation mechanisms control fluid flow and chemical and isotopic equilibration. The results attest to localised fluid infiltration within a single metamorphic terrain (12km) over a range of metamorphic grades; ecologite- blueschist to greenschist. For fluid infiltrating marbles during ductile deformation, chemical and isotopic signatures are now homogenous; whilst fluid infiltration associated with brittle deformation results in chemical and isotopic heterogeneity at a microscale. The findings demonstrate how ductile deformation enhances equilibration of δ18O at a grain scale whilst brittle deformation does not. The control of deformation mechanisms in equilibrating isotopic and chemical heterogeneities have implications for the understanding of fluid-rock interaction in the crust. Interpretation of bulk stable isotope data, particularly in the use of isotope profiles to determine fluid fluxes into relatively impermeable units that have been deformed need to be used with care when trying to determine fluid fluxes and infiltration mechanisms.

Inter-laboratory calibration of new silver orthophosphate comparison materials for the stable oxygen isotope analysis of phosphates.

PubMed

Halas, Stanislaw; Skrzypek, Grzegorz; Meier-Augenstein, Wolfram; Pelc, Andrzej; Kemp, Helen F

2011-03-15

Stable oxygen isotope compositions (δ(18)O values) of two commercial and one synthesized silver orthophosphate reagents have been determined on the VSMOW scale. The analyses were carried out in three different laboratories: lab (1) applying off-line oxygen extraction in the form of CO(2) which was analyzed on a dual inlet and triple collector isotope ratio mass spectrometer, while labs (2) and (3) employed an isotope ratio mass spectrometer coupled to a high-temperature conversion/elemental analyzer (TC/EA) where Ag(3)PO(4) samples were analyzed as CO in continuous flow mode. The δ(18)O values for the proposed new comparison materials were linked to the generally accepted δ(18)O values for Vennemann's TU-1 and TU-2 standards as well as for Ag(3)PO(4) extracted from NBS120c. The weighted average δ(18)O(VSMOW) values for the new comparison materials UMCS-1, UMCS-2 and AGPO-SCRI were determined to be + 32.60 (± 0.12), + 19.40 (± 0.12) and + 14.58 (± 0.13)‰, respectively. Copyright © 2011 John Wiley & Sons, Ltd.

Identifying Source Water and Flow Paths in a Semi-Arid Watershed

NASA Astrophysics Data System (ADS)

Gulvin, C. J.; Miller, S. N.

2016-12-01

Processes controlling water delivery to perennial streams in the semi-arid mountain west are poorly understood, yet necessary to characterize water distribution across the landscape and better protect and manage diminishing water resources. Stream water chemistry profiling and hydrograph separation using stable isotopes can help identify source waters. Weekly stream water samples tested for stable water isotope fractionations, and major cations and anions at seven sites collocated with continuously recording stream depth gauges within a small watershed in southeastern Wyoming is a necessary first-step to identifying seasonally changing source water and flow paths. Sample results will help establish appropriate end members for a mixing analysis, as well as, characterize flow path heterogeneity, transit time distributions, and landscape selectively features. Hourly stream sampling during late-summer thunderstorms and rapid spring melt will help demonstrate if and how stream discharge change is affected by the two different events. Soil water and water extracted from tree xylem will help resolve how water is partitioned in the first 10m of the subsurface. In the face of land use change and a growing demand for water in the area, understanding how the water in small mountain streams is sustained is crucial for the future of agriculture, municipal water supplies, and countless ecosystem services.

Tracing ground water input to base flow using sulfate (S, O) isotopes

USGS Publications Warehouse

Gu, A.; Gray, F.; Eastoe, C.J.; Norman, L.M.; Duarte, O.; Long, A.

2008-01-01

Sulfate (S and O) isotopes used in conjunction with sulfate concentration provide a tracer for ground water contributions to base flow. They are particularly useful in areas where rock sources of contrasting S isotope character are juxtaposed, where water chemistry or H and O isotopes fail to distinguish water sources, and in arid areas where rain water contributions to base flow are minimal. Sonoita Creek basin in southern Arizona, where evaporite and igneous sources of sulfur are commonly juxtaposed, serves as an example. Base flow in Sonoita Creek is a mixture of three ground water sources: A, basin ground water with sulfate resembling that from Permian evaporite; B, ground water from the Patagonia Mountains; and C, ground water associated with Temporal Gulch. B and C contain sulfate like that of acid rock drainage in the region but differ in sulfate content. Source A contributes 50% to 70%, with the remainder equally divided between B and C during the base flow seasons. The proportion of B generally increases downstream. The proportion of A is greatest under drought conditions.

The effect of saline groundwater exchange, evaporation and variable river flows and on stable isotopes (18O and 2H) and major ion concentrations along the Darling River, NSW, Australia

NASA Astrophysics Data System (ADS)

Meredith, K. T.; Hughes, C. E.; Hollins, S. E.; Cendón, D. I.; Hankin, S.

2009-04-01

Australia's longest river, the Darling River, faces extreme pressure from drought and over extraction of water from its catchment. The lack of detailed baseline hydrochemical and isotopic data for the Darling River has prompted research aimed at using hydrological tracers to assess water gains and losses within the Darling River Drainage Basin. This study uses temporal hydrochemical and stable isotope data (18O and 2H) that has been monitored from gauging stations along the Barwon-Darling catchment over a five-year period from 2002 to 2007 as part of the Global Network for Isotopes in Rivers (GNIR) monitoring programme. Stream flow data, monthly δ18O and δ2H values and major ion chemistry is presented. Individual flow events were found to be isotopically distinct but the LELs that develop after these events have a very similar slope indicating similar climatic conditions across this region. During low flow conditions, salt concentrations increase systematically, δ18O and δ2H become enriched and d-excess becomes more negative indicating significant evaporation. Flow events input isotopically depleted fresh waters to the system and the d-excess returns towards the local meteoric water line. The major ions increase in concentration at a greater rate at Louth than they do at upstream at Bourke or downstream at Wilcannia, despite similar decreases in flow rates for all three sites. The hydrological response of the river to drought has had detrimental affects on the surface water system because it provides a pathway for saline groundwater to discharge into the river system.

Evaporation from an Irrigated Terraced Rice Field Evaluated by Using Stable Isotopes: A Case Study in Batad, Philippines

NASA Astrophysics Data System (ADS)

Benavides, P.; Shimada, J.; Kagabu, M.; Loreto, F.; Leong, J.

2013-12-01

Bench terracing is an agricultural technique done by creating a step-like feature, serving as paddies, along the contours of the mountain to make the land more arable. Inundation of the paddies is done in different ways and one way is through a gravity-driven flow mechanism which is observed in Batad. This mechanism involved the flow of water to the next lower terrace in a cascading manner by diverting the water to small canals called spillways. The study aims to detect evaporation of the irrigation water flowing across a continuous terrace using water stable isotopes as tracers. Sampling was done during the planting season to ensure that irrigation water is flowing across the terraces. Samples were taken along the spillways of each terrace. Thirty irrigation water samples from four terraces facing different directions: NE, E, SE and S, and one precipitation sample were analyzed for major ions concentrations and H and O isotope ratios. Stiff and Piper diagrams show that the water samples are of surface and Mg-HCO3 type, implying that the water has juvenile features and has experienced little or no chemical differentiation. Water chemistry does not show any significant trend as the water moves across a terrace. Isotopic compositions range from -51.8‰ to -14.6‰ and from -8.24‰ to -2.39‰ for δ2H and δ18O, respectively. The lowest isotopic compositions are observed mostly in the source waters of the terraces while the highest are at the lowest paddy of the NE-facing terrace. The data plotted in a δ2H-δ18O diagram for each terrace shows linear plots with slopes deviating from the Philippine Meteoric Water Line (PMWL). Highest deviation is observed for the NE-facing terrace with a slope of 6.22, while the lowest is 6.91 from the SE-facing terrace, all of which are significantly lower than the PMWL's slope of 8 (Gerardo-Abaya, 2005). In addition, enrichment in isotopic composition is observed as the water moves away from the source. These findings confirm that evaporation takes place as the water moves across the terrace. Using the Rayleigh distillation equation, the degree of evaporation loss ranges from 23.13% and 24.34% from the SE-facing terrace to 32.50% and 35.80% from the NE-facing terrace for the δ2H and δ18O, respectively. Variations in the results for each terraces can be attributed to the different ambient meteorological conditions during sampling. More sampling is needed to further investigate whether different terrace orientations with similar meteorological conditions can also have an effect with the evaporation.

Multiple stable isotope fronts during non-isothermal fluid flow

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

Radium isotope quartet in groundwater as a proxy for identification of aquifer rocks and mechanisms of water-rock interactions: examples from the Negev, Israel

NASA Astrophysics Data System (ADS)

Vengosh, A.; Pery, N.; Paytan, A.; Haquin, G.; Elhanani, S.; Pankratov, I.

2006-05-01

Many aquifer systems are composed of multiple rock types. Previous attempts to evaluate the specific aquifer rocks that control the groundwater chemistry and possible flow paths within these multiple lithological systems have used major ion chemistry and isotopic tracers (e.g., strontium isotopes). Here we propose an additional isotopic proxy that is based on the distribution of radium isotopes in groundwater. Radium has four radioactive isotopes that are part of the decay chains of uranium-238, thorium-232, and uranium-235. The abundance of radium isotope quartet (226Ra-half life 1600 y; 228Ra-5.6 y; 224Ra-3.6 d; 223Ra-11.4 d) in groundwater reflects the Th/U ratios in the rocks. Investigation of groundwater from the Negev, Israel, enabled us to discriminate between groundwaters flowing in the Lower Cretaceous Nubian Sandstone and the Upper Cretaceous Judea Group carbonate aquifers. Groundwater flowing in the sandstone aquifer has distinguishably high 228Ra/226Ra and 224Ra/223Ra ratios due to the high Th/U ratio in sandstone. In contrast, the predominance of uranium in carbonate rocks results in low 228Ra/226Ra and 224Ra/223Ra ratios in the associated groundwater. We show that the radium activity in groundwater in the two-aquifer systems is correlated with temperature, dissolved oxygen, and salinity. The increase of radium activity is also associated with changes in the isotopic ratios; 228Ra/226Ra ratios increase and decrease in the sandstone and carbonate aquifers, respectively. Given that the dissolution of radium isotopes depends on their decay constants, the use of the four radium isotopes with different decay constants enabled us to distinguish between dissolution (higher abundance of the long-lived isotopes) and recoil (predominance of the short-lived isotopes) processes. In spite of these isotopic fractionations, the radium isotopic discrimination between carbonate and sandstone aquifers is significant.

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

PubMed

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

2016-07-15

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

Flow-path textures and mineralogy in tuffs of the unsaturated zone

USGS Publications Warehouse

Levy, Schön; Chipera, Steve; WoldeGabriel, Giday; Fabryka-Martin, June; Roach, Jeffrey; Sweetkind, Donald S.; Haneberg, William C.; Mozley, Peter S.; Moore, J. Casey; Goodwin, Laurel B.

1999-01-01

The high concentration of chlorine-36 (36Cl) produced by above-ground nuclear tests (bomb-pulse) provides a fortuitous tracer for infiltration during the last 50 years, and is used to detect fast flow in the unsaturated zone at Yucca Mountain, Nevada, a thick deposit of welded and nonwelded tuffs. Evidence of fast flow as much as 300 m into the mountain has been found in several zones in a 7.7-km tunnel. Many zones are associated with faults that provide continuous fracture flow paths from the surface. In the Sundance fault zone, water with the bomb-pulse signature has moved into subsidiary fractures and breccia zones. We found no highly distinctive mineralogic associations of fault and fracture samples containing bomb-pulse 36Cl. Bomb-pulse sites are slightly more likely to have calcite deposits than are non-bomb-pulse sites. Most other mineralogic and textural associations of fast-flow paths reflect the structural processes leading to locally enhanced permeability rather than the effects of ground-water percolation. Water movement through the rock was investigated by isotopic analysis of paired samples representing breccia zones and fractured wall rock bounding the breccia zones. Where bomb-pulse 36Cl is present, the waters in bounding fractures and intergranular pores of the fast pathways are not in equilibrium with respect to the isotopic signal. In structural domains that have experienced extensional deformation, fluid flow within a breccia is equivalent to matrix flow in a particulate rock, whereas true fracture flow occurs along the boundaries of a breccia zone. Where shearing predominated over extension, the boundary between wall rock and breccia is rough and irregular with a tight wallrock/breccia contact. The absence of a gap between the breccia and the wall rock helps maintain fluid flow within the breccia instead of along the wallrock/breccia boundary, leading to higher 36Cl/Cl values in the breccia than in the wall rock.

Oxygen isotope exchange in rocks and minerals from the Cerro Prieto geothermal system: Indicators of temperature distribution and fluid flow

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

Williams, A.E.; Elders, W.A.

1981-01-01

Oxygen isotopic compositions have been measured in drill cuttings and core samples from more than 40 wells ranging in depth to more than 3.5 km in the Cerro Prieto geothermal field. Profiles of isotopic ratios versus sampling depths provide information on the three-dimensional distribution of temperature and fluid flow. These parameters also indicate variations in the history of hydrothermal processes in different areas of the geothermal field.

Applicability of 87Sr/86Sr in examining return flow of irrigation water in highly agricultural watersheds in Japan

NASA Astrophysics Data System (ADS)

Yoshida, T.; Nakano, T.; Shin, K. C.; Tsuchihara, T.; Miyazu, S.; Kubota, T.

2017-12-01

Water flows in watersheds containing extensive areas of irrigated paddies are complex because of the substantial volumes involved and the repeated cycles of water diversion from, and return to, streams. For better management of low-flow conditions, numerous studies have attempted to quantify the return flow using the stable isotopes of water; however, the temporal variation in these isotopic compositions due to fractionation during evaporation from water surfaces hinders their application to watersheds with extensive irrigated paddies. In this study, we tested the applicability of the strontium isotopes (87Sr/86Sr, hereafter Sr ratio) for studying hydrological processes in a typical agricultural watershed located on the alluvial fan of the Kinu River, namely the Gogyo River, in central Japan. The Sr ratio of water changes only because of interactions with the porous media it flows through, or because of mixing with water that has different Sr ratios. We sampled water both at a single rice paddy, and on the watershed scale in the irrigated and non-irrigated periods. The soil water under the paddy decreased as sampling depth increased, and the soil water at a depth of 1.5 m showed a similar Sr ratio to the spring. The water sampled in the drainage channel with a concrete lined bottom showed a similar Sr ratio to the irrigation water, whereas that with a soil bottom was plotted between the plots of the irrigation water and shallow aquifer. These results suggest the Sr ratio decreases as it mixes with the soil water through percolation; whereas the Sr ratio will be less likely to change when water drains from paddies via surface pathways. The streamflow samples were plotted linearly on the Sr ratio and 1/Sr plot, indicating that the streamflow was composed of two end-members; the irrigation water and the shallow aquifer. The continuous decline in the Sr ratio along the stream suggests an exfiltration of water from the shallow aquifers. The stream water during the non-irrigated period were lower in Sr ratios and higher in Sr concentrations, suggesting an increase in contributions of the water from the shallow aquifers. Understanding the return flow of irrigation water in highly agricultural watersheds is vital for measuring any temporal changes in flow to the lower parts of the watershed, and allows for improved water management.

Red deer bone and antler collagen are not isotopically equivalent in carbon and nitrogen.

PubMed

Stevens, Rhiannon E; O'Connell, Tamsin C

2016-09-15

Bone and antler collagen δ(13) C and δ(15) N values are often assumed to be equivalent when measured in palaeodietary, palaeoclimate and palaeocological studies. Although compositionally similar, bone grows slowly and is remodelled whereas antler growth is rapid and remodelling does not occur. These different patterns of growth could result in isotopic difference within antler and between the two tissue types. Here we test whether red deer (Cervus elaphus) bone and antler δ(13) C and δ(15) N values are equivalent, and whether intra-antler isotopic values are uniform. Bone and antler were isotopically analysed from six stags that lived in a temperate maritime climate on the Isle of Rum, Scotland. Multiple antlers from different years were sampled per individual, together with a single bone sample per individual. Up to 12 samples were taken along the length of each antler (total of 25 antlers, 259 samples) so that a chronological record of the isotopic composition during antler growth could be obtained. Collagen was extracted and its δ(13) C and δ(15) N values were measured by continuous-flow isotope ratio mass spectrometry. Intra-antler collagen isotope signatures vary, and show that not all antlers from an individual or a growth year are equivalent in carbon and nitrogen isotopic ratios. δ(15) N values typically increase with distance along antler length, but no overall trend is observed in δ(13) C values. An isotopic offset is visible between bone and antler, with bone δ(13) C and δ(15) N values being higher in most cases. Bone and antler collagen δ(13) C and δ(15) N values are not isotopically equivalent and are therefore not directly comparable in palaeodietary, palaeoclimate and palaeocological studies. Bone and antler collagen isotopic differences probably relate to differential metabolic processes during the formation of the two tissues. Intra- and inter-antler isotopic variations probably reflect the isotopic composition of an individual's diet rather than physiological parameters, and may have the potential to provide high-resolution individual-specific information in modern and ancient cervid populations. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Oxygen isotope analysis of phosphate: improved precision using TC/EA CF-IRMS.

PubMed

LaPorte, D F; Holmden, C; Patterson, W P; Prokopiuk, T; Eglington, B M

2009-06-01

Oxygen isotope values of biogenic apatite have long demonstrated considerable promise for paleothermometry potential because of the abundance of material in the fossil record and greater resistance of apatite to diagenesis compared to carbonate. Unfortunately, this promise has not been fully realized because of relatively poor precision of isotopic measurements, and exceedingly small size of some substrates for analysis. Building on previous work, we demonstrate that it is possible to improve precision of delta18O(PO4) measurements using a 'reverse-plumbed' thermal conversion elemental analyzer (TC/EA) coupled to a continuous flow isotope ratio mass spectrometer (CF-IRMS) via a helium stream [Correction made here after initial online publication]. This modification to the flow of helium through the TC/EA, and careful location of the packing of glassy carbon fragments relative to the hot spot in the reactor, leads to narrower, more symmetrically distributed CO elution peaks with diminished tailing. In addition, we describe our apatite purification chemistry that uses nitric acid and cation exchange resin. Purification chemistry is optimized for processing small samples, minimizing isotopic fractionation of PO4(-3) and permitting Ca, Sr and Nd to be eluted and purified further for the measurement of delta44Ca and 87Sr/86Sr in modern biogenic apatite and 143Nd/144Nd in fossil apatite. Our methodology yields an external precision of +/- 0.15 per thousand (1sigma) for delta18O(PO4). The uncertainty is related to the preparation of the Ag3PO4 salt, conversion to CO gas in a reversed-plumbed TC/EA, analysis of oxygen isotopes using a CF-IRMS, and uncertainty in constructing calibration lines that convert raw delta18O data to the VSMOW scale. Matrix matching of samples and standards for the purpose of calibration to the VSMOW scale was determined to be unnecessary. Our method requires only slightly modified equipment that is widely available. This fact, and the demonstrated improvement in precision, should help to make apatite paleothermometry far more accessible to paleoclimate researchers. Copyright 2009 John Wiley & Sons, Ltd.

[Measurements of stable isotopes in atmospheric CO2 and H2O by open-path Fourier transform infrared spectrometry].

PubMed

Wang, Wei; Liu, Wen-Qing; Zhang, Tian-Shu

2013-08-01

The development of spectroscopic techniques has offered continuous measurement of stable isotopes in the ambient air. The method of measuring environmental stable isotopes based on Fourier transform infrared spectrometry (FTIR) is described. In order to verify the feasibility of the method for continuous measurement of the stable isotopes, an open-path FTIR system was used to measure stable isotopes of CO2 and H2O in ambient air directly in a seven-day field experiment, including 12CO2, 3CO2, H2 16O and HD16 O. Also, the time course of carbon isotopic ratio delta13 C and deuterium isotope composition deltaD was calculated. The measurement precision is about 1.08 per thousand for delta13 C and 1.32 per thousand for deltaD. The measured stable isotopes of CO2 and H2O were analyzed on different time scales by Keeling plot methods, and the deuterium isotopic ratios of evapotranspiration were determined. The results of the field experiment demonstrate the potential of the open-path FTIR system for continuous measurement of stable isotopes in the air.

Using noble gases measured in spring discharge to trace hydrothermal processes in the Norris Geyser Basin, Yellowstone National Park, U.S.A.

USGS Publications Warehouse

Gardner, W.P.; Susong, D.D.; Solomon, D.K.; Heasler, H.P.

2010-01-01

Dissolved noble gas concentrations in springs are used to investigate boiling of hydrothermal water and mixing of hydrothermal and shallow cool water in the Norris Geyser Basin area. Noble gas concentrations in water are modeled for single stage and continuous steam removal. Limitations on boiling using noble gas concentrations are then used to estimate the isotopic effect of boiling on hydrothermal water, allowing the isotopic composition of the parent hydrothermal water to be determined from that measured in spring. In neutral chloride springs of the Norris Geyser Basin, steam loss since the last addition of noble gas charged water is less than 30% of the total hydrothermal discharge, which results in an isotopic shift due to boiling of ?? 2.5% ??D. Noble gas concentrations in water rapidly and predictably change in dual phase systems, making them invaluable tracers of gas-liquid interaction in hydrothermal systems. By combining traditional tracers of hydrothermal flow such as deuterium with dissolved noble gas measurements, more complex hydrothermal processes can be interpreted. ?? 2010 Elsevier B.V.

Landscape cultivation alters δ30Si signature in terrestrial ecosystems.

NASA Astrophysics Data System (ADS)

Vandevenne, F. I.; Delvaux, C.; Huyghes, H.; Ronchi, B.; Govers, G.; Barão, A. L.; Clymans, W.; Meire, P.; André, L.; Struyf, E.

2014-12-01

Despite increasing recognition of the importance of biological Si cycling in controlling dissolved Si (DSi) in soil and stream water, effects of human cultivation on the Si cycle remain poorly understood. Sensitive tracer techniques to identify and quantify Si in the soil-plant-water system could be highly relevant in addressing these uncertainties. Stable Si isotopes are promising tools to define Si sources and sinks along the ecosystem flow path, as intense fractionation occurs during chemical weathering and uptake of dissolved Si in plants. Yet they remain underexploited in the end product of the soil-plant system: the soil water. Here, stable Si isotope ratios (δ30Si) of dissolved Si in soil water were measured along a land use gradient (continuous forest, continuous pasture, young cropland and continuous cropland) with similar parent material (loess) and homogenous bulk mineralogical and climatological properties (Belgium). Soil water δ30Si signatures are clearly separated along the gradient, with highest average signatures in continuous cropland (+1.61‰), intermediate in pasture (+1.05‰) and young cropland (+0.89 ‰) and lowest in forest soil water (+0.62‰). Our data do not allow distinguishing biological from pedogenic/lithogenic processes, but point to a strong interaction of both. We expect that increasing export of light isotopes in disturbed land uses (i.e. through agricultural harvest), and higher recycling of 28Si and elevated weathering intensity (including clay dissolution) in forest systems will largely determine soil water δ30Si signatures of our systems. Our results imply that soil water δ30Si signature is biased through land management before it reaches rivers and coastal zones, where other fractionation processes take over (e.g. diatom uptake and reverse weathering in floodplains). In particular, a direct role of agriculture systems in lowering export Si fluxes towards rivers and coastal systems has been shown. Stable Si isotopes have a large potential to track human disturbance on the Si cycle, including subtle changes in clay evolution and biogenic sink/source functions as induced by land use conversions.

Landscape cultivation alters δ30Si signature in terrestrial ecosystems

NASA Astrophysics Data System (ADS)

Vandevenne, Floor; Delvaux, Claire; Hughes, Harold; Ronchi, Benedicta; Clymans, Wim; Barao, Ana Lucia; Govers, Gerard; Cornelis, Jean Thomas; André, Luc; Struyf, Eric

2015-04-01

Despite increasing recognition of the importance of biological Si cycling in controlling dissolved Si (DSi) in soil and stream water, effects of human cultivation on the Si cycle remain poorly understood. Sensitive tracer techniques to identify and quantify Si in the soil-plant-water system could be highly relevant in addressing these uncertainties. Stable Si isotopes are promising tools to define Si sources and sinks along the ecosystem flow path, as intense fractionation occurs during chemical weathering and uptake of dissolved Si in plants. Yet they remain underexploited in the end product of the soil-plant system: the soil water. Here, stable Si isotope ratios (δ30Si) of dissolved Si in soil water were measured along a land use gradient (continuous forest, continuous pasture, young cropland and continuous cropland) with similar parent material (loess) and homogenous bulk mineralogical and climatological (Belgium). Soil water δ30Si signatures are clearly separated along the gradient, with highest average signatures in continuous cropland (+1.61%), intermediate in pasture (+1.05%) and young cropland (+0.89%) and lowest in forest soil water (+0.62%). Our data do not allow distinguishing biological from pedogenic/lithogenic processes, but point to a strong interaction of both. We expect that increasing export of light isotopes in disturbed land uses (i.e. through agricultural harvest), and higher recycling of 28Si and elevated weathering intensity (including clay dissolution) in forest systems will largely determine soil water δ30Si signatures of our systems. Our results imply that soil water δ30Si signature is biased through land management before it reaches rivers and coastal zones, where other fractionation processes take over (e.g. diatom uptake and reverse weathering in floodplains). In particular, a direct role of agriculture systems in lowering export Si fluxes towards rivers and coastal systems has been shown. Stable Si isotopes have a large potential to track human disturbance on the Si cycle, including subtle changes in clay evolution and biogenic sink/source functions as induced by land use conversions.

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.

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.

Evaluation of online carbon isotope dilution mass spectrometry for the purity assessment of synthetic peptide standards.

PubMed

Cueto Díaz, Sergio; Ruiz Encinar, Jorge; García Alonso, J Ignacio

2014-09-24

We present a novel method for the purity assessment of peptide standards which is applicable to any water soluble peptide. The method is based on the online (13)C isotope dilution approach in which the peptide is separated from its related impurities by liquid chromatography (LC) and the eluent is mixed post-column with a continuous flow of (13)C-enriched sodium bicarbonate. An online oxidation step using sodium persulfate in acidic media at 99°C provides quantitative oxidation to (12)CO2 and (13)CO2 respectively which is extracted to a gaseous phase with the help of a gas permeable membrane. The measurement of the isotope ratio 44/45 in the mass spectrometer allows the construction of the mass flow chromatogram. As the only species that is finally measured in the mass spectrometer is CO2, the peptide content in the standard can be quantified, on the base of its carbon content, using a generic primary standard such as potassium hydrogen phthalate. The approach was validated by the analysis of a reference material (NIST 8327), and applied to the quantification of two commercial synthetic peptide standards. In that case, the results obtained were compared with those obtained using alternative methods, such as amino acid analysis and ICP-MS. The results obtained proved the value of the method for the fast, accurate and precise mass purity assignment of synthetic peptide standards. Copyright © 2014 Elsevier B.V. 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.

High Resolution Time Series Cave Ventilation Processes and the Effects on Cave Air Chemistry and Drip Waters: Speleoclimatology and Proxy Calibration

NASA Astrophysics Data System (ADS)

Kowalczk, A. J.; Froelich, P. N.; Gaffka, C.; Tremaine, D.

2008-12-01

Continuous high resolution (sub-hourly), long-term (Nov 2007-present) monitoring of cave air chemistry (Temperature, Relative Humidity, Barometric Pressure, Radon-222, CO2, Air flow, Wind speed and direction) in a shallow subtropical cave (Hollow Ridge) in N Florida reveals two major ventilation mechanisms: 1) ventilation driven by winds across the cave entrances, and 2) ventilation driven by density differences between atmospheric and cave air. The degree and type of ventilation strongly influence the 222Rn and CO2 of cave air, which in turn affects the timing and extent of calcite deposition in speleothems. The degree of ventilation is estimated using a cave air CO2-δ13CO2 Keeling Plot, or a simple radon deficiency model. Results show cave air has an atmospheric component ranging from 10-90%. During fall and winter, average CO2 (700 ppmv) and 222Rn (50-100 dpm/L) are lower than in spring and summer (CO2 = 1200 ppmv; 222Rn = 1000 dpm/L) due to increased winter ventilation. Decreased ventilation during the summer allows CO2 and 222Rn levels to rise. Winter daily ventilation is primarily a function of density gradients between cave air and atmospheric air, while summer daily ventilation is primarily a function of late morning NW-NE winds above the cave. Stable isotope analyses of drip water (fracture drip and pore flow drip) and aquifer water from Hollow Ridge agree with previous isotope studies of drip water at Florida Caverns State Park, 2 km to the NE. During summer, isotopic composition of pore flow drip water (δ18O -3.8 to -4.0 per mil; δD -17.3 to -20.2 per mil VSMOW) and aquifer water (δ18O -4.0 per mil; δD -18.0 to -21.1 per mil) are similar to average annual weighted isotopic composition of precipitation (δ18O -3.6 per mil) while fracture drip waters (δ18O -3 to -3.4 per mil; δD -11.9 to -14.3 per mil) likely reflect the isotopic composition of individual precipitation events. Pore flow drip waters δ18O are weakly correlated with drip rates (enriched δ18O during periods of higher drip rates) but show no correlation to precipitation amount. Knowledge of the type of drip flow is important when considering stalagmites for paleoclimate studies. A significant decrease in drip rate was observed from June (1034 drips/hour) through August 2008 (34 drips/hour). Higher water demands during summer months with increased evapotranspiration may be responsible for this decrease. A semi-diurnal drip rate cycle, negatively correlated with barometric pressure, is also observed throughout the period. This strong negative correlation is hypothesized to be controlled by atmospheric tidal oscillations. Observations into the fall and winter seasons should reveal seasonality, if any, and if there is an evapotranspiration effect present in the water cycle. High resolution studies of cave air chemistry and ventilation processes will enhance knowledge of the timing, extent, and isotopic and chemical composition of calcite deposition. When combined with drip water and precipitation isotope analyses, these studies will improve the understanding and interpretation of high- resolution (sub-annual) speleothem paleoclimate records.

Variation of brine compositions resulting from flow from matrix or fracture permeability, investigated by high pressure laboratory experiments

NASA Astrophysics Data System (ADS)

Poszwa, A. C.; Coleman, M. L.; Pouya, A.; Ader, M.; Bounenni, A.

2003-04-01

Planning oil production from a chalk reservoir oilfield is difficult because the matrix usually has low permeability despite its high porosity. Most oil is thought to come from fracture porosity but the matrix contribution should increase as compaction occurs during production. To better understand the respective contributions from matrix and fracture, we studied the geochemical characteristics of fluids using high-pressure brine flow experiments on chalk cores. During the experiment axial load was changed relative to confining pressure to induce fractures and to close them again. We used chlorine stable isotope variations to study fluid pathway, because chlorine is a chemically conservative element in sedimentary systems and its isotopes fractionate only with physical processes like diffusion or adsorption that could occur mainly in the chalk matrix. A first experiment was performed on a very porous chalk from Henley (on-shore UK) and using a low-salinity brine. Large variations of brine Cl isotope composition were observed (from -0.56 to +0.08 per mil). The variations were correlated positively with the brine flux through the chalk and the permeability of the rock, both parameters controlled by the rock fracturing. A second experiment used brine with salinity similar to that of seawater. In this case, chemical and isotopic variations were not significant. From the beginning, the chalk structure seems to have been destroyed very quickly (induced fracture porosity collapsed) possibly because of the fluid nature, so that whatever pressure was applied, the permeability did not change significantly. Using Valhall reservoir chalk (offshore Norwegian North Sea) and fluid half the salinity of seawater in a third experiment, we obtained a large range of permeabilities. Brine isotopic trends were very similar on average to those of the first experiment even though variations were smaller (Cl isotopes from -0.09 to +0.29 per mil) and not significantly correlated simply to permeability values. The highest isotopic values were in brine flowed through chalk when the permeability was high and fractures opened; the lowest values were in brine flowed through the chalk when its permeability was reduced by closing fractures and increasing the relative contribution from matrix flow where diffusion processes fractionated chlorine isotopes. From this work it seems that the relative contributions from fracture and matrix permeability in reservoirs can be estimated from the geochemical compositions of brines that flowed from them.

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Teng, Fang-Zhen; Arndt, Nicholas T.

2010-06-01

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (˜50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ 25Mg and δ 26Mg values of the bulk flow are -0.138 ± 0.021‰ and -0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ 56Fe and δ 57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ 56Fe and slightly heavy δ 26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

Stable isotopes reveal spatial variability in the trophic structure of a macro-benthic invertebrate community in a tropical coral reef.

PubMed

Kolasinski, Joanna; Nahon, Sarah; Rogers, Karyne; Chauvin, Anne; Bigot, Lionel; Frouin, Patrick

2016-02-15

Studies of organic matter fluxes in coral reefs are historically based on physical and biogeochemical approaches. It is important to link these approaches to community analysis as the abundance and behaviour of species, populations or trophic groups can have a profound effect on nutrient budgets. We determined the carbon and nitrogen isotopic compositions of coral reef organic matter sources and macro-benthic invertebrate communities using a Europa Geo 20/20 isotope ratio mass spectrometer interfaced to an ANCA-SL elemental analyzer in continuous flow mode. Isotopic ecology metrics and a mixing model were used to analyze and interpret the data. The coral reef macro-invertebrate community principally relies on detrital or recycled food sources. An increased reliance on reef nitrogen-derived sources was observed in the cold-dry season. The community food-web lengths differ noticeably across the coral reef and reflect the characteristics and origin of organic matter reservoirs. Anthropogenic and terrestrial inputs lead to a loss of biological diversity. Exclusive dominance of suspension-feeding species is observed in areas receiving direct surface riverine particulate organic matter. The accumulation of sediment organic matter in eutrophic areas leads to dominance of deposit-feeding species. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

The Upper Mantle Flow Field around South-Africa as Reflected by Isotopic Provinciality

NASA Astrophysics Data System (ADS)

Meyzen, C.; Blichert-Toft, J.; Ludden, J.; Humler, E.; Mevel, C.; Albarede, F.

2006-12-01

Isotopic studies of MORB have established the existence of broad isotopic provinces within the underlying asthenosphere, such as in the Indian Ocean (DUPAL). How these features relate to mantle circulation is, however, still unknown. The steepness of the transition between such isotopic provinces will define the geometry of the velocity field in the upper mantle. In this respect, the transition between the Indian and South Atlantic provinces, two domains that are isotopically contrasted, should be readily identifiable over this long ridge segment. Here, we present Hf isotope data for 60 samples dredged along the SWIR between 35° and 69°E. The new Hf isotope data show that the Indian asthenosphere does not spill directly into the South Atlantic upper mantle: the general decreasing southward gradient observed for ^{176}Hf/^{177}Hf down the mid- Atlantic Ridge, and also for Sr isotopes and model Th/U ratios (derived from Pb isotopes), is overprinted by material with radiogenic Sr, unradiogenic Hf and high Th/U. The Indian domain grades into the South Atlantic around Bouvet, while the South Atlantic collides with the Atlantic province around Tristan. We interpret these features to represent fronts between three adjacent isotopic provinces similar to what has been suggested for the Australian-Antarctic Discordance. The common DUPAL signature of MORB and OIB from the Indian province and the geochemistry of Gulf of Aden MORB and the Afar plume suggest that the source of this distinctive mantle component is deep and lies to the north of the province. This is also what the three-dimensional flow field computed by Behn et al. (2004) from shear-wave splitting shows with a major lower mantle upwelling radiating at the base of the asthenosphere under the Afar plume. Lower mantle gushing out from this source flows southward unimpeded along the Indian ridges, whereas it only reaches the South Atlantic ridge after first having been deflected under the deep roots of the South African Archean cratons. Erosion of these roots by the asthenospheric drift confers a distinct continental signature on the source of South Atlantic MORB. This pattern is also consistent with the observation that the lowest He isotope values occur, on average, along the South Atlantic ridge. To some extent, the dynamics of the North Atlantic upper mantle mirrors the Indian situation: the flow field of Behn et al. (2004) shows that the North Atlantic asthenosphere also fills up through deep mantle upwellings, which is consistent with the Dupal-like isotopic signature of the Arctic ridges. M.D. Behn, C.P. Conrad and P.G. Silver (2004), Detection of upper mantle flow associated with the African Superplume, Earth. Planet. Sci. Lett., 224, 259-274.

The influence of melt infiltration on the Li and Mg isotopic composition of the Horoman Peridotite Massif

NASA Astrophysics Data System (ADS)

Lai, Yi-Jen; Pogge von Strandmann, Philip A. E.; Dohmen, Ralf; Takazawa, Eiichi; Elliott, Tim

2015-09-01

We have analysed the Li and Mg isotope ratios of a suite of samples from the Horoman Peridotite Massif. Our results show that most Li and all Mg isotopic compositions of the Horoman peridotites are constant over 100 metres of continuous outcrop, yielding values for pristine mantle of δ7Li = 3.8 ± 1.4‰ (2SD, n = 9), δ25Mg = -0.12 ± 0.02‰ and δ26Mg = -0.23 ± 0.04‰ (2SD, n = 17), in keeping with values for undisturbed mantle xenoliths. However, there are also some anomalously low δ7Li values (-0.2‰ to 1.6‰), which coincide with locations that show enrichment of incompatible elements, indicative of the prior passage of small degree melts. We suggest Li diffused from infiltrating melts with high [Li] into the low [Li] minerals and kinetically fractionated 7Li/6Li as a result. Continued diffusion after the melt flow had ceased would have resulted in the disappearance of this isotopically light signature in less than 15 Ma. In order to preserve this feature, the melt infiltration must have been a late stage event and the massif must have subsequently cooled over a maximum of ∼0.3 Ma from peak temperature (950 °C, assuming the melts were hydrous) to Li closure temperature (700 °C), likely during emplacement. The constant δ26Mg values of Horoman peridotites suggest that chemical potential gradients caused by melt infiltration were insufficient to drive associated δ26Mg fractionation greater than our external precision of 0.03‰.

Estimation of snow and glacier melt contribution to Liddar stream in a mountainous catchment, western Himalaya: an isotopic approach.

PubMed

Jeelani, Gh; Shah, Rouf A; Jacob, Noble; Deshpande, Rajendrakumar D

2017-03-01

Snow- and glacier-dominated catchments in the Himalayas are important sources of fresh water to more than one billion people. However, the contribution of snowmelt and glacier melt to stream flow remains largely unquantified in most parts of the Himalayas. We used environmental isotopes and geochemical tracers to determine the source water and flow paths of stream flow draining the snow- and glacier-dominated mountainous catchment of the western Himalaya. The study suggested that the stream flow in the spring season is dominated by the snowmelt released from low altitudes and becomes isotopically depleted as the melt season progressed. The tracer-based mixing models suggested that snowmelt contributed a significant proportion (5-66 %) to stream flow throughout the year with the maximum contribution in spring and summer seasons (from March to July). In 2013 a large and persistent snowpack contributed significantly (∼51 %) to stream flow in autumn (September and October) as well. The average annual contribution of glacier melt to stream flow is little (5 %). However, the monthly contribution of glacier melt to stream flow reaches up to 19 % in September during years of less persistent snow pack.

Trends in North Pacific Ocean-Atmosphere Variability During the Common Era Inferred From a New Mt. Hunter (Denali, Alaska) 1200-Year Ice Core Stable Isotope Record

NASA Astrophysics Data System (ADS)

Kreutz, K. J.; Osterberg, E. C.; Winski, D.; Wake, C. P.; Campbell, S. W.; Introne, D.; Ferris, D. G.

2016-12-01

The mechanisms and outcomes of teleconnections between the tropical and North Pacific regions over the past 2000 years remain elusive. Correctly assessing the impact on the Aluetian Low, storm tracks, and general hydroclimate during the Medieval Climate Anomaly (MCA), transition to the Little Ice Age (LIA), and then into the 20th century likely requires a suite of high resolution paleoclimate data from the region. Here we present an ice core stable water isotope developed from two surface to bedrock ice cores recovered in 2013 from the high elevation Mt. Hunter plateau in Denali National Park, Alaska. The cores were processed using a continuous flow analysis (CFA) system, and dated using a combination of annual chemical and dust signals, and radioactive and volcanic horizons. The resulting annually-resolved timescale currently spans 2013-810AD. We analyzed 6000 stable water isotope samples for d18O, dD, and the derived deuterium excess (dxs) parameter, yielding a subannually resolved isotope record from 2013-1234AD, and 1-3 year resolution from 1233-810AD. We initially focus on the dxs record, as there are trends in the data that correspond to the large scale climate features of the Common Era. The dxs record shows decreased values during the MCA and a rise into the LIA, consistent with several other regional paleoclimate records. The most obvious feature of the dxs record is a pronounced decrease beginning in the mid 19th century and continuing to present. We note that this trend mirrors a rise in snow accumulation rate in the Denali ice core record, suggesting coherent changes in North Pacific climate dynamics over the past 150 years. Understanding the dxs record in terms of ocean source region temperature and/or relative humidity remains a challenge, and we discuss progress on interpreting the Denali isotope record and fitting these data into a broader paleoclimate context.

Plume mapping and isotopic characterisation of anthropogenic methane sources

NASA Astrophysics Data System (ADS)

Zazzeri, G.; Lowry, D.; Fisher, R. E.; France, J. L.; Lanoisellé, M.; Nisbet, E. G.

2015-06-01

Methane stable isotope analysis, coupled with mole fraction measurement, has been used to link isotopic signature to methane emissions from landfill sites, coal mines and gas leaks in the United Kingdom. A mobile Picarro G2301 CRDS (Cavity Ring-Down Spectroscopy) analyser was installed on a vehicle, together with an anemometer and GPS receiver, to measure atmospheric methane mole fractions and their relative location while driving at speeds up to 80 kph. In targeted areas, when the methane plume was intercepted, air samples were collected in Tedlar bags, for δ13C-CH4 isotopic analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). This method provides high precision isotopic values, determining δ13C-CH4 to ±0.05 per mil. The bulk signature of the methane plume into the atmosphere from the whole source area was obtained by Keeling plot analysis, and a δ13C-CH4 signature, with the relative uncertainty, allocated to each methane source investigated. Both landfill and natural gas emissions in SE England have tightly constrained isotopic signatures. The averaged δ13C-CH4 for landfill sites is -58 ± 3‰. The δ13C-CH4 signature for gas leaks is also fairly constant around -36 ± 2‰, a value characteristic of homogenised North Sea supply. In contrast, signatures for coal mines in N. England and Wales fall in a range of -51.2 ± 0.3‰ to -30.9 ± 1.4‰, but can be tightly constrained by region. The study demonstrates that CRDS-based mobile methane measurement coupled with off-line high precision isotopic analysis of plume samples is an efficient way of characterising methane sources. It shows that isotopic measurements allow type identification, and possible location of previously unknown methane sources. In modelling studies this measurement provides an independent constraint to determine the contributions of different sources to the regional methane budget and in the verification of inventory source distribution.

Review of progress in understanding the fluid geochemistry of the Cerro Prieto Geothermal System

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

Truesdell, A.H.; Nehring, N.L.; Thompson, J.M.

1982-08-10

Fluid geochemistry has played a major role in the authors present understanding of the Cerro Prieto geothermal system. Fluid chemical and isotopic compositions have been used to indicate the origin of water, salts, and gases, original subsurface temperature and fluid flow, fluid-production mechanims, and production-induced aquifer boiling and cold-water entry. The extensive geochemical data and interpretation for Cerro Prieto published from 1964 to 1981 are reviewed and discussed. Fluid geochemistry must continue to play an important role in the further development of the Cerro Prieto field.

Stable isotope analyses of oxygen (18O:17O:16O) and chlorine (37Cl:35Cl) in perchlorate: reference materials, calibrations, methods, and interferences

USGS Publications Warehouse

Böhlke, John Karl; Mroczkowski, Stanley J.; Sturchio, Neil C.; Heraty, Linnea J.; Richman, Kent W.; Sullivan, Donald B.; Griffith, Kris N.; Gu, Baohua; Hatzinger, Paul B.

2017-01-01

RationalePerchlorate (ClO4−) is a common trace constituent of water, soils, and plants; it has both natural and synthetic sources and is subject to biodegradation. The stable isotope ratios of Cl and O provide three independent quantities for ClO4− source attribution and natural attenuation studies: δ37Cl, δ18O, and δ17O (or Δ17O or 17Δ) values. Documented reference materials, calibration schemes, methods, and interferences will improve the reliability of such studies.MethodsThree large batches of KClO4 with contrasting isotopic compositions were synthesized and analyzed against VSMOW-SLAP, atmospheric O2, and international nitrate and chloride reference materials. Three analytical methods were tested for O isotopes: conversion of ClO4− to CO for continuous-flow IRMS (CO-CFIRMS), decomposition to O2 for dual-inlet IRMS (O2-DIIRMS), and decomposition to O2 with molecular-sieve trap (O2-DIIRMS+T). For Cl isotopes, KCl produced by thermal decomposition of KClO4 was reprecipitated as AgCl and converted into CH3Cl for DIIRMS.ResultsKClO4 isotopic reference materials (USGS37, USGS38, USGS39) represent a wide range of Cl and O isotopic compositions, including non-mass-dependent O isotopic variation. Isotopic fractionation and exchange can affect O isotope analyses of ClO4− depending on the decomposition method. Routine analyses can be adjusted for such effects by normalization, using reference materials prepared and analyzed as samples. Analytical errors caused by SO42−, NO3−, ReO42−, and C-bearing contaminants include isotope mixing and fractionation effects on CO and O2, plus direct interference from CO2 in the mass spectrometer. The results highlight the importance of effective purification of ClO4− from environmental samples.ConclusionsKClO4 reference materials are available for testing methods and calibrating isotopic data for ClO4− and other substances with widely varying Cl or O isotopic compositions. Current ClO4−extraction, purification, and analysis techniques provide relative isotope-ratio measurements with uncertainties much smaller than the range of values in environmental ClO4−, permitting isotopic evaluation of environmental ClO4− sources and natural attenuation.

Hydrogeology, geochemistry, and quality of water of The Basin and Oak Spring areas of the Chisos Mountains, Big Bend National Park, Texas

USGS Publications Warehouse

Baker, E.T.; Buszka, P.M.

1993-01-01

Water-chemistry data, hydrochemical facies, and isotopic data also indicate that water from Oak Spring originates principally from precipitation onto the land surface of the Oak Spring area. Tritium data indicate that Oak Spring water is "modern," with an average age of recharge less than 14 years. The flow rates recorded almost continuously at Oak Spring beginning in December 1986 show a close relation between precipitation and discharge. The highest recorded spring flow of 167 gallons per minute in December 1986 is attributed to record high precipitation in the area during 1986. The lowest recorded flow of 22.4 gallons per minute, in December 1989, followed a period of 20 out of 26 months of below-normal precipitation. Flow at Oak Spring typically lags behind precipitation by about 1 month. This fairly rapid response indicates the spring is fed by a shallow aquifer having good permeability and effective recharge areas with the ability to absorb precipitation rapidly.

Carbon and hydrogen isotope fractionation under continuous light: implications for paleoenvironmental interpretations of the High Arctic during Paleogene warming.

PubMed

Yang, Hong; Pagani, Mark; Briggs, Derek E G; Equiza, M A; Jagels, Richard; Leng, Qin; Lepage, Ben A

2009-06-01

The effect of low intensity continuous light, e.g., in the High Arctic summer, on plant carbon and hydrogen isotope fractionations is unknown. We conducted greenhouse experiments to test the impact of light quantity and duration on both carbon and hydrogen isotope compositions of three deciduous conifers whose fossil counterparts were components of Paleogene Arctic floras: Metasequoia glyptostroboides, Taxodium distichum, and Larix laricina. We found that plant leaf bulk carbon isotopic values of the examined species were 1.75-4.63 per thousand more negative under continuous light (CL) than under diurnal light (DL). Hydrogen isotope values of leaf n-alkanes under continuous light conditions revealed a D-enriched hydrogen isotope composition of up to 40 per thousand higher than in diurnal light conditions. The isotope offsets between the two light regimes is explained by a higher ratio of intercellular to atmospheric CO(2) concentration (C (i)/C (a)) and more water loss for plants under continuous light conditions during a 24-h transpiration cycle. Apparent hydrogen isotope fractionations between source water and individual lipids (epsilon(lipid-water)) range from -62 per thousand (Metasequoia C(27) and C(29)) to -87 per thousand (Larix C(29)) in leaves under continuous light. We applied these hydrogen fractionation factors to hydrogen isotope compositions of in situ n-alkanes from well-preserved Paleogene deciduous conifer fossils from the Arctic region to estimate the deltaD value in ancient precipitation. Precipitation in the summer growing season yielded a deltaD of -186 per thousand for late Paleocene, -157 per thousand for early middle Eocene, and -182 per thousand for late middle Eocene. We propose that high-latitude summer precipitation in this region was supplemented by moisture derived from regionally recycled transpiration of the polar forests that grew during the Paleogene warming.

Estimating SGD flux in the Pingtung Plain coastal area by using Radon and Radium isotopes

NASA Astrophysics Data System (ADS)

Li Chang, Yao; Chieh Su, Chih

2015-04-01

In the past two decades, submarine groundwater discharge (SGD) has been recognized as an important pathway to transport material into coastal area. Our study area is located at Pingtung Plain which is the second largest plain in Taiwan with three major rivers, including Gaoping, Donggang and Linbian Rivers, flow through the plain. The Gaoping River, which has the largest drainage area, flows throughout the central part of the plain. The Pingtung Plain composed by four aquifers in different depths (0, 50, 100, and 200 m) and each layer extends to coastal area. Groundwater is an important water resource for local agriculture and aquaculture. However, the long-term over-pumping induced subsidence problem makes salinization at some coastal area. Some previous studies pointed out the SGD accounts for 80% or more of the mass of freshwater in Fangshan coast, depends on salinity and stable isotopes research. In this study, the radioactive tracers, Radon (222Rn, T1/2=3.8 d) and short-lived Ra isotopes (223Ra, T1/2=11.4 d & 224Ra, T1/2=3.6 d) are used in tracing SGD off the Pingtung Plain. During 2013 to 2014, the terrestrial water samples were collected from Gaoping, Donggang, Linbian Rivers and springs in different seasons. We also conducted two coastal waters cruises by using R/V Ocean Researcher 3 (OR3-1768 and 1799 cruises in May and September 2014). Continuous 222Rn was measured by RAD7 equipped with RAD-AQUA system and large volume (20 L) seawater samples were collected by CTD/Rosette water sampler with Niskin sterile bottles. Water samples were flow through Mn-fiber (flow rate < 1 LPM) to concentrate the Ra isotopes, and counted via RaDeCC system. In spatial variation, our result shows the excess 224Ra in the downstream of Gaoping River (2.39 dpm 100L-1) is higher than upstream (1.09 dpm 100L-1). It indicates the groundwater input may play an important role at the downstream of Gaoping River. For temporal variation, excess 224Ra in the Gaoping River are higher in wet season (May-August) than dry season (Nov-Feb). Furthermore, in some drainage area which groundwater recharged by shallow aquifer, the 222Rn and excess 224Ra will diluted by large rainfall in August. The analysis results from coastal waters shows the activities of radium isotopes in surface water are higher than bottom water. Compare with the data collected from Pingtung Plain, the radon and radium isotopes activities are also higher in wet season (OR3-1799 in Sep 2014). The highest excess 224Ra value (2.90 dpm 100L-1) is located at the offshore of Linbian River and it is much higher than the value in the Linbian River (0.54 dpm 100L-1, salinity 0.2) which collected in August 2014.

Long-term data set analysis of stable isotopic composition in German rivers

NASA Astrophysics Data System (ADS)

Reckerth, Anne; Stichler, Willibald; Schmidt, Axel; Stumpp, Christine

2017-09-01

Stable isotopes oxygen-18 (18O) and deuterium (2H) are commonly used to investigate hydrological processes in catchments. However, only a few isotope studies have been conducted on a large scale and rarely over long time periods. The objective of this study was to identify the spatial and seasonal variability of isotopic composition in river water and how it is affected by geographical and hydrological factors. The stable isotopic composition of river water has been measured in nine large river catchments in Germany for a time period of 12 years or 26 years. We conducted time series and correlation analyses to identify spatial and temporal patterns of the isotopic composition in the rivers. Further, we compared it to isotopic composition in local precipitation and catchments characteristics. In the majority of the rivers, the spatial and temporal patterns of precipitation were directly reflected in river water. The isotopic signals of the river water were time shifted and show attenuated amplitudes. Further deviations from isotopic compositions in local precipitation were observed in catchments with complex flow systems. These deviations were attributed to catchment processes and influences like evaporation, damming and storage. The seasonality of the isotopic composition was mainly determined by the discharge regimes of the rivers. We found correlations between isotopic long-term averages and catchment altitude as well as latitude and longitude, resulting in a northwest-southeast gradient. Furthermore, it was shown that long-term averages of d-excess were inversely related to flow length and catchment size, which indicates that evaporation enrichment has an impact on the isotopic composition even in catchments of humid climates. This study showed that isotopic composition in rivers can serve as a proxy for the local precipitation and can be utilized as an indicator for hydrological processes even in large river basins. In future, such long time series will help to also understand the impact of changes in the hydrological cycle on the larger scales. They can also be used for calibration and validation of flow and transport models at catchment and sub-catchment scale.

Variability of isotope and major ion chemistry in the Allequash Basin, Wisconsin

USGS Publications Warehouse

Walker, John F.; Hunt, Randall J.; Bullen, Thomas D.; Krabbenhoft, David P.; Kendall, Carol

2003-01-01

As part of ongoing research conducted at one of the U.S. Geological Survey's Water, Energy, and Biogeochem-ical Budgets sites, work was undertaken to describe the spatial and temporal variability of stream and ground water isotopic composition and cation chemistry in the Trout Lake watershed, to relate the variability to the watershed flow system, and to identify the linkages of geochemical evolution and source of water in the watershed. The results are based on periodic sampling of sites at two scales along Allequash Creek, a small headwater stream in northern Wisconsin. Based on this sampling, there are distinct water isotopic and geochemical differences observed at a smaller hillslope scale and the larger Allequash Creek scale. The variability was larger than expected for this simple watershed, and is likely to be seen in more complex basins. Based on evidence from multiple isotopes and stream chemistry, the flow system arises from three main source waters (terrestrial-, lake-, or wetland-derived recharge) that can be identified along any flowpath using water isotopes together with geochemical characteristics such as iron concentrations. The ground water chemistry demonstrates considerable spatial variability that depends mainly on the flow-path length and water mobility through the aquifer. Calcium concentrations increase with increasing flowpath length, whereas strontium isotope ratios increase with increasing extent of stagnation in either the unsaturated or saturated zones as waters move from source to sink. The flowpath distribution we identify provides important constraints on the calibration of ground water flow models such as that undertaken by Pint et al. (this issue).

Strontium isotope geochemistry of groundwater in the central part of the Dakota (Great Plains) aquifer, USA

USGS Publications Warehouse

Gosselin, D.C.; Harvey, F.E.; Frost, C.; Stotler, R.; Macfarlane, P.A.

2004-01-01

The Dakota aquifer of the central and eastern Great Plains of the United States is an important source of water for municipal supplies, irrigation and industrial use. Although the regional flow system can be characterized generally as east to northeasterly from the Rocky Mountains towards the Missouri River, locally the flow systems are hydrologically complex. This study uses Sr isotopic data from groundwater and leached aquifer samples to document the complex subsystems within the Dakota aquifer in Nebraska and Kansas. The interaction of groundwater with the geologic material through which it flows has created spatial patterns in the isotopic measurements that are related to: long-term water-rock interaction, during which varying degrees of isotopic equilibrium between water and rock has been achieved; and the alteration of NaCl fluids by water-rock interaction. Specifically, Sr isotopic data distinguish brines from Kansas and western Nebraska from those in eastern Nebraska: the former are interpreted to reflect interaction with Permian rocks, whereas the latter record interaction with Pennsylvanian rocks. The Sr isotopic composition of groundwater from other parts of Nebraska and Kansas are a function of the dynamic interaction between groundwater and unlithified sediments (e.g., glacial till and loess), followed by interaction with oxidized and unoxidized sediments within the Dakota Formation. This study illustrates the power of combining Sr chemistry with more conventional geochemical data to obtain a more complete understanding of groundwater flow systems within regional aquifer systems where extensive monitoring networks do not exist. ?? 2003 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Distinguishing sources of ground water recharge by using δ2H and δ18O

USGS Publications Warehouse

Blasch, Kyle W.; Bryson, Jeannie R.

2007-01-01

Stable isotope values of hydrogen and oxygen from precipitation and ground water samples were compared by using a volumetrically based mixing equation and stable isotope gradient to estimate the season and location of recharge in four basins. Stable isotopes were sampled at 11 precipitation sites of differing elevation during a 2-year period to quantify seasonal stable isotope contributions as a function of elevation. Supplemental stable isotope data collected by the International Atomic Energy Association during a 14-year period were used to reduce annual variability of the mean seasonal stable isotope data. The stable isotope elevation relationships and local precipitation elevation relationships were combined by using a digital elevation model to calculate the total volumetric contribution of water and stable isotope values as a function of elevation within the basins. The results of these precipitation calculations were compared to measured ground water stable isotope values at the major discharge points near the terminus of the basins. Volumetric precipitation contributions to recharge were adjusted to isolate contributing elevations. This procedure provides an improved representation of recharge contributions within the basins over conventional stable isotope methods. Stable isotope values from wells and springs at the terminus of each basin were used to infer the elevations of precipitation important for recharge of the regional ground water flow system. Ancillary climatic, geologic, and stable isotope values were used to further constrain the location where precipitation is entering the ground water flow system.

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.

Water budgets of Italian and Dutch gravel pit lakes: a study using a fen as a natural evaporation pan, stable isotopes and conservative tracer modeling.

NASA Astrophysics Data System (ADS)

Nella Mollema, Pauline; Antonellini, Marco

2015-04-01

Gravel pits are excavated in aquifers to fulfill the need for construction materials. Flow-through lakes form where the gravel pits are below the water table and fill with groundwater. Their presence changes the drainage patterns, water- and hydrochemical budgets of a watershed. We have studied the water budget of two gravel pit lakes systems using stable H and O isotopes of water as well as conservative tracer (Cl) modeling. The Dutch gravel pit lakes are a fluvial fresh water system of 70 lakes along the Meuse River and the Italian gravel pit lakes are a brackish system along the Adriatic coast. Surface water evaporation from the gravel pit lakes is larger than the actual evapotranspiration of the grass land and forests that were replaced. The ratio of evaporation to total flow into the Dutch lakes was determined by using a Fen as a natural evaporation pan: the isotope content of the Tuspeel Fen, filled with rain water and sampled in a dry and warm summer period (August 2012), is representative for the limiting isotopic enrichment under local hydro meteorological conditions. The Local Evaporation line (LEL) was determined δ2 H = 4.20 δ 18O - 14.10 (R² = 0.99) and the ratio of total inflow to evaporation for three gravel pit lakes were calculated to be 22.6 for the De Lange Vlieter lake used for drinking water production, 11.3 for the Boschmolen Lake and 8.9 for the Anna's Beemd lake showing that groundwater flow is much larger than evaporation. The Italian gravel pit lakes are characterized by high salinity (TDS = 4.6-12.3 g L-1). Stable isotope data show that these latter gravel pit lakes are fed by groundwater, which is a mix between fresh Apennine River water and brackish (Holocene) Adriatic Sea water. The local evaporation line is determined: δ2H = 5.02 δ18O - 10.49. The ratio of total inflow to evaporation is 5. Conservative tracer modeling indicates that the chloride concentration in the Italian gravel pit lakes stabilizes after a short period of rapid increase, because water leaving the lake via groundwater flow, driven by the drainage system, removes part of the Cl that accumulates in the lake due to evapo-concentration. Under climate change, rising sea levels and continuing land subsidence as well as increasing precipitation would increase the need for drainage which would enhance groundwater flow through the lake. The resulting steady-state Cl concentration of the lakes could become less than the current Cl concentration. This effect would be larger than increasing evapo- concentration. Both gravel pit lake systems have a large flux of groundwater into and out of the lakes driven by evaporation and (artificial) drainage with important consequences for the water- and hydrochemical budgets of the whole watershed and in particular on freshwater quantity and groundwater salinity.

Longitudinal dispersion coefficient depending on superficial velocity of hydrogen isotopes flowing in column packed with zeolite pellets at 77.4 K

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

Kotoh, K.; Graduate School of Engineering, Kyushu University, Nishi-ku, Fukuoka; Kubo, K.

2015-03-15

Authors have been developing a cryogenic pressure swing adsorption system for hydrogen isotope separation. In the problem of its design and operation, it is necessary to predict the concentration profiles developing in packed beds of adsorbent pellets. The profiling is affected by the longitudinal dispersion of gas flowing in packed beds, in addition to the mass transfer resistance in porous media of adsorbent pellets. In this work, an equation is derived for estimating the packed-bed dispersion coefficient of hydrogen isotopes, by analyzing the breakthrough curves of trace D{sub 2} or HD replacing H{sub 2} adsorbed in synthetic zeolite particles packedmore » columns at the liquefied nitrogen temperature 77.4 K. Since specialized for hydrogen isotopes, this equation can be considered to estimate the dispersion coefficients more reliable for the cryogenic hydrogen isotope adsorption process, than the existing equations. (authors)« less

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

Jamieson-Hanes, Julia H.; Shrimpton, Heather K.; Veeramani, Harish

A flow-through cell experiment was conducted to evaluate Zn isotope fractionation during ZnS precipitation under microbially-mediated sulfate-reducing conditions. Synthetic groundwater containing 0.90 mM Zn was pumped through a cell containing creek sediment that was biostimulated to promote sulfate reducing conditions. Real-time, in situ X-ray absorption spectroscopy (XAS) was applied at the Zn K-edge to collect spectra via a Kapton® window in the front of the cell over the course of the experiment. Aqueous effluent samples were collected and analysed to determine concentrations of anions and cations, and Zn isotope ratios. The flow rate was increased step-wise during the experiment tomore » modify the residence time and produce changes in the extent of sulfate reduction, which in turn controlled the extent of ZnS precipitation. Greater enrichment in the heavier isotope in the aqueous phase relative to the input solution was associated with more extensive Zn removal. A Rayleigh curve was fit to the isotope data, where ε = -0.27 ± 0.06‰ (2σ). Evaluation of Zn isotope fractionation under controlled flow conditions is critical to improve the efficacy of this powerful analytical technique when applied to natural systems or remediation projects in the field.« less

An integrated model for the natural flow regime in the Cerro Prieto hydrothermal system based upon petrological and isotope geochemical criteria

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

Elders, W.A.; Williams, A.E.; Hoagland, J..

1981-01-01

Studies of cuttings and cores at Cerro Prieto have now been extended to more than 50 boreholes. The aims of this petrological and isotopic work are to determine the shape of the reservoir, its physical properties, and its temperature distribution and flow regime before the steam field was produced.

Cadmium isotope fractionation during adsorption to Mn-oxyhydroxide

NASA Astrophysics Data System (ADS)

Wasylenki, L. E.; Swihart, J. W.

2013-12-01

The heavy metal cadmium is of interest both as a toxic contaminant in groundwater and as a critical nutrient for some marine diatoms [1], yet little is known about the biogeochemistry of this element. Horner et al. [2] suggested that Cd stable isotopes could potentially enable reconstruction of biological use of Cd in the marine realm: since cultured diatoms fractionate Cd isotopes [3], and ferromanganese crusts appear to incorporate a faithful record of deepwater Cd isotopes [2], depth profiles in such crusts may yield information about the extent of Cd assimilation of isotopically light Cd by diatoms over time. Although no work has yet been published regarding the use of stable isotopes to track reactive transport of Cd in contaminated aquifers, others have recently demonstrated the potential of isotopes to track reactions affecting the mobility of other toxic metals (e.g., [4]). With both of these potential applications in mind, we conducted two sets of experiments, at low and high ionic strength, in which Cd partially adsorbed to potassium birnessite. Our goals are to quantify the fractionations and to constrain the mechanisms governing Cd isotope behavior during adsorption to an environmentally abundant scavenger of Cd. Suspensions of synthetic birnessite were doped with various amounts of dissolved Cd2+ at pH ~8.3. Following reaction, the dissolved and adsorbed pools of Cd were separated by filtration, purified by anion exchange chromatography, and analyzed by multicollector ICP-MS using a double-spike routine. In all cases, lighter isotopes preferentially adsorbed to the birnessite particles. At low ionic strength (I<0.01m), we observed a small fractionation of 0.15‰×0.05 (Δ114/112) that was constant as a function of the fraction of Cd adsorbed. This indicates a small equilibrium isotope effect, likely driven by a subtle shift in coordination geometry for Cd during adsorption. In a groundwater system with continuous flow of dissolved Cd, this fractionation might manifest as an open system Rayleigh trend, with isotope signatures along the flow path reflecting the extent to which adsorption attenuates mobility of Cd. In simplified synthetic seawater (I=0.7m), the magnitude of fractionation decreases slightly with increasing proportion of Cd adsorbed, suggesting a kinetic or Rayleigh effect (irreversible sorption). A time series (1-192 hours) shows that the fractionation decreases from 0.3‰ to 0.2‰ over the course of 8 days. A longer experiment is underway to determine whether our study supports the observation of Horner et al. that Cd partitioned between deepwater and ferromanganese crusts is isotopically homogeneous [2]. The difference in Cd isotope behavior between low and high ionic strength conditions is likely due to different speciation of Cd in solution; chloro- complexes dominate Cd speciation in artificial seawater, while Cd2+ dominates at low ionic strength. [1] Price & Morel (1990) Nature 344, 658. [2] Horner et al (2010) G-cubed doi:10.1029/2009GC002987. [3] Lacan et al. (2006) Geochim. Cosmochim. Acta. 70, 5104. [4] Berna et al. (2010) Env. Sci. & Tech. 44, 1043.

Cotransport of hydroxyapatite nanoparticles and hematite colloids in saturated porous media: Mechanistic insights from mathematical modeling and phosphate oxygen isotope fractionation

NASA Astrophysics Data System (ADS)

Wang, Dengjun; Jin, Yan; Jaisi, Deb P.

2015-11-01

The fate and transport of individual type of engineered nanoparticles (ENPs) in porous media have been studied intensively and the corresponding mechanisms controlling ENPs transport and deposition are well-documented. However, investigations regarding the mobility of ENPs in the concurrent presence of another mobile colloidal phase such as naturally occurring colloids (colloid-mediated transport of ENPs) are largely lacking. Here, we investigated the cotransport and retention of engineered hydroxyapatite nanoparticles (HANPs) with naturally occurring hematite colloids in water-saturated sand columns under environmentally relevant transport conditions, i.e., pH, ionic strength (IS), and flow rate. Particularly, phosphate oxygen isotope fractionation of HANPs during cotransport was explored at various ISs and flow rates to examine the mechanisms controlling the isotope fractionation of HANPs in abiotic transport processes (physical transport). During cotransport, greater mobility of both HANPs and hematite occurred at higher pHs and flow rates, but at lower ISs. Intriguingly, the mobility of both HANPs and hematite was substantially lower during cotransport than the individual transport of either, attributed primarily to greater homo- and hetero-aggregation when both particles are copresent in the suspension. The shapes of breakthrough curves (BTCs) and retention profiles (RPs) during cotransport for both particles evolved from blocking to ripening with time and from flat to hyperexponential with depth, respectively, in response to decreases in pH and flow rate, and increases in IS. The blocking BTCs and RPs that are flat or hyperexponential can be well-approximated by a one-site kinetic attachment model. Conversely, a ripening model that incorporates attractive particle-particle interaction has to be employed to capture the ripening BTCs that are impacted by particle aggregation during cotransport. A small phosphate oxygen isotope fractionation (≤ 1.8‰) occurred among HANPs populations during cotransport responding to IS and flow rate changes. This fractionation is most likely a result of hetero-aggregation between hematite and HANPs that favors light phosphate isotopes (P16O4). This interpretation is further supported by the increase in isotope fractionation at higher ISs (i.e., greater aggregation). However, the fractionation was progressively erased by decreasing flow rate, ascribed to the reduced mass transfer of HANPs between the influent and effluent. Together our findings suggest that the cotransport and retention of HANPs and hematite colloids are highly sensitive to the considered physicochemical factors, and isotope tracing could serve as a promising tool to identify the sources and transport of phosphate-based NPs in complex subsurface environments due to insignificant transport-related isotope fractionation.

Pico-CSIA: Picomolar Scale Compound-Specific Isotope Analyses

NASA Astrophysics Data System (ADS)

Baczynski, A. A.; Polissar, P. J.; Juchelka, D.; Schwieters, J. B.; Hilkert, A.; Freeman, K. H.

2016-12-01

The basic approach to analyzing molecular isotopes has remained largely unchanged since the late 1990s. Conventional compound-specific isotope analyses (CSIA) are conducted using capillary gas chromatography (GC), a combustion interface, and an isotope-ratio mass spectrometer (IRMS). Commercially available GC-IRMS systems are comprised of components with inner diameters ≥0.25 mm and employ helium flow rates of 1-4 mL/min. These flow rates are an order of magnitude larger than what the IRMS can accept. Consequently, ≥90% of the sample is lost through the open split, and 1-10s of nanomoles of carbon are required for analysis. These sample requirements are prohibitive for many biomarkers, which are often present in picomolar concentrations. We utilize the resolving power and low flows of narrow-bore capillary GC to improve the sensitivity of CSIA. Narrow bore capillary columns (<0.25 mm ID) allow low helium flow rates of ≤0.5mL/min for more efficient sample transfer to the ion source of the IRMS while maintaining the high linear flow rates necessary to preserve narrow peak widths ( 250 ms). The IRMS has been fitted with collector amplifiers configured to 25 ms response times for rapid data acquisition across narrow peaks. Previous authors (e.g., Sacks et al., 2007) successfully demonstrated improved sensitivity afforded by narrow-bore GC columns. They reported an accuracy and precision of 1.4‰ for peaks with an average width at half maximum of 720 ms for 100 picomoles of carbon on column. Our method builds on their advances and further reduces peak widths ( 600 ms) and the amount of sample lost prior to isotopic analysis. Preliminary experiments with 100 picomoles of carbon on column show an accuracy and standard deviation <1‰. With further improvement, we hope to demonstrate robust isotopic analysis of 10s of picomoles of carbon, more than 2 orders of magnitude lower than commercial systems. The pico-CSIA method affords high-precision isotopic analyses for picomoles of carbon in organic biomarkers, which significantly lowers sample size requirements and broadens analytical windows in paleoclimate, astrobiological, and biogeochemical research.

Partitioning groundwater recharge between rainfall infiltration and irrigation return flows using stable isotopes: the Crau aquifer.

NASA Astrophysics Data System (ADS)

Seraphin, Pierre; Vallet-Coulomb, Christine; Gonçalvès, Julio

2016-04-01

Traditional flood irrigation is used since the 16th century in the Crau plain (Southern France) for hay production. To supply this high consuming irrigation practice, water is diverted from the Durance River, originating from the Alps, and the large amount of irrigation return flows constitutes the main recharge of the Crau aquifer, which is in turn largely exploited for domestic, industrial and agricultural water use. A possible reduction of irrigation fluxes due to a need of water saving or to a future land-use change could endanger the groundwater resource. A robust quantification of the groundwater mass balance is thus required to assess a sustainable water management in the region. The high isotopic contrast between these exogenous irrigation waters and local precipitations allows the use of stable isotopes of water as conservative tracers to deduce their contributions to the surface recharge. An extensive groundwater sampling was performed to obtain δ18O and δ2H over the whole aquifer. Based on a new piezometric contour map, combined with a reestimate of the aquifer geometry, the isotopic data are implemented in a geostatistical approach to produce a conceptual equivalent-homogeneous reservoir, in order to apply a simple water and isotope mass balance mixing model. The isotopic composition of the two end-members is assessed, and the quantification of groundwater flows is then used to calculate the two recharge fluxes. Near to steady-state condition, the set of isotopic data treated by geostatistics leads to a recharge by irrigation of 5.20 ± 0.93 m3 s-1 i.e. 1173 ± 210 mm yr-1, and a natural recharge of 2.26 ± 0.91 m3 s-1 i.e. 132 ± 53 mm yr-1. Thus, 70 ± 9% of the effective surface recharge comes from the irrigation return flow, consistent with the literature (between 67% and 78%). This study constitutes a straightforward and independent approach to assess groundwater surface recharges with uncertainties and will help to constrain a future transient groundwater flow model of the Crau aquifer.

Sediment Tracking Using Carbon and Nitrogen Stable Isotopes

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A.

2002-12-01

As landscapes are stripped of valuable, nutrient rich topsoils and streams are clouded with habitat degrading fine sediment, it becomes increasingly important to identify and mitigate erosive surfaces. Particle tracking using vegetative derived carbon (C) and nitrogen (N) isotopic signatures and carbon/nitrogen (C/N) atomic ratios offer a promising technique to identify such problematic sources. Consultants and researchers successfully use C, N, and other stable isotopes of water for hydrologic purposes, such as quantifying groundwater vs. surface water contribution to a hydrograph. Recently, C and N isotopes and C/N atomic ratios of sediment were used to determine sediment mass balance within estuarine environments. The current research investigates C and N isotopes and C/N atomic ratios of source sediment for two primary purposes: (1) to establish a blueprint methodology for estimating sediment source and erosion rates within a watershed using this isotopic technology coupled with mineralogy fingerprinting techniques, radionuclide transport monitoring, and erosion-transport models, and (2) to complete field studies of upland erosion processes, such as, solifluction, mass wasting, creep, fluvial erosion, and vegetative induced erosion. Upland and floodplain sediment profiles and riverine suspended sediment were sampled on two occasions, May 2002 and August 2002, in the upper Palouse River watershed of northern Idaho. Over 300 samples were obtained from deep intermountain valley (i.e. forest) and rolling crop field (i.e. agriculture) locations. Preliminary sample treatment was completed at the Washington State University Water Quality Laboratory where samples were dried, removed of organic constituents, and prepared for isotopic analysis. C and N isotope and C/N atomic ratio analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. Results indicate distinct N isotopic signatures and C/N atomic ratios for forest and agriculture sediment sources. In addition, unique C and N isotopic signatures and C/N atomic ratios exist within floodplain and upland surfaces, and within the 10 centimeter profiles of erosion and deposition locations. Suspended sediment analyses are preliminary at this time. Conclusions indicate that sediment C and N isotopic signature and C/N atomic ratio are dependent upon land use and soil moisture conditions, and will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

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.

Tracing Carbon Flow Through Food Webs on Isolated Coral Reefs in the Central Pacific Ocean Using a Compound-Specific Stable Isotope Approach

NASA Astrophysics Data System (ADS)

Thorrold, S.; McMahon, K.; Braun, C.; Berumen, M. L.; Houghton, L. A.

2016-02-01

Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world's oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column or benthic primary production and recycled detrital carbon. We coupled analyses of stable carbon isotopes in essential amino acids with Bayesian mixing models to quantify carbon flow from pelagic primary producers, benthic macroalgae and autotrophic symbionts in corals, along with detrital carbon, to coral reef fishes across several feeding guilds and trophic positions, including apex predators (gray reef and black tip reef sharks), on reefs in the Phoenix Islands Protected Area. Excellent separation in multivariate isotope space among end-members at the base of the food web allowed us to quantify the relative proportion of carbon produced by each of the end-members that is assimilated by focal reef fish species. Low local human impacts on the study reefs provided the opportunity to examine carbon fluxs in fully functioning reef food webs, thereby providing an important baseline for examingn human impacts in food webs on stressed reefs in more populated regions in the tropics. Moreover the study reefs are located along a significant gradient in dissolved N concentrations, allowing us to test if end-member proportions vary as a function of pelagic primary productivity levels. Our work provides insights into the roles that diverse carbon sources may play in the structure, function and resilience of coral reef ecosystems.

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.

Recent advances in understanding atmospheric CO based on stable isotope measurements

NASA Astrophysics Data System (ADS)

Popa, Maria Elena; Naus, Stijn; Ferrero Lopez, Noelia; Vijverberg, Sem; de Leeuw, Selma; Röckmann, Thomas

2017-04-01

Carbon monoxide (CO) plays an important role for atmospheric chemistry and for carbon cycling in the atmosphere. Via its reaction with the OH radical it influences concentrations of many other trace gases, it is an important precursor for O3 formation, and its oxidation leads to the formation of about 1 Pg C per year of CO2. The natural and anthropogenic sources of CO are subject to relatively large temporal changes due to natural variability (e.g. biomass burning), industrial activity and mitigation measures (e.g. fossil fuel burning), variations in precursor compounds (e.g. CH4 and VOC) and variations in the abundance of the OH radical in the atmosphere, which are difficult to quantify. Isotope measurements can be used to distinguish between the effects of individual sources and sinks to put tighter constrains on its budget, but the isotopic characterization of the CO sources is in many cases still based on a few relatively old measurements that did not allow to account for dependence on parameters. We will present an update of the isotopic composition of several sources and removal processes of CO that have been carried out in the past years with the automated continuous-flow IRMS system at Utrecht University. This includes: - the previously unknown isotopic composition of direct biogenic CO emissions - a surprisingly large variability in the isotopic composition of CO emitted by different vehicles and single vehicles under various driving conditions - previously very poorly investigated signatures, like the fractionation in the removal of CO by soils, and its interaction with CO that is simultaneously emitted from soil. These results from process specific investigations will be linked to recent atmospheric measurements at various locations.

METHOD FOR REMOVAL OF LIGHT ISOTOPE PRODUCT FROM LIQUID THERMAL DIFFUSION UNITS

DOEpatents

Hoffman, J.D.; Ballou, J.K.

1957-11-19

A method and apparatus are described for removing the lighter isotope of a gaseous-liquid product from a number of diffusion columns of a liquid thermal diffusion system in two stages by the use of freeze valves. The subject liquid flows from the diffusion columns into a heated sloping capsule where the liquid is vaporized by the action of steam in a heated jacket surrounding the capsule. When the capsule is filled the gas flows into a collector. Flow between the various stages is controlled by freeze valves which are opened and closed by the passage of gas and cool water respectively through coils surrounding portions of the pipes through which the process liquid is passed. The use of the dual stage remover-collector and the freeze valves is an improvement on the thermal diffusion separation process whereby the fraction containing the lighter isotope many be removed from the tops of the diffusion columns without intercolumn flow, or prior stage flow while the contents of the capsule is removed to the final receiver.

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

PubMed

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

2017-07-01

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

Evaluating the Duration and Continuity of Potential Climate Records From the Allan Hills Blue Ice Area, East Antarctica

NASA Astrophysics Data System (ADS)

Kehrl, Laura; Conway, Howard; Holschuh, Nicholas; Campbell, Seth; Kurbatov, Andrei V.; Spaulding, Nicole E.

2018-05-01

The current ice core record extends back 800,000 years. Geologic and glaciological evidence suggests that the Allan Hills Blue Ice Area, East Antarctica, may preserve a continuous record that extends further back in time. In this study, we use ice-penetrating radar and existing age constraints to map the internal stratigraphy and age structure of the Allan Hills Main Ice Field. The dated isochrones provide constraints for an ice flow model to estimate the age of ice near the bed. Previous drilling in the region recovered stratigraphically disturbed sections of ice up to 2.7 million years old. Our study identifies a site 5 km upstream, which likely preserves a continuous record through Marine Isotope Stage 11 with the possibility that the record extends back 1 million years. Such records would provide new insight into the past climate and glacial history of the Ross Sea Sector.

An isotope hydrology study of the Kilauea volcano area, Hawaii

USGS Publications Warehouse

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

1995-01-01

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

Automated determination of the stable carbon isotopic composition (δ13C) of total dissolved inorganic carbon (DIC) and total nonpurgeable dissolved organic carbon (DOC) in aqueous samples: RSIL lab codes 1851 and 1852

USGS Publications Warehouse

Révész, Kinga M.; Doctor, Daniel H.

2014-01-01

The purposes of the Reston Stable Isotope Laboratory (RSIL) lab codes 1851 and 1852 are to determine the total carbon mass and the ratio of the stable isotopes of carbon (δ13C) for total dissolved inorganic carbon (DIC, lab code 1851) and total nonpurgeable dissolved organic carbon (DOC, lab code 1852) in aqueous samples. The analysis procedure is automated according to a method that utilizes a total carbon analyzer as a peripheral sample preparation device for analysis of carbon dioxide (CO2) gas by a continuous-flow isotope ratio mass spectrometer (CF-IRMS). The carbon analyzer produces CO2 and determines the carbon mass in parts per million (ppm) of DIC and DOC in each sample separately, and the CF-IRMS determines the carbon isotope ratio of the produced CO2. This configuration provides a fully automated analysis of total carbon mass and δ13C with no operator intervention, additional sample preparation, or other manual analysis. To determine the DIC, the carbon analyzer transfers a specified sample volume to a heated (70 °C) reaction vessel with a preprogrammed volume of 10% phosphoric acid (H3PO4), which allows the carbonate and bicarbonate species in the sample to dissociate to CO2. The CO2 from the reacted sample is subsequently purged with a flow of helium gas that sweeps the CO2 through an infrared CO2 detector and quantifies the CO2. The CO2 is then carried through a high-temperature (650 °C) scrubber reactor, a series of water traps, and ultimately to the inlet of the mass spectrometer. For the analysis of total dissolved organic carbon, the carbon analyzer performs a second step on the sample in the heated reaction vessel during which a preprogrammed volume of sodium persulfate (Na2S2O8) is added, and the hydroxyl radicals oxidize the organics to CO2. Samples containing 2 ppm to 30,000 ppm of carbon are analyzed. The precision of the carbon isotope analysis is within 0.3 per mill for DIC, and within 0.5 per mill for DOC.

Environmental isotope investigation of groundwater flow in the Honey Lake Basin, California and Nevada

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

Rose, T.P.; Davisson, M.L.; Hudson, G.B.

The hydrology of Honey Lake Basin was studied using environmental isotope measurements of approximately 130 water samples collected during 1995 and 1996. The principal analytical methods included hydrogen, oxygen and carbon stable isotope ratio measurements, radiocarbon and tritium dating, and measurements of dissolved noble gas abundances.

Use of flow cytometry and stable isotope analysis to determine phytoplankton uptake of wastewater derived ammonium in a nutrient-rich river

NASA Astrophysics Data System (ADS)

Schmidt, Calla M.; Kraus, Tamara E. C.; Young, Megan B.; Kendall, Carol

2018-01-01

Anthropogenic alteration of the form and concentration of nitrogen (N) in aquatic ecosystems is widespread. Understanding availability and uptake of different N sources at the base of aquatic food webs is critical to establishment of effective nutrient management programs. Stable isotopes of N (14N, 15N) are often used to trace the sources of N fueling aquatic primary production, but effective use of this approach requires obtaining a reliable isotopic ratio for phytoplankton. In this study, we tested the use of flow cytometry to isolate phytoplankton from bulk particulate organic matter (POM) in a portion of the Sacramento River, California, during river-scale nutrient manipulation experiments that involved halting wastewater discharges high in ammonium (NH4+). Field samples were collected using a Lagrangian approach, allowing us to measure changes in phytoplankton N source in the presence and absence of wastewater-derived NH4+. Comparison of δ15N-POM and δ15N-phytoplankton (δ15N-PHY) revealed that their δ15N values followed broadly similar trends. However, after 3 days of downstream travel in the presence of wastewater treatment plant (WWTP) effluent, δ15N-POM and δ15N-PHY in the Sacramento River differed by as much as 7 ‰. Using a stable isotope mixing model approach, we estimated that in the presence of effluent between 40 and 90 % of phytoplankton N was derived from NH4+ after 3 days of downstream transport. An apparent gradual increase over time in the proportion of NH4+ in the phytoplankton N pool suggests that either very low phytoplankton growth rates resulted in an N turnover time that exceeded the travel time sampled during this study, or a portion of the phytoplankton community continued to access nitrate even in the presence of elevated NH4+ concentrations.

Use of flow cytometry and stable isotope analysis to determine phytoplankton uptake of wastewater derived ammonium in a nutrient-rich river

USGS Publications Warehouse

Schmidt, Calla M.; Kraus, Tamara; Young, Megan B.; Kendall, Carol

2018-01-01

Anthropogenic alteration of the form and concentration of nitrogen (N) in aquatic ecosystems is widespread. Understanding availability and uptake of different N sources at the base of aquatic food webs is critical to establishment of effective nutrient management programs. Stable isotopes of N (14N, 15N) are often used to trace the sources of N fueling aquatic primary production, but effective use of this approach requires obtaining a reliable isotopic ratio for phytoplankton. In this study, we tested the use of flow cytometry to isolate phytoplankton from bulk particulate organic matter (POM) in a portion of the Sacramento River, California, during river-scale nutrient manipulation experiments that involved halting wastewater discharges high in ammonium (NH4+). Field samples were collected using a Lagrangian approach, allowing us to measure changes in phytoplankton N source in the presence and absence of wastewater-derived NH4+. Comparison of δ15N-POM and δ15N-phytoplankton (δ15N-PHY) revealed that their δ15N values followed broadly similar trends. However, after 3 days of downstream travel in the presence of wastewater treatment plant (WWTP) effluent, δ15N-POM and δ15N-PHY in the Sacramento River differed by as much as 7 ‰. Using a stable isotope mixing model approach, we estimated that in the presence of effluent between 40 and 90 % of phytoplankton N was derived from NH4+ after 3 days of downstream transport. An apparent gradual increase over time in the proportion of NH4+ in the phytoplankton N pool suggests that either very low phytoplankton growth rates resulted in an N turnover time that exceeded the travel time sampled during this study, or a portion of the phytoplankton community continued to access nitrate even in the presence of elevated NH4+ concentrations.

Modeling stable isotope transport in metamorphic and hydrothermal systems

NASA Astrophysics Data System (ADS)

Baumgartner, L. P.; Mueller, T.; Skora, S.; Begue, F.

2007-12-01

Stable isotopes are powerful tools for deciphering the fluid flow histories of metamorphic terrains. The nature of fluid flow, fluid sources, and fluid fluxes can be delineated in well constrained studies. Continuum mechanics models for stable isotope fluid-rock exchange were developed and used over the last three decades in an attempt to accurately interpret the signatures left behind by fluid flow in the earths crust. The efforts have been hampered by the realization that the exchange of many stable isotopes, e.g. oxygen and carbon, by intracrystalline diffusion, hence without re-organization of the crystal lattice, appears to be too slow to achieve significant exchange. This should lead to relatively flat isotopic exchange profiles on hand-, outcrop, or aureole scale. Nevertheless, isotopic fronts are typically sharp (sub mm to cm scale), when measured in the field. This has lead to the suggestion that these sharp fronts correspond to the sides of infiltration fronts, implying the data to have been collected at a high angle to the infiltration direction. Nevertheless, the fact that the oxygen and carbon fronts are located at the same place is not explained by this. A review of published carbon and oxygen data reveals that many contact aureoles show linear trends in oxygen-carbon isotope ratio diagrams for carbonate sample suits. This implies that the fluid composition infiltrating the aureoles had essentially an X(CO2) of 0.5. This is in contrast to skarn mineralogy developed, which requires a water-rich fluid, in agreement with the general notion that igneous fluids are water-rich. These and other observations indicate that the mass transport equation used for stable isotope exchange needs to be improved to model appropriately the actual isotope kinetics during fluid-rock exchange. Detailed isotope studies on systems where net transport reactions are driven by mass transport have led us to identify different exchange mechanisms, including: a) the stable isotope exchange is given by instantaneous mass balance written for the isotope during reaction; b) equilibrium precipitation of products, but slow exchange kinetics for reactants. These observations require that the reactive term in the stable isotope reactive transport equation is re-written to include the net transfer reactions, which in turn implies the solution of the transport equation for the elements driving the reaction.

Infiltration and hydraulic connections from the Niagara River to a fractured-dolomite aquifer in Niagara Falls, New York

USGS Publications Warehouse

Yager, R.M.; Kappel, W.M.

1998-01-01

The spatial distribution of hydrogen and oxygen stable-isotope values in groundwater can be used to distinguish different sources of recharge and to trace groundwater flow directions from recharge boundaries. This method can be particularly useful in fractured-rock settings where multiple lines of evidence are required to delineate preferential flow paths that result from heterogeneity within fracture zones. Flow paths delineated with stable isotopes can be combined with hydraulic data to form a more complete picture of the groundwater flow system. In this study values of ??D and ??18O were used to delineate paths of river-water infiltration into the Lockport Group, a fractured dolomite aquifer, and to compute the percentage of fiver water in groundwater samples from shallow bedrock wells. Flow paths were correlated with areas of high hydraulic diffusivity in the shallow bedrock that were delineated from water-level fluctuations induced by diurnal stage fluctuations in man-made hydraulic structures. Flow paths delineated with the stable-isotope and hydraulic data suggest that fiver infiltration reaches an unlined storm sewer in the bedrock through a drainage system that surrounds aqueducts carrying river water to hydroelectric power plants. This finding is significant because the storm sewer is the discharge point for contaminated groundwater from several chemical waste-disposal sites and the cost of treating the storm sewer's discharge could be reduced if the volume of infiltration from the river were decreased.The spatial distribution of hydrogen and oxygen stable-isotope values in groundwater can be used to distinguish different sources of recharge and to trace groundwater flow directions from recharge boundaries. This method can be particularly useful in fractured-rock settings where multiple lines of evidence are required to delineate preferential flow paths that result from heterogeneity within fracture zones. Flow paths delineated with stable isotopes can be combined with hydraulic data to form a more complete picture of the groundwater flow system. In this study values of ??D and ??18O were used to delineate paths of river-water infiltration into the Lockport Group, a fractured dolomite aquifer, and to compute the percentage of river water in groundwater samples from shallow bedrock wells. Flow paths were correlated with areas of high hydraulic diffusivity in the shallow bedrock that were delineated from water-level fluctuations induced by diurnal stage fluctuations in man-made hydraulic structures. Flow paths delineated with the stable-isotope and hydraulic data suggest that river infiltration reaches an unlined storm sewer in the bedrock through a drainage system that surrounds aqueducts carrying river water to hydroelectric power plants. This finding is significant because the storm sewer is the discharge point for contaminated groundwater from several chemical waste-disposal sites and the cost of treating the storm sewer's discharge could be reduced if the volume of infiltration from the river were decreased.

Isotopic constraints on the cooling of the continental lithosphere

NASA Astrophysics Data System (ADS)

Bedini, R.-M.; Blichert-Toft, J.; Boyet, M.; Albarède, F.

2004-06-01

A new model of continuous diffusion of radiogenic isotopes was applied to mineral 147Sm- 143Nd and 176Lu- 176Hf data on low-temperature garnet-peridotite xenoliths from Cretaceous South African kimberlites. The radiometric ages are younger than the Archean whole-rock Re-Os and U-Pb ages and reflect that both the Sm-Nd and Lu-Hf chronometric systems remained open under the thermal conditions of the lithospheric mantle. The radiogenic character of Hf in garnets, however, indicates that even if essentially no pyroxene remained immune to the effects of metasomatic events, the core of many garnets may preserve memory of the long history of this mineral in the subcontinental lithosphere. The cooling rates deduced from the garnet Sm-Nd ages in the South African lithosphere are fairly low (40-105 °C Gy -1), but compare well with values obtained on similar samples from different regions. These unexpectedly low values imply that the heat flow at the base of the subcontinental lithospheric mantle has changed only very slowly through time. They further support the recent suggestion that, as a result of viscous dissipation by plate bending, convection vigor and heat flow are to some extent decoupled, which argues against a thermal feedback on geodynamics. Modern convection may still be mining fossil heat stored in the lower mantle.

Changes in Holocene to LGM water mass stratification near Southern Africa inferred from Nd isotopes

NASA Astrophysics Data System (ADS)

Jones, K. M.; Goldstein, S. L.; Hemming, S. R.; Hall, I. R.; Zahn, R.

2009-12-01

Global thermohaline circulation (THC) is an important component of the climate system that initiates or amplifies abrupt climate change. A major driver of THC is the formation of North Atlantic Deep Water (NADW), which is sandwiched by northward flowing Southern Ocean water masses as it is advected southward. An important exit route of NADW out of the South Atlantic is through flow around the southern tip of Africa, which makes the South African Margin an excellent location to investigate changes in THC and water mass stratification through time. We measured the Nd isotopes of modern seawater from three depth profiles collected along the South African Margin, which were collected on RSS Charles Darwin Cruise 154. All seawater profiles show a similar pattern with higher ɛNd values at intermediate depths (ɛNd ~ -9.5 at 600-1200m), lower values for the core of NADW (ɛNd ~ -11.5 at 2000-3500m), and higher values in the deepest waters sampled (ɛNd -9.8 at 4150m). This pattern is consistent with conservative mixing of major North Atlantic and Southern Ocean end-member water masses and is not consistent with inputs from, or exchange with margin sediments, for most depths. We also measured the Nd isotopes of multiple sedimentary archives in proximal Holocene coretop sediments collected from depths spanning intermediate to deep/bottom waters. The Nd isotopes of a fish tooth, several foram coating leachates, and multiple bulk sediment Fe-Mn leachates display the same pattern as the local seawater. We had no seawater for comparison with our deepest core (VM19-224; depth ~ 4600m), but the eNd value from it (ɛNd = -8.4) is consistent with Antarctic Bottom Water (ɛNd ~ -8.5). These results suggest: (1) that Nd isotopes of seawater in the region behave conservatively; (2) that the local margin sediments faithfully record the Nd isotope composition of the waters they are bathed in and (3) this “ground-truthing” implies that it is valid to use Nd isotopes as a circulation proxy in this region to reconstruct THC and water mass stratification along this margin through time. Nd isotopes were also measured on bulk sediment and foram coating Fe-Mn leachates of radiocarbon dated LGM sediments. The leachate Nd isotope composition of the deepest sample (VM19-224; ɛNd = -7.0) is within error of LGM samples from RC11-83 in the Cape Basin (depth ~ 4700m; ɛNd = -6.6). Cores from shallower depths (2800 to 3600m) are also offset toward higher higher ɛNd consistent with weaker NADW. The shallowest core (VM14-77; depth ~ 1800m) displays an opposite shift from higher values in the Holocene (ɛNd = -9.9) to lower values during the LGM (ɛNd = -12.0). However, this core is in the region of the Tugela River Cone and may be impacted by that river. These data are consistent with a significant reduction of NADW export to the Southern Ocean during the LGM but the LGM value of the shallowest core is also consistent with the shoaling of NADW during this time interval as it continued to flow out of the Atlantic.

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

NASA Astrophysics Data System (ADS)

Millot, R.; Widory, D.; Innocent, C.; Guerrot, C.; Bourrain, X.; Johnson, T. M.

2012-12-01

The contribution of human activities such as industries, agriculture and domestic inputs, becomes more and more significant in the chemical composition (major ions and pollutants such as metals) of the dissolved load of rivers. Furthermore, this influence can also be evidenced in the suspended solid matter known to play an important role in the transport of heavy metals through river systems. Human factors act as a supplementary key process. Therefore the mass-balance for the budget of catchments and river basins include anthropogenic disturbances. The Loire River in central France is approximately 1010 km long and drains an area of 117,800 km2. Initially, the Loire upstream flows in a south to north direction originating in the Massif Central, and continues up to the city of Orléans, 650 km from the source. In the upper basin, the bedrock is old plutonic rock overlain by much younger volcanic rocks. The Loire River then follows a general east to west direction to the Atlantic Ocean. The intermediate basin includes three major tributaries flowing into the Loire River from the left bank: the Cher, the Indre and the Vienne rivers; the main stream flows westward and its valley stretches toward the Atlantic Ocean. Here, the Loire River drains the sedimentary series of the Paris Basin, mainly carbonate deposits. The lower Loire basin drains pre-Mesozoic basement of the Armorican Massif and its overlying Mesozoic to Cenozoic sedimentary deposits. The Loire River is one of the main European riverine inputs to the Atlantic ocean. Here we are reporting concentration and isotope data for heavy metals Zn-Cd-Pb-Hg in river waters and suspended sediments from the Loire River Basin. In addition, we also report concentration and isotope data for these metals for the different industrial sources within the Loire Basin, as well as data for biota samples such as mussels and oysters from the Bay of Biscay and North Brittany. These organisms are known to be natural accumulators of metal pollutants. The main objective of this study is to characterize the sources and the behavior of these heavy metals in the aquatic environment, and their spatial distribution using a multi-isotope approach. Each of these isotope systematics on their own reveals important information about their geogenic or anthropogenic origin but, considered together, provide a more integrated understanding of the budgets of these pollutants within the Loire River Basin.

Geochemical and Isotopic Variations Along the Southeast Indian Ridge (126°-140°E) Related to Mantle Flow Originating from Beneath Antarctica

NASA Astrophysics Data System (ADS)

Hanan, B. B.; Graham, D. W.; Hemond, C.; Dufour, F.; Briais, A.; Ceuleneer, G.; Maia, M.; Park, S. H.; Revillon, S.; Yang, Y. S.

2017-12-01

We present data for glassy basalts from 37 localities along the spreading axis of the Southeast Indian Ridge (SEIR) between 126°-140°E, eastward of the Australian-Antarctic Discordance (AAD). Each of the five ridge segments (A1 to A5, west to east) show well-defined major element trends. An isotopic and negative axial depth anomaly is present, centered on the overlapping tips of segments A3 and A4 at 135°E. Segment A4 basalts have distinct radiogenic Pb and He isotopes plus enriched MORB-like ɛHf, relative to segments to the west and east. Crystal fractionation is more extensive at the A3 and A5 overlapping segment tips adjacent to A4, and decreases both to the west and east. The along axis pattern suggests a mantle heterogeneity located beneath the A3-A4 segments. Pb-Pb isotopic co-variations for the 5 segments define two linear arrays, with a western trend (A1-A3) and an eastern trend (A4-A5) that intersects it at the composition of the anomalous A4 segment, at a 206Pb/204Pb 19. The western trend has higher 208Pb/204Pb for a given 206Pb/204Pb, revealing a gradient in the asthenosphere, with Δ208Pb/204Pb decreasing to the east away from the AAD. Overall, 206,207,208Pb/204Pb and 4He/3He of the A4 anomaly define trends that vector toward the fields for Cenozoic lavas from west Antarctica (Marie Byrd Land and Balleny Islands). West Antarctica has a history of mantle plume underplating and lithosphere modification by subduction [1,2], and there is a broad seismic anomaly below 250 km underlying the West Antarctic Rift system [3]. Our data supports a model in which flow of underplated material plus lithosphere may be guided by the underside topography of the lithosphere beneath the Transantarctic mountains. This flow emerges from beneath east Antarctica, where it leads to volcanism in the Balleny Islands [4]. The material apparently continues to flow northward to the SEIR at 135°E. The geochemical anomaly beneath Zone A is potentially explained by the presence of this residual plume/mobilized lithospheric material in the subridge mantle of the SEIR. [1] Hart et al., 1997, Chem Geol 139; [2] Aviado et al. 2015, G3 16; [3] Moelli and Danesi, 2004, GPC 42; [4] Sleep, 2006, ESR 77.

Silicon Isotope Fractionation by Banana Under Continuous Nutrient and Silica Flux

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Cardinal, D.; Henriet, C.; Delvaux, B.; André, L.

2004-12-01

Silicon is absorbed by plants as aqueous H4SiO4 with other essential nutrients, and precipitates in aerial parts of the plant as phytolith, a biogenic opal. Phytoliths are restored to the soil by decomposition of organic debris from plant material. The role of higher plants in the biogeochemical cycle of silicon is therefore major although it is still poorly studied. Biomineralization processes are known to fractionate the three stable silicon isotopes with a preferential uptake of light isotopes. Therefore, following some preliminary results from Douthitt (1982), and studies presented in recent conferences (Ziegler et al., 2002; Ding et al., 2003), we suspect that phytolith production by plants could also fractionate the silicon isotopes. Inversely, intensity of phytolith-related isotopic fractionations might contribute to a better understanding of the soil-plant silicon cycle. Our study focused on banana, a silicon accumulating plant (>1% Si, dry weight).Musa acuminata cv Grande Naine has been grown in hydroponics under controlled conditions (light, temperature, humidity, nutrients) during six weeks. The nutrient supply was kept constant: three batches of five plants were grown with a continuous nutrient solution flow of 5, 50 and 100 ppm SiO2 respectively. Si isotopic compositions were measured in the source solution, and in silica extracted from the various parts of banana (roots, pseudostems, midribs and petioles, leaves), using a Nu Plasma multicollector mass spectrometer (MC-ICP-MS) operating in dry plasma mode. The results are expressed as δ 29Si relatively to the NBS28 standard, with an average precision of ± 0.03‰ . Silicon contents and morphological studies of phytoliths were also achieved. Banana δ 29Si varied between -0.18 and -0.76‰ with a source solution at -0.02‰ . Values of δ 29Si were less fractionated, relatively to the nutrient solution, in roots, where no phytoliths have been observed until now, than in upper parts of banana where phytoliths were clearly abundant as long chain of typical cone shaped morphotypes truncated saddle-like. The bulk isotopic composition of the leaves in the five plants grown at 100 ppm SiO2 displayed a homogeneous negative signature (-0.44 ± 0.08‰ ) indicating a small inter-specimen variability. The difference between δ 29Si in roots and in upper parts of the plant was much larger with a silica offer of 100 ppm SiO2 (0.58‰ ) than with 50 ppm SiO2 (0.08‰ ). However, silicon isotope fractionation in leaves was not affected by a change in Si supply. Our preliminary results show that biomineralization of silica in bananas fractionates silicon isotopes in a similar extent as marine diatoms.

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

DOE PAGES

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

2014-12-31

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

The Most Useful Actinide Isotope: Americium-241.

ERIC Educational Resources Information Center

Navratil, James D.; And Others

1990-01-01

Reviewed is the discovery, nuclear and chemical properties, and uses of an isotope of Americium (Am-241). Production and separation techniques used in industry are emphasized. Processes are illustrated in flow sheets. (CW)

The influence of microclimates and fog on stable isotope signatures used in interpretation of regional hydrology: East Maui, Hawaii

USGS Publications Warehouse

Scholl, M.A.; Gingerich, S.B.; Tribble, G.W.

2002-01-01

Stable isotopes of precipitation, ground water and surface water measured on the windward side of East Maui from 0 to 3055 m altitude were used to determine recharge sources for stream flow and ground water. Correct interpretation of the hydrology using rainfall ??18O gradients with altitude required consideration of the influence of fog, as fog samples had isotopic signatures enriched by as much as 3??? in ??18O and 21??? in ??D compared to volume-weighted average precipitation at the same altitude. The isotopic analyses suggested that fog drip was a major component of stream flow and shallow ground water at higher altitudes in the watershed. 18O/altitude gradients in rainfall were comparable for similar microclimates on Maui (this study) and Hawaii Island (1990-1995 study), however, East Maui ??18O values for rain in trade-wind and high-altitude microclimates were enriched compared to those from Hawaii Island. Isotopes were used to interpret regional hydrology in this volcanic island aquifer system. In part of the study area, stable isotopes indicate discharge of ground water recharged at least 1000 m above the sample site. This deep-flowpath ground water was found in springs from sea level up to 240 m altitude, indicating saturation to altitudes much higher than a typical freshwater lens. These findings help in predicting the effects of ground water development on stream flow in the area. Published by Elsevier Science B.V.

Arctic Marine Water Isotope Characteristics: In-situ, Continuous Surface and Water Column Isoscapes (δ18O and δ2H) and Linkages into the Marine Food Web

NASA Astrophysics Data System (ADS)

Welker, J. M.; Klein, E. S.; Collins, E.; Iken, K.; Hopcroft, R. R.; Norcross, B.

2016-12-01

The Arctic is under going rapid and profound sea ice, temperature, food web, ocean current, precipitation and synoptic weather changes. Delineating these changes requires a suite of tools, especially those that have the ability to depict the interactive nature of the marine system. Understanding the marine water isotope cycle is paramount to recognizing the unique isotopic properties of this region and to characterize possibly the reorganization of the Arctic. The Arctic marine water isotope system has been primarily examined with shore-based stations and or episodic station sampling; without continuous surface water sampling in combination with station-specific water column and organismic measurements. New technologies that allow in situ and continuous water isotope measurements (vapor and liquid) and the integration of inorganic and organic water isotope geochemistry provide a means to reveal in more detail the fundamental traits of the Arctic marine water isotope system. In July and August of 2016, we are measuring seawater surface (8 m depth) isotopes (δ18O and δ2H) in-situ and continuously (Picarro CWS system) along a research transect (60oN to 77oN) from the Gulf of Alaska to the Arctic Ocean Basin. These continuous surface water isotope measurements are being combined with periodic water column isotope profiling and corresponding organic δ18O and δ2H measurements of pelagic and benthic organisms (microbes to fish) to depths of up to 2600m. We measured surface seawater δ18O that from -1‰ to -6‰; while seawater profiles followed vertical separation in the water column; possibly reflecting divergent currents of the Arctic. Station based δ18O and δ2H values of surface water did not vary by more than 1‰ δ18O over the course of our 24-36 hour sampling periods. The δ18O and δ2H values of marine organism throughout the water column and by trophic level will be analyzed and a seawater-food web model will be developed in addition to surface and water column isoscapes. Our Arctic marine water isotope cycle research is providing the most detailed depiction ever of the western Arctic and sub-Arctic surface water, water column and marine food web O/H isotope properties. Our findings will provide an important new understanding of the Arctic and the high definition of its water isotope cycle.

Meteoritic Sulfur Isotopic Analysis

NASA Technical Reports Server (NTRS)

Thiemens, Mark H.

1996-01-01

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

Stable isotope composition (δ(13)C and δ(15)N values) of slime molds: placing bacterivorous soil protozoans in the food web context.

PubMed

Tiunov, Alexei V; Semenina, Eugenia E; Aleksandrova, Alina V; Tsurikov, Sergey M; Anichkin, Alexander E; Novozhilov, Yuri K

2015-08-30

Data on the bulk stable isotope composition of soil bacteria and bacterivorous soil animals are required to estimate the nutrient and energy fluxes via bacterial channels within detrital food webs. We measured the isotopic composition of slime molds (Myxogastria, Amoebozoa), a group of soil protozoans forming macroscopic spore-bearing fruiting bodies. An analysis of largely bacterivorous slime molds can provide information on the bulk stable isotope composition of soil bacteria. Fruiting bodies of slime molds were collected in a monsoon tropical forest of Cat Tien National Park, Vietnam, and analyzed by continuous-flow isotope ratio mass spectrometry. Prior to stable isotope analysis, carbonates were removed from a subset of samples by acidification. To estimate the trophic position of slime molds, their δ(13) C and δ(15) N values were compared with those of plant debris, soil, microbial destructors (litter-decomposing, humus-decomposing, and ectomycorrhizal fungi) and members of higher trophic levels (oribatid mites, termites, predatory macroinvertebrates). Eight species of slime molds represented by at least three independent samples were 3-6‰ enriched in (13) C and (15) N relative to plant litter. A small but significant difference in the δ(13) C and δ(15) N values suggests that different species of myxomycetes can differ in feeding behavior. The slime molds were enriched in (15) N compared with litter-decomposing fungi, and depleted in (15) N compared with mycorrhizal or humus-decomposing fungi. Slime mold sporocarps and plasmodia largely overlapped with oribatid mites in the isotopic bi-plot, but were depleted in (15) N compared with predatory invertebrates and humiphagous termites. A comparison with reference groups of soil organisms suggests strong trophic links of slime molds to saprotrophic microorganisms which decompose plant litter, but not to humus-decomposing microorganisms or to mycorrhizal fungi. Under the assumption that slime molds are primarily feeding on bacteria, the isotopic similarity of slime molds and mycophagous soil animals indicates that saprotrophic soil bacteria and fungi are similar in bulk isotopic composition. Copyright © 2015 John Wiley & Sons, Ltd.

An Improved Extraction and Analysis Technique for Determination of Carbon Monoxide Stable Isotopes and Mixing Ratios from Ice Core and Atmospheric Air Samples.

NASA Astrophysics Data System (ADS)

Place, P., Jr.; Petrenko, V. V.; Vimont, I.

2017-12-01

Carbon Monoxide (CO) is an important atmospheric trace gas that affects the oxidative capacity of the atmosphere and contributes indirectly to anthropogenic radiative forcing. Carbon monoxide stable isotopes can also serve as a tracer for variations in biomass burning, particularly in the preindustrial atmosphere. A good understanding of the past variations in CO mole fractions and isotopic composition can help improve the skill of chemical transport models and constrain biomass burning changes. Ice cores may preserve a record of past atmospheric CO for analysis and interpretation. To this end, a new extraction system has been developed for analysis of stable isotopes (δ13CO and δC18O) of atmospheric carbon monoxide from ice core and atmospheric air samples. This system has been designed to measure relatively small sample sizes (80 cc STP of air) to accommodate the limited availability of ice core samples. Trapped air is extracted from ice core samples via melting in a glass vacuum chamber. This air is expanded into a glass expansion loop and then compressed into the sample loop of a Reducing Gas Detector (Peak Laboratories, Peak Performer 1 RCP) for the CO mole fraction measurement. The remaining sample gas will be expelled from the melt vessel into a larger expansion loop via headspace compression for isotopic analysis. The headspace compression will be accomplished by introduction of clean degassed water into the bottom of the melt vessel. Isotopic analysis of the sample gas is done utilizing the Schütze Reagent to convert the carbon monoxide to carbon dioxide (CO2) which is then measured using continuous-flow isotope ratio mass spectrometry (Elementar Americas, IsoPrime 100). A series of cryogenic traps are used to purify the sample air, capture the converted sample CO2, and cryofocus the sample CO2 prior to injection.

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.

A Review of Flow Analysis Methods for Determination of Radionuclides in Nuclear Wastes and Nuclear Reactor Coolants

DOE PAGES

Trojanowicz, Marek; Kolacinska, Kamila; Grate, Jay W.

2018-02-13

Here, the safety and security of nuclear power plant operations depend on the application of the most appropriate techniques and methods of chemical analysis, where modern flow analysis methods prevail. Nevertheless, the current status of the development of these methods is more limited than it might be expected based on their genuine advantages. The main aim of this paper is to review the automated flow analysis procedures developed with various detection methods for the nuclear energy industry. The flow analysis methods for the determination of radionuclides, that have been reported to date, are primarily focused on their environmental applications. Themore » benefits of the application of flow methods in both monitoring of the nuclear wastes and process analysis of the primary circuit coolants of light water nuclear reactors will also be discussed. The application of either continuous flow methods (CFA) or injection methods (FIA, SIA) of the flow analysis with the β–radiometric detection shortens the analysis time and improves the precision of determination due to mechanization of certain time-consuming operations of the sample processing. Compared to the radiometric detection, the mass spectrometry (MS) detection enables one to perform multicomponent analyses as well as the determination of transuranic isotopes with much better limits of detection.« less

A Review of Flow Analysis Methods for Determination of Radionuclides in Nuclear Wastes and Nuclear Reactor Coolants

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

Trojanowicz, Marek; Kolacinska, Kamila; Grate, Jay W.

Here, the safety and security of nuclear power plant operations depend on the application of the most appropriate techniques and methods of chemical analysis, where modern flow analysis methods prevail. Nevertheless, the current status of the development of these methods is more limited than it might be expected based on their genuine advantages. The main aim of this paper is to review the automated flow analysis procedures developed with various detection methods for the nuclear energy industry. The flow analysis methods for the determination of radionuclides, that have been reported to date, are primarily focused on their environmental applications. Themore » benefits of the application of flow methods in both monitoring of the nuclear wastes and process analysis of the primary circuit coolants of light water nuclear reactors will also be discussed. The application of either continuous flow methods (CFA) or injection methods (FIA, SIA) of the flow analysis with the β–radiometric detection shortens the analysis time and improves the precision of determination due to mechanization of certain time-consuming operations of the sample processing. Compared to the radiometric detection, the mass spectrometry (MS) detection enables one to perform multicomponent analyses as well as the determination of transuranic isotopes with much better limits of detection.« less

A review of flow analysis methods for determination of radionuclides in nuclear wastes and nuclear reactor coolants.

PubMed

Trojanowicz, Marek; Kołacińska, Kamila; Grate, Jay W

2018-06-01

The safety and security of nuclear power plant operations depend on the application of the most appropriate techniques and methods of chemical analysis, where modern flow analysis methods prevail. Nevertheless, the current status of the development of these methods is more limited than it might be expected based on their genuine advantages. The main aim of this paper is to review the automated flow analysis procedures developed with various detection methods for the nuclear energy industry. The flow analysis methods for the determination of radionuclides, that have been reported to date, are primarily focused on their environmental applications. The benefits of the application of flow methods in both monitoring of the nuclear wastes and process analysis of the primary circuit coolants of light water nuclear reactors will also be discussed. The application of either continuous flow methods (CFA) or injection methods (FIA, SIA) of the flow analysis with the β-radiometric detection shortens the analysis time and improves the precision of determination due to mechanization of certain time-consuming operations of the sample processing. Compared to the radiometric detection, the mass spectrometry (MS) detection enables one to perform multicomponent analyses as well as the determination of transuranic isotopes with much better limits of detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Partitioning groundwater recharge between rainfall infiltration and irrigation return flow using stable isotopes: The Crau aquifer

NASA Astrophysics Data System (ADS)

Séraphin, Pierre; Vallet-Coulomb, Christine; Gonçalvès, Julio

2016-11-01

This study reports an assessment of the water budget of the Crau aquifer (Southern France), which is poorly referenced in the literature. Anthropogenically controlled by a traditional irrigation practice, this alluvial type aquifer requires a robust quantification of the groundwater mass balance in order to establish sustainable water management in the region. In view of the high isotopic contrast between exogenous irrigation waters and local precipitations, stable isotopes of water can be used as conservative tracers to deduce their contributions to the surface recharge. Extensive groundwater sampling was performed to obtain δ18O and δ2H over the whole aquifer. Based on a new piezometric contour map, combined with an updated aquifer geometry, the isotopic data were implemented in a geostatistical approach to produce a conceptual equivalent homogeneous reservoir. This makes it possible to implement a parsimonious water and isotope mass-balance mixing model. The isotopic compositions of the two end-members were assessed, and the quantification of groundwater flows was then used to calculate the two recharge fluxes (natural and irrigation). Nearly at steady-state, the set of isotopic data treated by geostatistics gave a recharge by irrigation of 4.92 ± 0.89 m3 s-1, i.e. 1109 ± 202 mm yr-1, and a natural recharge of 2.19 ± 0.85 m3 s-1, i.e. 128 ± 50 mm yr-1. Thus, 69 ± 9% of the surface recharge is caused by irrigation return flow. This study constitutes a straightforward and independent approach to assess groundwater surface recharges including uncertainties and will help to constrain future transient groundwater models of the Crau aquifer.

Experimental investigation of concentration and stable isotopes signals during organic contaminants back diffusion

NASA Astrophysics Data System (ADS)

Jin, Biao; Nika, Chrysanthi-Elisabeth; Rolle, Massimo

2017-04-01

Back diffusion of organic contaminants is often the cause of groundwater plumes' persistence and can significantly hinder cleanup interventions [1, 2]. In this study we perform a high-resolution investigation of back diffusion in a well-controlled flow-through laboratory setup. We considered cis-dichloroethene (cis-DCE) as model contaminant and we investigated its back diffusion from an impermeable source into a permeable saturated layer, in which advection-dominated flow conditions were established. We used concentration and stable chlorine isotope measurements to investigate the plumes originated by cis-DCE back diffusion in a series of flow-through experiments, performed in porous media with different hydraulic conductivity and at different seepage velocities (i.e., 0.4, 0.8 and 1.2 m/day). A two-centimeter thick agarose gel layer was placed at the bottom of the setup to simulate the source of cis-DCE back diffusion from an impervious layer. Intensive sampling (>1000 measurements) was carried out, including the withdrawal of aqueous samples at closely spaced (1 cm) outlet ports, as well as the high-resolution sampling of the source zone (agarose gel) at the end of each experiment. The transient behavior of the plumes originated by back diffusion was investigated by sampling the outlet ports at regular intervals in the experiments, each run for a total time corresponding to 15 pore volumes. The high-resolution sampling allowed us to resolve the spatial and temporal evolution of concentration and stable isotope gradients in the flow-through setup. In particular, steep concentration and stable isotope gradients were observed at the outlet. Lateral isotope gradients corresponding to chlorine isotope fractionation up to 20‰ were induced by cis-DCE back diffusion and subsequent advection-dominated transport in all flow-through experiments. A numerical modeling approach, tracking individually all chlorine isotopologues, based on the accurate parameterization of local dispersion, as well as on the values of aqueous diffusion coefficients and diffusion-induced isotope fractionation from a previous study [3], provided a good agreement with the experimental data. References [1] Mackay, D. M.; Cherry, J. A. Groundwater contamination: Pumpand-treat remediation. Environ. Sci. Technol. 1989, 23, 630-636. [2] Parker, B. L.; Chapman, S. W.; Guilbeault, M. A. Plume persistence caused by back diffusion from thin clay layers in a sand aquifer following TCE source-zone hydraulic isolation. J. Contam. Hydrol. 2008, 102, 19-19. [3] Jin, B., Rolle, M., Li, T., Haderlein, S.B., 2014. Diffusive fractionation of BTEX and chlorinated ethenes in aqueous solution: quantification of spatial isotope gradients. Environ. Sci. Technol. 48, 6141-6150.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

21 CFR 886.1670 - Ophthalmic isotope uptake probe.

Code of Federal Regulations, 2014 CFR

2014-04-01

... 21 Food and Drugs 8 2014-04-01 2014-04-01 false Ophthalmic isotope uptake probe. 886.1670 Section... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1670 Ophthalmic isotope uptake probe. (a) Identification. An ophthalmic isotope uptake probe is an AC-powered device intended to measure...

21 CFR 886.1670 - Ophthalmic isotope uptake probe.

Code of Federal Regulations, 2013 CFR

2013-04-01

... 21 Food and Drugs 8 2013-04-01 2013-04-01 false Ophthalmic isotope uptake probe. 886.1670 Section... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1670 Ophthalmic isotope uptake probe. (a) Identification. An ophthalmic isotope uptake probe is an AC-powered device intended to measure...

21 CFR 886.1670 - Ophthalmic isotope uptake probe.

Code of Federal Regulations, 2012 CFR

2012-04-01

... 21 Food and Drugs 8 2012-04-01 2012-04-01 false Ophthalmic isotope uptake probe. 886.1670 Section... (CONTINUED) MEDICAL DEVICES OPHTHALMIC DEVICES Diagnostic Devices § 886.1670 Ophthalmic isotope uptake probe. (a) Identification. An ophthalmic isotope uptake probe is an AC-powered device intended to measure...

Continuous and scalable polymer capsule processing for inertial fusion energy target shell fabrication using droplet microfluidics.

PubMed

Li, Jin; Lindley-Start, Jack; Porch, Adrian; Barrow, David

2017-07-24

High specification, polymer capsules, to produce inertial fusion energy targets, were continuously fabricated using surfactant-free, inertial centralisation, and ultrafast polymerisation, in a scalable flow reactor. Laser-driven, inertial confinement fusion depends upon the interaction of high-energy lasers and hydrogen isotopes, contained within small, spherical and concentric target shells, causing a nuclear fusion reaction at ~150 M°C. Potentially, targets will be consumed at ~1 M per day per reactor, demanding a 5000x unit cost reduction to ~$0.20, and is a critical, key challenge. Experimentally, double emulsions were used as templates for capsule-shells, and were formed at 20 Hz, on a fluidic chip. Droplets were centralised in a dynamic flow, and their shapes both evaluated, and mathematically modeled, before subsequent shell solidification. The shells were photo-cured individually, on-the-fly, with precisely-actuated, millisecond-length (70 ms), uniform-intensity UV pulses, delivered through eight, radially orchestrated light-pipes. The near 100% yield rate of uniform shells had a minimum 99.0% concentricity and sphericity, and the solidification processing period was significantly reduced, over conventional batch methods. The data suggest the new possibility of a continuous, on-the-fly, IFE target fabrication process, employing sequential processing operations within a continuous enclosed duct system, which may include cryogenic fuel-filling, and shell curing, to produce ready-to-use IFE targets.

Tritium monitor

DOEpatents

Chastagner, Philippe

1994-01-01

A system for continuously monitoring the concentration of tritium in an aqueous stream. The system pumps a sample of the stream to magnesium-filled combustion tube which reduces the sample to extract hydrogen gas. The hydrogen gas is then sent to an isotope separation device where it is separated into two groups of isotopes: a first group of isotopes containing concentrations of deuterium and tritium, and a second group of isotopes having substantially no deuterium and tritium. The first group of isotopes containing concentrations of deuterium and tritium is then passed through a tritium detector that produces an output proportional to the concentration of tritium detected. Preferably, the detection system also includes the necessary automation and data collection equipment and instrumentation for continuously monitoring an aqueous stream.

Tritium monitor

DOEpatents

Chastagner, P.

1994-06-14

A system is described for continuously monitoring the concentration of tritium in an aqueous stream. The system pumps a sample of the stream to magnesium-filled combustion tube which reduces the sample to extract hydrogen gas. The hydrogen gas is then sent to an isotope separation device where it is separated into two groups of isotopes: a first group of isotopes containing concentrations of deuterium and tritium, and a second group of isotopes having substantially no deuterium and tritium. The first group of isotopes containing concentrations of deuterium and tritium is then passed through a tritium detector that produces an output proportional to the concentration of tritium detected. Preferably, the detection system also includes the necessary automation and data collection equipment and instrumentation for continuously monitoring an aqueous stream. 1 fig.

The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

NASA Astrophysics Data System (ADS)

Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

2016-04-01

Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

Tracing carbon flow through coral reef food webs using a compound-specific stable isotope approach.

PubMed

McMahon, Kelton W; Thorrold, Simon R; Houghton, Leah A; Berumen, Michael L

2016-03-01

Coral reefs support spectacularly productive and diverse communities in tropical and sub-tropical waters throughout the world's oceans. Debate continues, however, on the degree to which reef biomass is supported by new water column production, benthic primary production, and recycled detrital carbon (C). We coupled compound-specific stable C isotope ratio (δ(13)C) analyses with Bayesian mixing models to quantify C flow from primary producers to coral reef fishes across multiple feeding guilds and trophic positions in the Red Sea. Analyses of reef fishes with putative diets composed primarily of zooplankton (Amblyglyphidodon indicus), benthic macroalgae (Stegastes nigricans), reef-associated detritus (Ctenochaetus striatus), and coral tissue (Chaetodon trifascialis) confirmed that δ(13)C values of essential amino acids from all baseline C sources were both isotopically diagnostic and accurately recorded in consumer tissues. While all four source end-members contributed to the production of coral reef fishes in our study, a single-source end-member often dominated dietary C assimilation of a given species, even for highly mobile, generalist top predators. Microbially reworked detritus was an important secondary C source for most species. Seascape configuration played an important role in structuring resource utilization patterns. For instance, Lutjanus ehrenbergii showed a significant shift from a benthic macroalgal food web on shelf reefs (71 ± 13 % of dietary C) to a phytoplankton-based food web (72 ± 11 %) on oceanic reefs. Our work provides insights into the roles that diverse C sources play in the structure and function of coral reef ecosystems and illustrates a powerful fingerprinting method to develop and test nutritional frameworks for understanding resource utilization.

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Precipitation induced stream flow: An event based chemical and isotopic study of a small stream in the Great Plains region of the USA

USGS Publications Warehouse

Machavaram, M.V.; Whittemore, Donald O.; Conrad, M.E.; Miller, N.L.

2006-01-01

A small stream in the Great Plains of USA was sampled to understand the streamflow components following intense precipitation and the influence of water storage structures in the drainage basin. Precipitation, stream, ponds, ground-water and soil moisture were sampled for determination of isotopic (D, 18O) and chemical (Cl, SO4) composition before and after two intense rain events. Following the first storm event, flow at the downstream locations was generated primarily through shallow subsurface flow and runoff whereas in the headwaters region - where a pond is located in the stream channel - shallow ground-water and pond outflow contributed to the flow. The distinct isotopic signatures of precipitation and the evaporated pond water allowed separation of the event water from the other sources that contributed to the flow. Similarly, variations in the Cl and SO4 concentrations helped identify the relative contributions of ground-water and soil moisture to the streamflow. The relationship between deuterium excess and Cl or SO4 content reveals that the early contributions from a rain event to streamflow depend upon the antecedent climatic conditions and the position along the stream channel within the watershed. The design of this study, in which data from several locations within a watershed were collected, shows that in small streams changes in relative contributions from ground water and soil moisture complicate hydrograph separation, with surface-water bodies providing additional complexity. It also demonstrates the usefulness of combined chemical and isotopic methods in hydrologic investigations, especially the utility of the deuterium excess parameter in quantifying the relative contributions of various source components to the stream flow. ?? 2006 Elsevier B.V. All rights reserved.

Unraveling of permafrost hydrological variabilities on Central Qinghai-Tibet Plateau using stable isotopic technique.

PubMed

Yang, Yuzhong; Wu, Qingbai; Hou, Yandong; Zhang, Zhongqiong; Zhan, Jing; Gao, Siru; Jin, Huijun

2017-12-15

Permafrost degradation on the Qinghai-Tibet Plateau (QTP) will substantially alter the surface runoff discharge and generation, which changes the recharge processes and influences the hydrological cycle on the QTP. Hydrological connections between different water bodies and the influence of thawing permafrost (ground ice) are not well understood on the QTP. This study applied water stable isotopic method to investigate the permafrost hydrological variabilities in Beiluhe Basin (BLB) on Central QTP. Isotopic variations of precipitation, river flow, thermokarst lake, and near-surface ground ice were identified to figure out the moisture source of them, and to elaborate the hydrological connections in permafrost region. Results suggested that isotopic seasonalities in precipitation is evident, it is showing more positive values in summer seasons, and negative values in winter seasons. Stable isotopes of river flow are mainly distributed in the range of precipitation which is indicative of important replenishment from precipitation. δ 18 O, δD of thermokarst lakes are more positive than precipitation, indicating of basin-scale evaporation of lake water. Comparison of δ I values in different water bodies shows that hydrology of thermokarst lakes was related to thawing of permafrost (ground ice) and precipitation. Near-surface ground ice in BLB exhibits different isotopic characteristics, and generates a special δD-δ 18 O relationship (freezing line): δD=5.81δ 18 O-23.02, which reflects typical freezing of liquid water. From isotopic analysis, it is inferred that near-surface ground ice was mainly recharged by precipitation and active layer water. Stable isotopic and conceptual model is suggestive of striking hydrological connections between precipitation, river flow, thermokarst lake, and ground ice under degrading permafrost. This research provides fundamental comprehensions into the hydrological processes in permafrost regions on QTP, which should be considered in investigating the influence of thawing permafrost on the hydrological cycle on QTP. Copyright © 2017 Elsevier B.V. All rights reserved.

Evaporation and abstraction determined from stable isotopes during normal flow on the Gariep River, South Africa

NASA Astrophysics Data System (ADS)

Diamond, Roger E.; Jack, Sam

2018-04-01

Changes in the stable isotope composition of water can, with the aid of climatic parameters, be used to calculate the quantity of evaporation from a water body. Previous workers have mostly focused on small, research catchments, with abundant data, but of limited scope. This study aimed to expand such work to a regional or sub-continental scale. The first full length isotope survey of the Gariep River quantifies evaporation on the river and the man-made reservoirs for the first time, and proposes a technique to calculate abstraction from the river. The theoretically determined final isotope composition for an evaporating water body in the given climate lies on the empirically determined local evaporation line, validating the assumptions and inputs to the Craig-Gordon evaporation model that was used. Evaporation from the Gariep River amounts to around 20% of flow, or 40 m3/s, of which about half is due to evaporation from the surface of the Gariep and Vanderkloof Reservoirs, showing the wastefulness of large surface water impoundments. This compares well with previous estimates based on evapotranspiration calculations, and equates to around 1300 GL/a of water, or about the annual water consumption of Johannesburg and Pretoria, where over 10 million people reside. Using similar evaporation calculations and applying existing transpiration estimates to a gauged length of river, the remaining quantity can be attributed to abstraction, amounting to 175 L/s/km in the lower middle reaches of the river. Given that high water demand and climate change are global problems, and with the challenges of maintaining water monitoring networks, stable isotopes are shown to be applicable over regional to national scales for modelling hydrological flows. Stable isotopes provide a complementary method to conventional flow gauging for understanding hydrology and management of large water resources, particularly in arid areas subject to significant evaporation.

Isotope specific arbitrary material flow meter

DOEpatents

Barty, Christopher P. J.; Post, John C.; Jones, Edwin

2016-10-25

A laser-based mono-energetic gamma-ray source is used to provide non-destructive and non-intrusive, quantitative determination of the absolute amount of a specific isotope contained within pipe as part of a moving fluid or quasi-fluid material stream.

Methane seeps along boundaries of receding glaciers in Alaska and Greenland

NASA Astrophysics Data System (ADS)

Walter Anthony, K. M.; Anthony, P. M.; Grosse, G.; Chanton, J.

2012-12-01

Glaciers, ice sheets, and permafrost form a 'cryosphere cap' that traps methane formed in the subsurface, restricting its flow to the Earth's surface and atmosphere. Despite model predictions that glacier melt and degradation of permafrost open conduits for methane's escape, there has been a paucity of field evidence for 'subcap' methane seepage to the atmosphere as a direct result of cryosphere disintegration in the terrestrial Arctic. Here, we document for the first time the release of sub-cryosphere methane to lakes, rivers, shallow marine fjords and the atmosphere from abundant gas seeps concentrated along boundaries of receding glaciers and permafrost thaw in Alaska and Greenland. Through aerial and ground surveys of 6,700 lakes and fjords in Alaska we mapped >150,000 gas seeps identified as bubbling-induced open holes in seasonal ice. Using gas flow rates, stable isotopes, and radiocarbon dating, we distinguished recent ecological methane from subcap, geologic methane. Subcap seeps had anomalously high bubbling rates, 14C-depletion, and stable isotope values matching microbial sources associated with sedimentary deposits and coal beds as well as thermogenic methane accumulations in Alaska. Since differential ice loading can overpressurize fluid reservoirs and cause sediment fracturing beneath ice sheets, and since the loss of glacial ice reduces normal stress on ground, opens joints, and activates faults and fissures, thereby increasing permeability of the crust to fluid flow, we hypothesized that in the previously glaciated region of Southcentral Alaska, where glacial wastage continues presently, subcap seeps should be disproportionately associated with neotectonic faults. Geospatial analysis confirmed that subcap seep sites were associated with faults within a 7 km belt from the modern glacial extent. The majority of seeps were located in areas affected by seismicity from isostatic rebound associated with deglaciation following the Little Ice Age (LIA; ca. 1650-1850 C.E.). Across Alaska, we found a relationship between methane stable isotopes, radiocarbon age, and distance to faults. Faults appear to allow the escape of deeper, more 14C-depleted methane to the atmosphere, whereas seeps away from faults entrained 14C-enriched methane formed in shallower sediments from microbial decomposition of younger organic matter. Additionally, we observed younger subcap methane seeps in lakes of Greenland's Sondrestrom Fjord that were associated with ice-sheet retreat since the LIA. These correlations suggest that in a warming climate, continued disintegration of glaciers, permafrost, and parts of the polar ice sheets will weaken subsurface seals and further open conduits, allowing a transient expulsion of methane currently trapped by the cryosphere cap.

Asthenospheric outflow from the shrinking Philippine Sea Plate: Evidence from Hf-Nd isotopes of southern Mariana lavas

NASA Astrophysics Data System (ADS)

Ribeiro, Julia M.; Stern, Robert J.; Martinez, Fernando; Woodhead, Jon; Chen, Min; Ohara, Yasuhiko

2017-11-01

At subduction zones, sinking of the downgoing lithosphere is thought to enable a return flow of asthenospheric mantle around the slab edges, so that the asthenosphere from underneath the slab invades the ambient mantle flowing underneath the volcanic arc and the backarc basin. For instance at the northern end of the Lau Basin, trench retreat and slab rollback enable toroidal return flow of Samoan mantle beneath a transform margin to provide a supply of fresh, undepleted Indian mantle that feeds the backarc spreading center. Questions, however, arise about the sense of mantle flow when plate kinematics predict that the trench is advancing, as seen in the Mariana convergent margin. Does the mantle flow in or does it escape outward through slab tears or gaps? Here, we address the origin and sense of asthenospheric mantle flow supplying the southern Mariana convergent margin, a region of strong extension occurring above the subducting Pacific plate. Does the asthenosphere flow northward, from underneath the Pacific plate and Caroline hotspot through a slab tear or gap, or does it flow outward from the Mariana Trough, which possesses a characteristic Indian Ocean isotopic signature? To address these questions, we integrate geodetic data along with new Hf-Nd isotopic data for fresh basaltic lavas from three tectonic provinces in the southernmost Marianas: the Fina Nagu volcanic complex, the Malaguana-Gadao backarc spreading ridge and the SE Mariana forearc rift. Our results indicate that Indian mantle flows outward and likely escapes through slab tears or gaps to accommodate shrinking of the Philippine Sea plate. We thus predict that asthenospheric flow around the Pacific slab at the southern Mariana Trench is opposite to that predicted by most subduction-driven mantle flow models.

A new organic reference material, L-glutamic acid, USGS41a, for δ13C and δ15N measurements − a replacement for USGS41

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Mroczkowski, Stanley J.; Brand, Willi A.; Brandes, Lauren; Geilmann, Heike; Schimmelmann, Arndt

2016-01-01

RationaleThe widely used l-glutamic acid isotopic reference material USGS41, enriched in both 13C and 15N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41.MethodsUSGS41a was prepared by dissolving analytical grade l-glutamic acid enriched in 13C and 15N together with l-glutamic acid of normal isotopic composition. The δ13C and δ15N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate (δ13CVPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate (δ13CVPDB = −46.6 mUr), and IAEA-N-1 ammonium sulfate (δ15NAir = +0.43 mUr) and USGS32 potassium nitrate (δ15N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry.ResultsUSGS41a is isotopically homogeneous; the reproducibility of δ13C and δ15N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ13C value of +36.55 mUr relative to VPDB and a δ15N value of +47.55 mUr relative to N2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41.ConclusionsThe new isotopic reference material USGS41a can be used with USGS40 (having a δ13CVPDB value of −26.39 mUr and a δ15NAir value of −4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

A new organic reference material, l-glutamic acid, USGS41a, for δ(13) C and δ(15) N measurements - a replacement for USGS41.

PubMed

Qi, Haiping; Coplen, Tyler B; Mroczkowski, Stanley J; Brand, Willi A; Brandes, Lauren; Geilmann, Heike; Schimmelmann, Arndt

2016-04-15

The widely used l-glutamic acid isotopic reference material USGS41, enriched in both (13) C and (15) N, is nearly exhausted. A new material, USGS41a, has been prepared as a replacement for USGS41. USGS41a was prepared by dissolving analytical grade l-glutamic acid enriched in (13) C and (15) N together with l-glutamic acid of normal isotopic composition. The δ(13) C and δ(15) N values of USGS41a were directly or indirectly normalized with the international reference materials NBS 19 calcium carbonate (δ(13) CVPDB = +1.95 mUr, where milliurey = 0.001 = 1 ‰), LSVEC lithium carbonate (δ(13) CVPDB = -46.6 mUr), and IAEA-N-1 ammonium sulfate (δ(15) NAir = +0.43 mUr) and USGS32 potassium nitrate (δ(15) N = +180 mUr exactly) by on-line combustion, continuous-flow isotope-ratio mass spectrometry, and off-line dual-inlet isotope-ratio mass spectrometry. USGS41a is isotopically homogeneous; the reproducibility of δ(13) C and δ(15) N is better than 0.07 mUr and 0.09 mUr, respectively, in 200-μg amounts. It has a δ(13) C value of +36.55 mUr relative to VPDB and a δ(15) N value of +47.55 mUr relative to N2 in air. USGS41 was found to be hydroscopic, probably due to the presence of pyroglutamic acid. Experimental results indicate that the chemical purity of USGS41a is substantially better than that of USGS41. The new isotopic reference material USGS41a can be used with USGS40 (having a δ(13) CVPDB value of -26.39 mUr and a δ(15) NAir value of -4.52 mUr) for (i) analyzing local laboratory isotopic reference materials, and (ii) quantifying drift with time, mass-dependent isotopic fractionation, and isotope-ratio-scale contraction for isotopic analysis of biological and organic materials. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA. Published in 2016. This article is a U.S. Government work and is in the public domain in the USA.

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.

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

DOE PAGES

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.; ...

2018-03-01

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

Hg isotopes reveal in-stream processing and legacy inputs in East Fork Poplar Creek, Oak Ridge, Tennessee, USA

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

Demers, Jason D.; Blum, Joel D.; Brooks, Scott C.

In this paper, natural abundance stable Hg isotope measurements were used to place new constraints on sources, transport, and transformations of Hg along the flow path of East Fork Poplar Creek (EFPC), a point-source contaminated headwater stream in Oak Ridge, Tennessee. Particulate-bound Hg in the water column of EFPC within the Y-12 National Security Complex, was isotopically similar to average metallic Hg(0) used in industry, having a mean δ 202Hg value of -0.42 ± 0.09‰ (1SD) and near-zero Δ 199Hg. On average, particulate fraction δ 202Hg values increased downstream by 0.53‰, while Δ 199Hg decreased by -0.10‰, converging with themore » Hg isotopic composition of the fine fraction of streambed sediment along the 26 km flow path. The dissolved fraction behaved differently. Although initial Δ 199Hg values of the dissolved fraction were also near-zero, these values increased transiently along the flow path. Initial δ 202Hg values of the dissolved fraction were more variable than in the particulate fraction, ranging from -0.44 to 0.18‰ among three seasonal sampling campaigns, but converged to an average δ 202Hg value of 0.01 ± 0.10‰ (1SD) downstream. Dissolved Hg in the hyporheic and riparian pore water had higher and lower δ 202Hg values, respectively, compared to dissolved Hg in stream water. Finally, variations in Hg isotopic composition of the dissolved and suspended fractions along the flow path suggest that: (1) physical processes such as dilution and sedimentation do not fully explain decreases in total mercury concentrations along the flow path; (2) in-stream processes include photochemical reduction, but microbial reduction is likely more dominant; and (3) additional sources of dissolved mercury inputs to EFPC at baseflow during this study predominantly arise from the hyporheic zone.« less

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.

Stable isotope measurements of evapotranspiration partitioning in a maize field

NASA Astrophysics Data System (ADS)

Hogan, Patrick; Parajka, Juraj; Oismüller, Markus; Strauss, Peter; Heng, Lee; Blöschl, Günter

2017-04-01

Evapotranspiration (ET) is one of the most important processes in describing land surface - atmosphere interactions as it connects the energy and water balances. Furthermore knowledge of the individual components of evapotranspiration is important for ecohydrological modelling and agriculture, particularly for irrigation efficiency and crop productivity. In this study, we tested the application of the stable isotope method for evapotranspiration partitioning to a maize crop during the vegetative stage, using sap flow sensors as a comparison technique. Field scale ET was measured using an eddy covariance device and then partitioned using high frequency in-situ measurements of the isotopic signal of the canopy water vapor. The fraction of transpiration (Ft) calculated with the stable isotope method showed good agreement with the sap flow method. High correlation coefficient values were found between the two techniques, indicating the stable isotope method can successfully be applied in maize. The results show the changes in transpiration as a fraction of evapotranspiration after rain events and during the subsequent drying conditions as well as the relationship between transpiration and solar radiation and vapor pressure deficit.

Diet-tissue discrimination factors and turnover of carbon and nitrogen stable isotopes in tissues of an adult predatory coral reef fish, Plectropomus leopardus.

PubMed

Matley, J K; Fisk, A T; Tobin, A J; Heupel, M R; Simpfendorfer, C A

2016-01-15

Stable isotope ratios (δ(13)C and δ(15)N values) provide a unique perspective into the ecology of animals because the isotope ratio values of consumers reflect the values in food. Despite the value of stable isotopes in ecological studies, the lack of species-specific experimentally derived diet-tissue discrimination factors (DTDFs) and turnover rates limits their application at a broad scale. Furthermore, most aquatic feeding experiments use temperate, fast-growing fish species and few have considered medium- to large-sized adults with low growth rates from tropical ecosystems. A controlled-diet stable isotope feeding trial was conducted over a 196-day period for the adult predatory reef fish leopard coralgrouper (Plectropomus leopardus). This study calculated δ(13)C and δ(15)N DTDFs and turnover rates in five tissues (liver, plasma, red blood cells (RBC), fin, and muscle) using a continuous flow isotope ratio mass spectrometer equipped with an elemental analyzer. In addition, the effect of chemical lipid extraction (LE) on stable isotope values was examined for each tissue. Turnover was mainly influenced by metabolism (as opposed to growth) with LE δ(15)N half-life values lowest in fin (37 days) and plasma (66 days), and highest in RBC (88 days) and muscle (126 days). The diet-tissue discrimination factors for δ(15)N values in all tissues (Δ(15)N: -0.15 to 1.84‰) were typically lower than commonly reported literature values. Lipid extraction altered both δ(15) N and δ(13)C values compared with untreated samples; however, for the δ(15)N values, the differences were small (mean δ(15)N(LE-Bulk) <0.46‰ in all tissues). This study informs future interpretation of stable isotope data for medium- to large-sized fish and demonstrates that DTDFs developed for temperate fish species, particularly for δ(15)N values, may not apply to tropical species. Sampling of muscle and/or RBC is recommended for a relatively long-term representation of feeding habits, while plasma and/or fin should be used for a more recent indication of diet. Copyright © 2015 John Wiley & Sons, Ltd.

Role of isotope mass and evidence of fluctuating zonal flows during the L–H transition in the TJ-II stellarator

NASA Astrophysics Data System (ADS)

Losada, U.; Estrada, T.; Liu, B.; van Milligen, B.; Cheng, J.; Silva, C.; Pastor, I.; Fontdecaba, J. M.; Hidalgo, C.; TJ-II team1, the

2018-07-01

Mean radial electric fields as well as low frequency Zonal Flow-like global oscillations in radial electric field have been identified during the low to high (L–H) transition in Hydrogen and Deuterium dominated plasmas in the stellarator TJ-II. No evidence of isotope effect on the L–H transition dynamics was observed in the investigated TJ-II plasma scenarios. These observations emphasize the critical role of both zero frequency (equilibrium) and low frequency varying large-scale flows for stabilizing turbulence during the triggering of the L–H transition in magnetically confined toroidal plasmas.

Assessment of hydrochemical processes and groundwater hydrodynamics in a multilayer aquifer system under long-term irrigation condition: A case study of Nefzaoua basin, southern Tunisia.

PubMed

Tarki, M; Ben Hammadi, M; El Mejri, H; Dassi, L

2016-04-01

The hydrochemical and isotopic investigation of the Nefzaoua aquifer system demonstrates that groundwater mineralization in is controlled by natural and anthropogenic processes including water-rock interaction and irrigation return flow. It identifies all of the water bodies that flow within the aquifer system and their circulation patterns. The isotopically depleted paleowaters, identified within the deep and intermediate aquifers, undergo significant enrichment by evaporation during irrigation and recharged the shallow aquifer by return flow. Subsequently, they infiltrate to the intermediate aquifer which receives also rainfall modern recharge. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tracing sources of crustal contamination using multiple S and Fe isotopes in the Hart komatiite-associated Ni-Cu-PGE sulfide deposit, Abitibi greenstone belt, Ontario, Canada

NASA Astrophysics Data System (ADS)

Hiebert, R. S.; Bekker, A.; Houlé, M. G.; Wing, B. A.; Rouxel, O. J.

2016-10-01

Assimilation by mafic to ultramafic magmas of sulfur-bearing country rocks is considered an important contributing factor to reach sulfide saturation and form magmatic Ni-Cu-platinum group element (PGE) sulfide deposits. Sulfur-bearing sedimentary rocks in the Archean are generally characterized by mass-independent fractionation of sulfur isotopes that is a result of atmospheric photochemical reactions, which produces isotopically distinct pools of sulfur. Likewise, low-temperature processing of iron, through biological and abiotic redox cycling, produces a range of Fe isotope values in Archean sedimentary rocks that is distinct from the range of the mantle and magmatic Fe isotope values. Both of these signals can be used to identify potential country rock assimilants and their contribution to magmatic sulfide deposits. We use multiple S and Fe isotopes to characterize the composition of the potential iron and sulfur sources for the sulfide liquids that formed the Hart deposit in the Shaw Dome area within the Abitibi greenstone belt in Ontario (Canada). The Hart deposit is composed of two zones with komatiite-associated Ni-Cu-PGE mineralization; the main zone consists of a massive sulfide deposit at the base of the basal flow in the komatiite sequence, whereas the eastern extension consists of a semi-massive sulfide zone located 12 to 25 m above the base of the second flow in the komatiite sequence. Low δ56Fe values and non-zero δ34S and Δ33S values of the komatiitic rocks and associated mineralization at the Hart deposit is best explained by mixing and isotope exchange with crustal materials, such as exhalite and graphitic argillite, rather than intrinsic fractionation within the komatiite. This approach allows tracing the extent of crustal contamination away from the deposit and the degree of mixing between the sulfide and komatiite melts. The exhalite and graphitic argillite were the dominant contaminants for the main zone of mineralization and the eastern extension zone of the Hart deposit, respectively. Critically, the extent of contamination, as revealed by multiple S and Fe isotope systematics, is greatest within the deposit and decreases away from it within the komatiite flow. This pattern points to a local source of crustal contamination for the mantle-derived komatiitic melt and a low degree of homogenization between the mineralization and the surrounding lava flow. Coupled S and Fe isotope patterns like those identified at the Hart deposit may provide a useful tool for assessing the potential of a komatiitic sequence to host Ni-Cu-(PGE).

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

NASA Astrophysics Data System (ADS)

Xu, Naizheng; Gong, Jianshi; Yang, Guoqiang

2018-01-01

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

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea)

PubMed Central

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ 15N, δ 13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ 13C and δ 15N and C/N atomic values. Chemical preservatives caused δ 13C enrichment as great as 1.5‰, and δ 15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ 15N depletion up to 1.8‰. Freezing depleted δ 13C and δ 15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets. PMID:26390400

Automated calibration of laser spectrometer measurements of δ18 O and δ2 H values in water vapour using a Dew Point Generator.

PubMed

Munksgaard, Niels C; Cheesman, Alexander W; Gray-Spence, Andrew; Cernusak, Lucas A; Bird, Michael I

2018-06-30

Continuous measurement of stable O and H isotope compositions in water vapour requires automated calibration for remote field deployments. We developed a new low-cost device for calibration of both water vapour mole fraction and isotope composition. We coupled a commercially available dew point generator (DPG) to a laser spectrometer and developed hardware for water and air handling along with software for automated operation and data processing. We characterised isotopic fractionation in the DPG, conducted a field test and assessed the influence of critical parameters on the performance of the device. An analysis time of 1 hour was sufficient to achieve memory-free analysis of two water vapour standards and the δ 18 O and δ 2 H values were found to be independent of water vapour concentration over a range of ≈20,000-33,000 ppm. The reproducibility of the standard vapours over a 10-day period was better than 0.14 ‰ and 0.75 ‰ for δ 18 O and δ 2 H values, respectively (1 σ, n = 11) prior to drift correction and calibration. The analytical accuracy was confirmed by the analysis of a third independent vapour standard. The DPG distillation process requires that isotope calibration takes account of DPG temperature, analysis time, injected water volume and air flow rate. The automated calibration system provides high accuracy and precision and is a robust, cost-effective option for long-term field measurements of water vapour isotopes. The necessary modifications to the DPG are minor and easily reversible. Copyright © 2018 John Wiley & Sons, Ltd.

Preservation Methods Alter Carbon and Nitrogen Stable Isotope Values in Crickets (Orthoptera: Grylloidea).

PubMed

Jesus, Fabiene Maria; Pereira, Marcelo Ribeiro; Rosa, Cassiano Sousa; Moreira, Marcelo Zacharias; Sperber, Carlos Frankl

2015-01-01

Stable isotope analysis (SIA) is an important tool for investigation of animal dietary habits for determination of feeding niche. Ideally, fresh samples should be used for isotopic analysis, but logistics frequently demands preservation of organisms for analysis at a later time. The goal of this study was to establish the best methodology for preserving forest litter-dwelling crickets for later SIA analysis without altering results. We collected two cricket species, Phoremia sp. and Mellopsis doucasae, from which we prepared 70 samples per species, divided among seven treatments: (i) freshly processed (control); preserved in fuel ethanol for (ii) 15 and (iii) 60 days; preserved in commercial ethanol for (iv) 15 and (v) 60 days; fresh material frozen for (vi) 15 and (vii) 60 days. After oven drying, samples were analyzed for δ15N, δ13C values, N(%), C(%) and C/N atomic values using continuous flow isotope ratio mass spectrometry. All preservation methods tested, significantly impacted δ13C and δ15N and C/N atomic values. Chemical preservatives caused δ13C enrichment as great as 1.5‰, and δ15N enrichment as great as 0.9‰; the one exception was M. doucasae stored in ethanol for 15 days, which had δ15N depletion up to 1.8‰. Freezing depleted δ13C and δ15N by up to 0.7 and 2.2‰, respectively. C/N atomic values decreased when stored in ethanol, and increased when frozen for 60 days for both cricket species. Our results indicate that all preservation methods tested in this study altered at least one of the tested isotope values when compared to fresh material (controls). We conclude that only freshly processed material provides adequate SIA results for litter-dwelling crickets.

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

PubMed

Xu, Naizheng; Gong, Jianshi; Yang, Guoqiang

2018-01-01

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

Estimating pathway-specific contributions to biodegradation in aquifers based on dual isotope analysis: theoretical analysis and reactive transport simulations.

PubMed

Centler, Florian; Heße, Falk; Thullner, Martin

2013-09-01

At field sites with varying redox conditions, different redox-specific microbial degradation pathways contribute to total contaminant degradation. The identification of pathway-specific contributions to total contaminant removal is of high practical relevance, yet difficult to achieve with current methods. Current stable-isotope-fractionation-based techniques focus on the identification of dominant biodegradation pathways under constant environmental conditions. We present an approach based on dual stable isotope data to estimate the individual contributions of two redox-specific pathways. We apply this approach to carbon and hydrogen isotope data obtained from reactive transport simulations of an organic contaminant plume in a two-dimensional aquifer cross section to test the applicability of the method. To take aspects typically encountered at field sites into account, additional simulations addressed the effects of transverse mixing, diffusion-induced stable-isotope fractionation, heterogeneities in the flow field, and mixing in sampling wells on isotope-based estimates for aerobic and anaerobic pathway contributions to total contaminant biodegradation. Results confirm the general applicability of the presented estimation method which is most accurate along the plume core and less accurate towards the fringe where flow paths receive contaminant mass and associated isotope signatures from the core by transverse dispersion. The presented method complements the stable-isotope-fractionation-based analysis toolbox. At field sites with varying redox conditions, it provides a means to identify the relative importance of individual, redox-specific degradation pathways. © 2013.

Stable isotope ratio mass spectrometry of nanogram quantities of boron and sulfur

NASA Astrophysics Data System (ADS)

Wieser, Michael Eugene

1998-09-01

Instrumentation and analytical techniques were developed to measure isotope abundances from nanograms of sulfur and boron. Sulfur isotope compositions were determined employing continuous flow isotope ratio mass spectroscopy (CF-IRMS) procedures and AsS+ thermal ionization mass spectrometry techniques (AsS+-TIMS). Boron isotope abundances were determined by BO2/sp--TIMS. CF-IRMS measurements realized δ34S values from 10 μg sulfur with precisions of ±0.3/perthous. To extend sulfur isotope measurements to much smaller samples, a TIMS procedure was developed to measure 75As32S+ and 75As34S+ at masses 108 and 109 from 200 ng S on a Finnigan MAT 262 with an ion counter. This is possibly the smallest amount of sulfur which has been successfully analyzed isotopically. The internal precision of 32S/34S ratios measured by AsS+-TIMS was better than ±0.15 percent. δ34S-values calculated relative to the measured 32S/34S value of an IAEA AG2S standard (S-1) agreed with those determined by CF-IRMS to within ±3/perthous. The increasing sensitivity of S-isotope analyses permits hiterto impossible investigations e.g. sulfur in tree rings and ice cores. Boron isotope abundances were measured as BO2/sp- from 50 ng B using an older thermal ionization mass spectrometer which had been extensively upgraded including the addition of computer control electronics, sensitive ion current amplification and fiber optic data bus. The internal precisions of the measured 11B/10B ratios were ±0.15 percent and the precisions of δ11B values calculated relative to the accepted international standard (SRM-951) were ±3/perthous. Two applications of boron isotope abundance variations were initiated (1) ground waters of Northern Alberta and (2) coffee beans in different regions of the world. In the first it was demonstrated that boron isotopes could be used to trace boron released during steam injection of oil sands into the surrounding environment. Data from the second study suggest that boron isotopes can be used to improve cultivation of coffee particularly in regions where 'organically grown' coffee had markedly different δ11B values than beans grown with boron- containing fertilizers in neighbouring regions. A regional dependence on the δ11B values of the coffee allow the sources of commercial coffee blends to be identified.

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

NASA Astrophysics Data System (ADS)

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

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

Yucca Mountain Area Saturated Zone Dissolved Organic Carbon Isotopic Data

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

Thomas, James; Decker, David; Patterson, Gary

2007-06-25

Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC)more » were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, flow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated groundwater ages. The DIC calculated groundwater ages were compared with DOC calculated groundwater ages and both of these ages were compared to travel times developed in ground-water flow and transport models. If nuclear waste is stored in Yucca Mountain, the saturated zone is the final barrier against the release of radionuclides to the environment. The most recent rendition of the TSPA takes little credit for the presence of the saturated zone and is a testament to the inadequate understanding of this important barrier. If radionuclides reach the saturated zone beneath Yucca Mountain, then there is a travel time before they would leave the Yucca Mountain area and flow down gradient to the Amargosa Valley area. Knowing how long it takes groundwater in the saturated zone to flow from beneath Yucca Mountain to down gradient areas is critical information for potential radionuclide transport. Radionuclide transport in groundwater may be the quickest pathway for radionuclides in the proposed Yucca Mountain repository to reach land surface by way of groundwater pumped in Amargosa Valley. An alternative approach to ground-water flow and transport models to determine the travel time of radionuclides from beneath Yucca Mountain to down gradient areas in the saturated zone is by carbon-14 dating of both inorganic and organic carbon dissolved in the groundwater. A standard method of determining ground-water ages is to measure the carbon-13 and carbon-14 of DIC in the groundwater and then correct the measured carbon-14 along a flow path for geochemical reactions that involve carbon containing phases. These geochemical reactions are constrained by carbon-13 and isotopic fractionations. Without correcting for geochemical reactions, the ground-water ages calculated from only the differences in carbon-14 measured along a flow path (assuming the decrease in carbon-14 is due strictly to radioactive decay) could be tens of thousands of years too old. The computer program NETPATH, developed by the USGS, is the best geochemical program for correcting carbon-14 activities for geochemical reactions. The DIC carbon-14 corrected ages can be further constrained by measuring the carbon isotopes of DOC. Because the only source of organic carbon in aquifers is almost always greater than 40,000 years old, any organic carbon that may be added to the groundwater would contain no carbon-14. Thus, ground-water ages determined by carbon isotopes of DOC should be maximum ages that can be used to constrain DIC corrected ages.« less

Dual pressure-dual temperature isotope exchange process

DOEpatents

Babcock, D.F.

1974-02-12

A liquid and a gas stream, each containing a desired isotope, flow countercurrently through two liquid-gas contacting towers maintained at different temperatures and pressures. The liquid is enriched in the isotope in one tower while the gas is enriched within the other and a portion of at least one of the enriched streams is withdrawn from the system for use or further enrichment. The tower operated at the lower temperature is also maintained at the lower pressure to prevent formation of solid solvates. Gas flow between the towers passes through an expander-compressor apparatas to recover work from the expansion of gas to the lower pressure and thereby compress the gas returning to the tower of higher pressure. (Official Gazette)

Hydrological conditions and evaluation of sustainable groundwater use in the Sierra Vista Subwatershed, Upper San Pedro Basin, southeastern Arizona

USGS Publications Warehouse

Gungle, Bruce; Callegary, James B.; Paretti, Nicholas V.; Kennedy, Jeffrey R.; Eastoe, Christopher J.; Turner, Dale S.; Dickinson, Jesse; Levick, Lainie R.; Sugg, Zachary P.

2016-08-18

Looking at the subwatershed as a whole, base flow was in decline along the entire river reach, but determination of the specific cause of the decline was beyond the scope of this report. Conditions in the area from the municipal pumping center of Sierra Vista and Fort Huachuca northeast to the river (from about the Charleston to Tombstone gaging stations) were more commonly in decline than in regions further south. Both long-term indicators, such as regional aquifer groundwater levels and horizontal gradients, and the isotope analysis indicated that groundwater discharge to the river and thus base flow may continue to decline in that area. South of Charleston, indicators were more mixed. Some indicators in the Hereford reach suggest groundwater discharge to the San Pedro River may be increasing there, whereas some indicators in the Palominas reach suggest groundwater discharge to the river there may be declining.

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

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

USGS Publications Warehouse

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

1996-01-01

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

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

NASA Astrophysics Data System (ADS)

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

1996-12-01

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

Distribution of extravascular fluid volumes in isolated perfused lungs measured with H215O.

PubMed Central

Jones, T; Jones, H A; Rhodes, C G; Buckingham, P D; Hughes, J M

1976-01-01

The distributions per unit volume of extravascular water (EVLW), blood volume, and blood flow were measured in isolated perfused vertical dog lungs. A steady-state tracer technique was employed using oxygen-15, carbon-11, and nitrogen-13 isotopes and external scintillation counting of the 511-KeV annihilation radiation common to all three radionuclides. EVLW, and blood volume and flow increased from apex to base in all preparations, but the gradient of increasing flow exceeded that for blood and EVLW volumes. The regional distributions of EVLW and blood volume were almost identical. With increasing edema, lower-zone EVLW increased slightly relative to that in the upper zone. There was no change in the distribution of blood volume or flow until gross edema (100% wt gain) occurred when lower zone values were reduced. In four lungs the distribution of EVLW was compared with wet-to-dry ratios from lung biopsies taken immediately afterwards. Whereas the isotopically measured EVLW increased from apex to base, the wet-to-dry weight ratios remained essentially uniform. We concluded that isotopic methods measure only an "exchangeable" water pool whose volume is dependent on regional blood flow and capillary recruitment. Second, the isolated perfused lung can accommodate up to 60% wt gain without much change in the regional distribution of EVLW, volume, or flow. PMID:765354

The measurement of skin lymph flow by isotope clearance--reliability, reproducibility, injection dynamics, and the effect of massage

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

Mortimer, P.S.; Simmonds, R.; Rezvani, M.

1990-12-01

The measurement of skin lymph flow was investigated using an isotope clearance technique (ICT). Multiple lymph flow determinations were undertaken in the skin of anaesthetized large white pigs to test for reproducibility, ascertain the most suitable tracer, study the influence of injection dynamics, and observe the effect of massage as a stimulus to lymph flow. Blood clearance of tracer was also investigated. Results demonstrated that lymphatic clearance is a monoexponential function with good reproducibility under controlled laboratory conditions. 99mTc-colloid (TCK17 Cis) compared favorably with 131I-human serum albumin as a tracer and both performed better than colloid gold (198Au). Lymph flowmore » was significantly faster in one pig than in the other. No difference existed between left and right sides or between caudal and rostral sites on each flank, but clearance was significantly slower in thigh than flank skin. Sub-epidermal injections cleared faster and more consistently than either deep or subcutaneous injections. Neither injection volume nor needle tract backflow of tracer influenced results, but local massage significantly enhanced clearance. Escape of 99mTc-colloid by the blood was negligible. These results indicate that skin lymph flow can be reliably measured when conditions are controlled. Extrinsic factors such as massage strongly influence lymph flow. Greater sensitivity in detecting degrees of lymphatic insufficiency may be achieved if a standardized stimulus to lymph flow is administered during isotope clearance measurement.« less

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

Piper, Stephen C; Keeling, Ralph F

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

The chronology for the d18O record from Devils Hole, Nevada, extended into the Mid-Holocene

USGS Publications Warehouse

Landwehr, J.M.; Sharp, W.D.; Coplen, T.B.; Ludwig, K. R.; Winograd, I.J.

2011-01-01

This report presents the numeric values for the chronology of the paleoclimatically relevant mid-to-late Pleistocene record of the ratios of stable oxygen isotope (delta18O) in vein calcite from Devils Hole, Nev., which recently had been extended into the mid-Holocene. Dating was obtained using 230Th-234U-238U thermal ionization mass spectrometry. Devils Hole is a subaqueous cave of tectonic origin, which developed in the discharge zone of a regional aquifer in south-central Nevada. The primary groundwater recharge source area is the Spring Mountains, the highest mountain range in southern Nevada [altitude 3,630 meters (m)], approximately 80 kilometers to the east of the cavern. The walls of the open fault zone comprising the cave system are coated with dense vein calcite precipitated from the through-flowing groundwater. The calcite, up to 40 centimeters (cm) thick, contains a continuous record of the sequential variation of the composition of stable oxygen isotopes in the ground water over time. The vein calcite has also proven to be a suitable material for precise uranium-series dating via thermal ionization mass spectrometry utilizing the 230Th-234U-238U decay clock. Earlier work has presented data from the Devils Hole core DH-11, a 36-cm-long core of vein calcite recovered from a depth of about 30 m below the water table (about 45 m beneath the ground surface). The DH-11 core provided a continuous record of isotopic oxygen variation from 567,700 to 59,800 years before present. Recent work has extended this record up to 4,500 years before present, into the mid-Holocene epoch.

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Chemical, isotopic, and dissolved gas compositions of the hydrothermal system in Twin Falls and Jerome counties, Idaho

USGS Publications Warehouse

Mariner, R.H.; Young, H.W.; Evans, W. E.; Parliman, D.J.

1991-01-01

The chemical, isotopic, and gas compositions of the hydrothermal system in Twin Falls and Jerome counties, Idaho, change systematically as the water moves northward from the Idaho-Nevada boundary toward the Snake River. Sodium, chloride, fluoride, alkalinity, dissolved helium, and carbon-13 increase as calcium and carbon-14 decrease. Water-rock reactions may result in dissolution of plagioclase or volcanic glass and calcite, followed by precipitation of zeolites and clays. On the basis of carbon-14 age dating, apparent water ages range from 2,000 to more than 26,000 years; most apparent ages range from about 4,000 to 10,000 years. The older waters, north of the Snake River, are isotopically depleted in deuterium and are enriched in chloride relative to waters to the south. Thermal waters flowing northward beneath the Snake River may join a westward flow of older thermal water slightly north of the river. The direction of flow in the hydrothermal system seems to parallel the surface drainage.

Three-dimensional oxygen isotope imaging of convective fluid flow around the Big Bonanza, Comstock lode mining district, Nevada

USGS Publications Warehouse

Criss, R.E.; Singleton, M.J.; Champion, D.E.

2000-01-01

Oxygen isotope analyses of propylitized andesites from the Con Virginia and California mines allow construction of a detailed, three-dimensional image of the isotopic surfaces produced by the convective fluid flows that deposited the famous Big Bonanza orebody. On a set of intersecting maps and sections, the δ18O isopleths clearly show the intricate and conformable relationship of the orebody to a deep, ~500 m gyre of meteoric-hydrothermal fluid that circulated along and above the Comstock fault, near the contact of the Davidson Granodiorite. The core of this gyre (δ18O = 0 to 3.8‰) encompasses the bonanza and is almost totally surrounded by rocks having much lower δ18O values (–1.0 to –4.4‰). This deep gyre may represent a convective longitudinal roll superimposed on a large unicellular meteoric-hydrothermal system, producing a complex flow field with both radial and longitudinal components that is consistent with experimentally observed patterns of fluid convection in permeable media.

Estimating pothole wetland connectivity to Pipestem Creek, North Dakota: an isotopic approach

EPA Science Inventory

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, Nort...

Estimating pothole wetland connectivity to Pipestem Creek, North Dakota: an isotopic approach.

EPA Science Inventory

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 P...

Rb-Sr and Sm-Nd Ages of Zagami DML and SR Isotopic Heterogeneity in Zagami

NASA Technical Reports Server (NTRS)

Nyquist, L.aurenceE.; Shih, C.-Y.; Reese, Y. D.

2010-01-01

Zagami contains lithologic heterogeneity suggesting that it did not form in a homogeneous, thick lava flow [1]. We have previously investigated the Sr and Nd isotopic systematics of Coarse-Grained (CG) and Fine-Grained (FG) lithologies described by [2]. Both appear to belong to Normal Zagami (NZ) [1,3], but their initial Sr-isotopic compositions differ [4,5]. Here we report new analyses of the Dark Mottled Lithology (DML, [3]) that show its age and initial Sr and Nd isotopic compositions to be identical within error limits with those of CG, but Sr initial isotopic compositions differ from those of FG.

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

NASA Technical Reports Server (NTRS)

Coplen, T. B.; Hanshaw, B. B.

1973-01-01

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Using stable isotopes to examine watershed connectivity to ...

EPA Pesticide Factsheets

Water bodies within the USA are protected by the US Clean Water Act when they have a significant nexus to downstream navigable waters. As a research scientist with the US Environmental Protection Agency, I have used water stable isotopes to examine hydrologic connectivity dynamics. I will share two case studies. In the first case, 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. Prairie-Pothole wetlands are a special case of wetlands whose protection needs to be determined under the Clean Water Rule. Pipestem Creek exhibited an evaporated-water signal that had approximately half the isotopic-enrichment signal found in most evaporatively enriched prairie-pothole wetlands. 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 area of surface water necessary to generate the evaporation signal found within Pipestem Creek over two years. Our results indicated that prairie-pothole wetlands were important sources of stream flow in Pipestem Creek throughout the summer, as well as during snowmelt. They also demonstrated that at the lowest flows, the stream itself became disconnected from headwater stream reaches. In the second ca

Determination of the δ15N of total nitrogen in solids; RSIL lab code 2893

USGS Publications Warehouse

Revesz, Kinga; Qi, Haiping; Coplen, Tyler B.

2006-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 2893 is to determine the δ(15N/14N), abbreviated as δ15N , of total nitrogen in solid samples. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total nitrogen in a solid sample into N2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines relative difference in the isotope-amount ratios of stable nitrogen isotopes (15N/14N)of the product N2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated reaction tube that contains an oxidant, where the combustion takes place in a helium atmosphere containing an excess of oxygen gas. Combustion products are transported by a helium carrier through a reduction tube to remove excess oxygen and convert all nitrous oxides into N2 and through a drying tube to remove water. The gas-phase products, mainly CO2 and N2, are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which also is used to inject N2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector, two wide cups with a narrow cup in the middle, capable of measuring mass/charge (m/z) 28, 29, 30, simultaneously. The ion beams from N2 are as follows: m/z 28 = N2 = 14N14N; m/z 29 = N2 = 14N15N primarily; m/z 30 = NO = 14N16O primarily, which is a sign of contamination or incomplete reduction.

The preliminary result of the δ65Cu and δ34S values of major ore minerals in the Erdenetiin-Ovoo Cu-Mo porphyry deposit, Northern Mongolia

NASA Astrophysics Data System (ADS)

KIM, Y.; Lee, I.; Oyungerel, S.; Jargal, L.; Tsedenbal, T.; Ryu, J. S.

2016-12-01

The copper isotope (δ65Cu) and sulfur isotope (δ34S) compositions of major ore minerals from the Erdenetiin-Ovoo Cu-Mo porphyry deposit were measured to trace sources of copper and sulfur, and to evaluate the precipitation environment of ore minerals. The major ore minerals are pyrite, chalcopyrite, molybdenite and chalcocite developed in the QSP (Quartz-Sericite-Pyrite) alteration zone. The sulfide minerals such as sphalerite and covellite, and carbonate ore minerals like malachite, azurite are also identified. The copper isotope ratios (65Cu/63Cu) of copper ore minerals (chalcopyrite, chalcocite, malachite, azurite, covellite and chrysocolla) were analyzed by the MC-ICPMS in KBSI located in Ochang, South Korea. The measured δ65Cu values relative to NIST 976 range from -1.01 ‰ to 5.76 ‰. The average δ65Cu values of sulfide minerals such as chalcopyrite (1.03 ‰), chalcocite (0.62 ‰) and covellite (0.51 ‰) seem to be relatively lower than those of carbonate and silicate Cu minerals such as malachite (0.24 ‰), azurite (2.17 ‰) and chrysocolla (5.76 ‰). The sulfur isotope ratios (34S/32S) of major sulfide minerals were measured by EA-CF-IRMS (Elemental Analyzer - Continuous Flow - Isotope Ratio Mass Spectrometer) in NCIRF, Seoul National University. The average δ34SV-CDT value is -1.1 ‰ indicating the magmatic signature of sulfur. There is the difference of δ34S values between sulfide minerals. While the δ34S values of pyrite, chalcopyrite and molybdenite range from -0.9 to 0.8 ‰, the δ34S values of chalcocite range from -2.6 ‰ to -1.4 ‰. These lower values might be attributed to the sulfur isotope fractionation during its precipitation.

Assimilation of benzene carbon through multiple trophic levels traced by different stable isotope probing methodologies.

PubMed

Bastida, Felipe; Jechalke, Sven; Bombach, Petra; Franchini, Alessandro G; Seifert, Jana; von Bergen, Martin; Vogt, Carsten; Richnow, Hans H

2011-08-01

The flow of benzene carbon along a food chain consisting of bacteria and eukaryotes, including larvae (Diptera: Chironomidae), was evaluated by total lipid fatty acids (TLFAs)-, amino acid- and protein-stable isotope probing (SIP). A coconut-fibre textile, colonized by a benzene-degrading biofilm, was sampled in a system established for the remediation of benzene, toluene, ethylbenzene and xylenes (BTEX)-polluted groundwater and incubated with (12)C- and [(13)C(6)]-benzene (>99 at.%) in a batch-scale experiment for 2-8 days. After 8 days, Chironomus sp. larvae were added to study carbon flow to higher trophic levels. Gas chromatography-combustion-isotope ratio monitoring mass spectrometry of TLFA showed increased isotope ratios in the (13)C-benzene-incubated biofilm. A higher (13)C-enrichment was observed in TLFAs, indicative of Gram-negative bacteria than for Gram-positive. Fatty acid indicators of eukaryotes showed significant (13)C-incorporation, but to a lower extent than bacterial indicators. Fatty acids extracted from larvae feeding on (13)C-biofilm reached an isotopic ratio of 1.55 at.%, illustrating that the larvae feed, to some extent, on labelled biomass. No (13)C-incorporation was detectable in larval proteins after their separation by sodium-dodecyl sulphate-polyacrylamide gel electrophoresis and analysis by nano-liquid-chromatography-mass spectrometry. The flow of benzene-derived carbon could be traced in a food web consisting of bacteria and eukaryotes. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

How young water fractions can delineate travel time distributions in contrasting catchments

NASA Astrophysics Data System (ADS)

Lutz, Stefanie; Zink, Matthias; Merz, Ralf

2017-04-01

Travel time distributions (TTDs) are crucial descriptors of flow and transport processes in catchments. Tracking fluxes of environmental tracers such as stable water isotopes offers a practicable method to determine TTDs. The mean transit time (MTT) is the most commonly reported statistic of TTDs; however, MTT assessments are prone to large aggregation biases resulting from spatial heterogeneity and non-stationarity in real-world catchments. Recently, the young water fraction (Fyw) has been introduced as a more robust statistic that can be derived from seasonal tracer cycles. In this study, we aimed at improving the assessment of TTDs by using Fyw as additional information in lumped isotope models. First, we calculated Fyw from monthly δ18O-samples for 24 contrasting sub-catchments in a meso-scale catchment (3300 km2). Fyw ranged from 0.01 to 0.27 (mean= 0.11) and was not significantly correlated with catchment characteristics (e.g., mean slope, catchment area, and baseflow index) apart from the dominant soil type. Second, assuming gamma-shaped TTDs, we determined time-invariant TTDs for each sub-catchment by optimization of lumped isotope models using the convolution integral method. Whereas multiple optimization runs for the same sub-catchment showed a wide range of TTD parameters, the use of Fyw as additional information allowed constraining this range and thus improving the assessment of MTTs. Hence, the best model fit to observed isotope data might not be the desired solution, as the resulting TTD might define a young water fraction non-consistent with the tracer-cycle based Fyw. Given that the latter is a robust descriptor of fast-flow contribution, isotope models should instead aim at accurately describing both Fyw and the isotope time series in order to improve our understanding of flow and transport in catchments.

Variability of pesticides and nitrates concentrations along a river transect: chemical and isotopic evidence of groundwater - surface water interconnections

NASA Astrophysics Data System (ADS)

Baran, Nicole; Petelet-Giraud, Emmanuelle; Saplairoles, Maritxu

2015-04-01

Groundwater quality is increasingly monitored in Europe where various levels of nitrate and pesticide and/or metabolite contamination have been demonstrated (Loos et al., 2010, Stuart et al., 2012). The Groundwater Daughter Directive (2006/118/EC) to Water Framework Directive (WFD) particularly requires measures to prevent or limit inputs of pollutants into groundwater and compliance with good chemical status criteria (based on EU standards of nitrate and pesticides). The WFD mentioned the need to protect groundwater but also to have a particular regard to its impact and interrelationship with associated surface waters and directly dependent terrestrial Ecosystems. The Ariège river basin (SW France - 538 km²) is an alluvial plain under high agricultural pressure leading to a contamination of the aquifer by several pesticides and metabolites (Amalric et al., 2013). The Crieu is an allochtone river, crossing the plain (~ 10 km length) before joining the Ariège River. The Crieu is often dry in its middle section suggesting water leakage from surface water towards groundwater. At the opposite, the permanent flow observed downstream suggests an input of groundwater into surface water. In May 2014, while the Crieu flow was continuous through the plain, 7 river samples were collected and analyzed for pesticides, major ions, strontium concentration and isotopes. In situ measurements of electric conductivity were also performed as well as flow gauging. Two groundwaters close to the river were also sampled. The flow gauging measurements show a decreasing river discharge in the central area of the Crieu River, suggesting surface water leakage towards groundwater. Nevertheless, the electric conductivity increases along the river flow as well as some pesticides and nitrates concentrations. This chemical evolution of the river water is thus inconsistent with a simple water infiltration and another source of dissolved solutes is required to explain the increased of concentration. Finally, downstream the quantified pesticides were different from those observed in the upper part of the Crieu but similar to those observed in groundwater. Sr isotopes together with major elements and Sr concentrations allow to identify 3 distinct end-members to explain the river quality evolution : 1) surface water, 2) groundwater and 3) sub-surface water. On this basis, we first demonstrate that the contribution of the different end-members to the river flow is highly variable from upstream to downstream. Secondly, we evidence water exchanges between the river and the groundwater compartment and vice-versa. The combination of the isotopic and geochemical approaches was essential to understand the complex relations and exchanges between surface and ground-waters occurring in few kilometers along the Crieu River. This understanding allows the comprehension of spatial variability of surface water quality. This is of primary importance when to help water managers to select relevant sampling points to be monitored in the framework of the WFD. Amalric L., et al. (2013). International Journal of Environmental Analytical Chemistry, 93: 1660-1675 Loos R. et al. (2010). Water Research, 44: 4115-4126 Stuart M. et al. (2012). Science of the Total Environment, 416: 1-21.

Isotope and methane dynamics above and below the Trade Wind Inversion at Ascension Island using UAVs

NASA Astrophysics Data System (ADS)

Brownlow, R.; Lowry, D.; Nisbet, E. G.; Fisher, R. E.; France, J.; Lanoisellé, M.; Thomas, R.; Richardson, T.; Greatwood, C.; Freer, J. E.; MacKenzie, A. R.

2015-12-01

Ascension Island (8oS, 14 oW) is a South Atlantic background site for atmospheric measurement. Royal Holloway, in collaboration with the UK Met Office, installed a Picarro 1301 CRDS in 2010 for continuous methane monitoring. This has high precision and accuracy, with a 6-gas calibration and target suite, to measure long term methane mole fraction. Regular flask sampling is also carried out for NOAA and RHUL (co-located), to measure δ13CCH4 isotopic trends.Ascension Island experiences near-constant SE Trade winds below the Trade Wind Inversion (TWI), with air from the remote S. Atlantic. In flask samples and in continuous monitoring at the Airhead location, atmospheric methane mole fraction has been increasing since 2007 whilst the δ13CCH4 isotope record has shifted to more depleted values. Above the normally well-defined TWI (1200 - 1800m altitude), variable tropical air masses pass over Ascension. This air last mixed with the boundary layer over Africa or South America. Field work undertaken in September 2014 and July 2015, in collaboration with U. Bristol and U. Birmingham, using UAVs (octocopters) collected samples with Tedlar bags or aluminium flasks from different heights above and below the TWI. The maximum altitude reached was 2700masl. Sample bags were immediately analysed on Ascension for CH4 mole fraction using the Picarro CRDS and subsequently analysed at RHUL for δ13CCH4 using continuous-flow gas chromatography/isotope-ratio mass spectrometry (CF-GC/IRMS). The TWI was clearly identified by an increase in CH4 mole fraction above the TWI. Back trajectory analysis was used to distinguish the origins of the air masses, with air above showing inputs from the land surfaces of equatorial and southern Africa, and from southern S. America.The campaigns have extended the envelope of altitudes accessed by micro-UAVs for atmospheric science, demonstrating their utility for probing the remote free troposphere and for penetrating the TWI. Sampling at Ascension is able to measure both the deep S. Atlantic air and also the air that has been mixed by convective systems in the equatorial and southern savannah tropics. Biomass burning plumes in southern hemisphere winter may also be accessible. Ascension is thus potentially a measurement site of global significance.

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

Mignerey, A.C.; Helz, G.R.; Purdy, C.B.

The project has used isotopic tracers to study the waters of two of the three major aquifers in the Coastal Plain of Maryland, the Aquia and the Magothy. Estimates of the time water has been in the ground, as a function of flow distance from the outcrop, have been made based on the effect of sea level on the isotopic concentrations and ratios. An age of about 18,000 y is obtained for Aquia water 40 km from the outcrop. Assuming a constant flow rate throughout the aquifer puts the oldest water at approximately 40,000 y old. Although information on themore » Magothy aquifer is less complete, flow rates appear to be similar to those in the Aquia.« less

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains.

PubMed

Zaia Alves, Gustavo H; Hoeinghaus, David J; Manetta, Gislaine I; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems.

Dry season limnological conditions and basin geology exhibit complex relationships with δ13C and δ15N of carbon sources in four Neotropical floodplains

PubMed Central

Hoeinghaus, David J.; Manetta, Gislaine I.; Benedito, Evanilde

2017-01-01

Studies in freshwater ecosystems are seeking to improve understanding of carbon flow in food webs and stable isotopes have been influential in this work. However, variation in isotopic values of basal production sources could either be an asset or a hindrance depending on study objectives. We assessed the potential for basin geology and local limnological conditions to predict stable carbon and nitrogen isotope values of six carbon sources at multiple locations in four Neotropical floodplain ecosystems (Paraná, Pantanal, Araguaia, and Amazon). Limnological conditions exhibited greater variation within than among systems. δ15N differed among basins for most carbon sources, but δ13C did not (though high within-basin variability for periphyton, phytoplankton and particulate organic carbon was observed). Although δ13C and δ15N values exhibited significant correlations with some limnological factors within and among basins, those relationships differed among carbon sources. Regression trees for both carbon and nitrogen isotopes for all sources depicted complex and in some cases nested relationships, and only very limited similarity was observed among trees for different carbon sources. Although limnological conditions predicted variation in isotope values of carbon sources, we suggest the resulting models were too complex to enable mathematical corrections of source isotope values among sites based on these parameters. The importance of local conditions in determining variation in source isotope values suggest that isotopes may be useful for examining habitat use, dispersal and patch dynamics within heterogeneous floodplain ecosystems, but spatial variability in isotope values needs to be explicitly considered when testing ecosystem models of carbon flow in these systems. PMID:28358822

Sediment Fingerprinting Using Carbon and Nitrogen Stable Isotopes in the Upper Palouse Watershed, Northwestern Idaho

NASA Astrophysics Data System (ADS)

Fox, J. F.; Papanicolaou, A. T.

2003-12-01

Unwarranted soil erosion creates detrimental problems for watershed users and for habitats and human infrastructure that experience increased suspended sediment in surface water. Identification and mitigation of erosion prone uplands relies on the realization that land uses (i.e. agriculture, forest, industrial, pasture, etc.) "produce sediment differently" at the watershed scale. Quantification of sediment production from various land uses is deemed feasible by using sediment-particle fingerprinting. This technique utilizes vegetative derived carbon (C) and nitrogen (N) stable isotopes and the carbon/nitrogen (C/N) atomic ratio of sediments to identify sediment producing land uses. Past research has established differences between C and N isotopic signatures and C/N ratios for soils under forest vs. agriculture (i.e. grasses and wheat) land cover. The current research rigorously examines these distinct signatures through isotopic analysis of field soils from the Palouse River Watershed of Northwestern Idaho preceded with statistical analyses to establish soil uniqueness. In addition, stream sediments are preliminarily analyzed to identify their origin with the goal of establishing a blueprint methodology for estimating sediment source and erosion rates within the watershed. Prior to field sampling of source soils, a statistical-experimental design was established with the intent to capture spatial and temporal variations and random errors of C and N isotopic signatures and C/N ratios within the forest and agriculture land uses. Factors including, elevation, slope topography, and season, were assessed by excavating over 300 samples during 4 seasons (i.e. May 2002, August 2002, November 2002, and March 2003) and at numerous locations throughout the watershed. Atomic analyses was performed at the University of Idaho Natural Resources Stable Isotope Laboratory using a Costech 4010 Elemental Combustion System connected with a continuous flow inlet system to the Finnigan MAT Delta Plus isotope ratio mass spectrometer. The statistical analysis of variance (ANOVA) with C and N isotopic signatures and C/N ratios as three independent response variables was administered to identify the agriculture and forested uniqueness, and discriminant analysis was used to create an organic fingerprint parameter which weights the contribution of C and N isotopic signatures and C/N ratios to the land cover separation. Results indicate uniqueness of the N isotope C/N ratio for the forest and agriculture sediment sources and little distinction possible for the C isotope signature. The organic fingerprint parameter was then calculated and coupled with in-stream sediment isotopic data using a simple end-member model. Preliminary results indicate that C and N isotopic signatures and C/N ratios will serve as a useful technique in quantifying erosive source rates and understanding upland erosion processes.

Isotopic Zonation Within Sulfate Evaporite Mineral Crystals Reveal Quantitative Paleoenvironment Details

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Groundwater flow and potential effects on evaporite dissolution in the Paradox Basin, SE Utah

NASA Astrophysics Data System (ADS)

Reitman, N.; Ge, S.; Mueller, K. J.

2012-12-01

A hydrogeologic study was conducted in the portion of the Paradox Basin south of the Needles District of Canyonlands National Park, Utah. Geology of the study area comprises fractured and faulted Paleozoic sandstone, limestone, and shale, which are underlain by evaporite cycles of the Paradox Formation. The evaporite deposits deform and dissolve when they come in contact with groundwater, generating land subsidence, saline groundwater, and salt input to the Colorado River. Active faults in the region slip at a rate of approximately 2 mm/year, likely due to evaporite dissolution. The objective of this study is to better understand groundwater flow and solute transport dynamics and to help determine the rate and timing of subsurface salt dissolution, which is an important control on the salt tectonics in the region. Study methods include hydrologic fieldwork, laboratory tests, and numerical modeling. No groundwater wells exist in the study area. Water samples from springs and seeps were collected throughout the study area. Analysis of total dissolved solids (TDS), stable oxygen (δ18O) and deuterium (δD) isotopes, spring and seep locations, and prior data are used to gain a preliminary understanding of the shallow groundwater flow in the region. Stable isotope ratios of oxygen (18O/16O) and deuterium (D/H) are used to constrain the source of spring water. Measured δ values are compared to predicted δ values for precipitation from WaterIsotopes.org for each sample site. Measured isotopic values range from -14.9 ‰ to -10.7 ‰ for δ18O and -108 ‰ to -78 ‰ for δD. The majority of samples from above 2000 m match predicted isotopic values for precipitation. Most samples taken below 2000 m are lighter than predicted isotopic values for precipitation. The TDS of spring samples measured in the lab show they range from 184 mg/L to 1552 mg/L with the majority of samples between 220 - 430 mg/L. TDS shows a weak correlation (R2 = 0.54) with altitude, where lower TDS is measured in higher altitude samples. These measurements are consistent with high altitude samples representing precipitation and low altitude samples representing shallow groundwater. Location and altitude of springs sampled in this study, as well as those recorded by earlier studies, were used to create a potentiometric surface map in GIS. From the map, water flow direction is inferred to flow mostly from the Abajo Mountains in the southeast towards the Colorado River in the northwest. A transient groundwater flow and solute transport model is developed for a 2-D cross section from the Abajo Mountains in the SE to the Colorado River in the NW. Recharge is applied in the southeast, driving water flow towards the northwest. Most discharge flows into the Colorado River, primarily via seepage through cliff faces. Surface discharge occurs in topographic lows. The flow and solute concentration patterns from the model are generally consistent with field data. Evaporite dissolution varies laterally depending on groundwater flow pattern. Deep groundwater flow patterns and pore pressure data from the model will contribute to an understanding of subsurface salt dissolution and active salt tectonics in the study region. Additionally, the results of this study will help land and water managers protect scarce freshwater resources in this arid desert region.

URBAN STORMWATER TRACING WITH THE NATURALLY OCCURRING DEUTERIUM ISOTOPE

EPA Science Inventory

Measurements of the naturally-occurring deuterium isotope assist the tracing of water components during wet-weather flows in an urban watershed. A transect of installations in the vadose and saturated zones was completed in the vicinity of a small stream and storm sewer. High-r...

Using Stable Isotopes to Understand Degradation of Organic Contaminants in Ground Water

EPA Science Inventory

Stable isotopes are a powerful tool to understand biodegradation. However, there are two interactions that can substantially confuse the interpretation of CSIR data: heterogeneity in flow paths in the aquifer and proximity to NAPL or other source of contamination to ground wate...

Design and operation of a continuous 13C and 15N labeling chamber for uniform or differential, metabolic and structural, plant tissue isotope labeling

USDA-ARS?s Scientific Manuscript database

Tracing heavy stable isotopes from plant material through the ecosystem provides the most sensitive information about ecosystem processes; from CO2 fluxes and soil organic matter formation to small-scale stable-isotope biomarker probing. Coupling multiple stable isotopes such as 13C with 15N, 18O o...

Measurement of Muscle Protein Fractional Synthetic Rate by Capillary Gas Chromatography/Combustion Isotope Ratio Mass Spectrometry

PubMed Central

Yarasheski, Kevin E.; Smith, Kenneth; Rennie, Michael J.; Bier, Dennis M.

2014-01-01

The measurement of skeletal muscle protein fractional synthetic rate using an infusion of (1-13C)leucine and measuring the isotopic abundance of the tracer in skeletal muscle protein by preparative gas chromatography (GC)/ninhydrin isotope ratio mass spectrometry (IRMS) is laborious and subject to errors owing to contamination by 12C. The purpose of this study was to compare muscle (13C)leucine enrichment measured with the conventional preparative GC/ninhydrin IRMS approach to a new, continuous-flow technique using capillary GC/combustion IRMS. Quadriceps muscles were removed from four Sprague–Dawley rats after each was infused at a different rate with (1-13C)leucine for 6–8 h. Muscle leucine enrichment (at.% excess) measured by both methods differed by less than 4%, except at low (13C)leucine enrichments (<0.03 at.% excess). In addition, capillary GC/combustion IRMS was used to assess muscle (13C)leucine enrichment and fractional muscle protein synthesis rate in ten normal young men and women infused with (1,2-13C2)leucine for 12–14 h. This approach reduced the variability of the isotope abundance measure and gave estimates of muscle protein synthesis rate (0.050 ± 0.011% h−1 (mean ± SEM); range = 0.023–0.147% h−1) that agree with published values determined using the standard analytical approach. The measurement of (13C)leucine enrichment from skeletal muscle protein by capillary GC/combustion IRMS provides a simple, acceptable and practical alternative to preparative GC/ninhydrin IRMS. PMID:1420371

delta 13C analyses of vegetable oil fatty acid components, determined by gas chromatography--combustion--isotope ratio mass spectrometry, after saponification or regiospecific hydrolysis.

PubMed

Woodbury, S E; Evershed, R P; Rossell, J B

1998-05-01

The delta 13C values of the major fatty acids of several different commercially important vegetable oils were measured by gas chromatography--combustion--isotope ratio mass spectrometry. The delta 13C values obtained were found to fall into two distinct groups, representing the C3 and C4 plants classes from which the oils were derived. The delta 13C values of the oils were measured by continuous flow elemental isotope ratio mass spectrometry and were found to be similar to their fatty acids, with slight differences between individual fatty acids. Investigations were then made into the influence on the delta 13C values of fatty acids of the position occupied on the glycerol backbone. Pancreatic lipase was employed to selectively hydrolyse fatty acids from the 1- and 3-positions with the progress of the reaction being followed by high-temperature gas chromatography in order to determine the optimum incubation time. The 2-monoacylglycerols were then isolated by thin-layer chromatography and fatty acid methyl esters prepared. The delta 13C values obtained indicate that fatty acids from any position on the glycerol backbone are isotopically identical. Thus, whilst quantification of fatty acid composition at the 2-position and measurement of delta 13C values of oils and their major fatty acids are useful criteria in edible oil purity assessment, measurement of delta 13C values of fatty acids from the 2-position does not assist with oil purity assignments.

Oxygen-isotope exchange and mineral alteration in gabbros of the Lower Layered Series, Kap Edvard Holm Complex, East Greenland

USGS Publications Warehouse

Fehlhaber, Kristen L.; Bird, Dennis K.

1991-01-01

Multiple intrusions of gabbros, mafic dikes, and syenites in the Kap Edvard Holm Complex gave rise to prolonged circulation of meteoric hydrothermal solutions and extreme isotope exchange and mineral alteration in the 3600-m-thick Lower Layered Series gabbros. In the Lower Layered Series, δ18O of plagioclase varies from +0.3‰ to -5.8‰, and it decreases with an increase in the volume of secondary talc, chlorite, and actinolite. In the same gabbros, pyroxenes have a more restricted range in δ18O, from 5.0‰ to 3.8‰ and values of δ18Opyroxene are independent of the abundance of secondary minerals, which ranges from 14% to 30%. These relations indicate that large amounts of water continued to flow through the rocks at temperatures of <500-600°C, altering the gabbros to assemblages of talc + chlorite + actinolite ± epidote ±albite and causing significant oxygen-isotope exchange in plagioclase, but not in pyroxene. The extensive low-temperature secondary mineralization and 18O depletion of plagioclase in the Lower Layered Series are associated with the later emplacement of dikes and gabbros and syenites, which created new fracture systems and provided heat sources for hydrothermal fluid circulation. This produced subsolidus mineral alteration and isotope exchange in the Lower Layered Series that are distinct from those in the Skaergaard and Cuillin gabbros of the North Atlantic Tertiary province, but are similar to those observed in some oceanic gabbros.

Automated Sample Preparation for Radiogenic and Non-Traditional Metal Isotopes: Removing an Analytical Barrier for High Sample Throughput

NASA Astrophysics Data System (ADS)

Field, M. Paul; Romaniello, Stephen; Gordon, Gwyneth W.; Anbar, Ariel D.; Herrmann, Achim; Martinez-Boti, Miguel A.; Anagnostou, Eleni; Foster, Gavin L.

2014-05-01

MC-ICP-MS has dramatically improved the analytical throughput for high-precision radiogenic and non-traditional isotope ratio measurements, compared to TIMS. The generation of large data sets, however, remains hampered by tedious manual drip chromatography required for sample purification. A new, automated chromatography system reduces the laboratory bottle neck and expands the utility of high-precision isotope analyses in applications where large data sets are required: geochemistry, forensic anthropology, nuclear forensics, medical research and food authentication. We have developed protocols to automate ion exchange purification for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U) using the new prepFAST-MC™ (ESI, Nebraska, Omaha). The system is not only inert (all-flouropolymer flow paths), but is also very flexible and can easily facilitate different resins, samples, and reagent types. When programmed, precise and accurate user defined volumes and flow rates are implemented to automatically load samples, wash the column, condition the column and elute fractions. Unattended, the automated, low-pressure ion exchange chromatography system can process up to 60 samples overnight. Excellent reproducibility, reliability, recovery, with low blank and carry over for samples in a variety of different matrices, have been demonstrated to give accurate and precise isotopic ratios within analytical error for several isotopic systems (B, Ca, Fe, Cu, Zn, Sr, Cd, Pb and U). This illustrates the potential of the new prepFAST-MC™ (ESI, Nebraska, Omaha) as a powerful tool in radiogenic and non-traditional isotope research.

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.

Apparatus and method for monitoring of gas having stable isotopes

DOEpatents

Clegg, Samuel M; Fessenden-Rahn, Julianna E

2013-03-05

Gas having stable isotopes is monitored continuously by using a system that sends a modulated laser beam to the gas and collects and transmits the light not absorbed by the gas to a detector. Gas from geological storage, or from the atmosphere can be monitored continuously without collecting samples and transporting them to a lab.

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.

Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Geilmann, Heike; Brand, Willi A.; Böhlke, J.K.

2003-01-01

Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ13C value of −26.24‰ relative to VPDB and a δ15N value of −4.52‰ relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a δ13C value of +37.76‰ and a δ15N value of +47.57‰. The δ13C and δ15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (δ13C = +1.95‰), L-SVEC lithium carbonate (δ13C = −46.48‰), IAEA-N-1 ammonium sulfate (δ15N = 0.43‰), and USGS32 potassium nitrate (δ15N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ13C is better than 0.13‰, and that of δ15N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ13C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

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.

Groundwater Recharge and Flow Processes in Taihang Mountains, a Semi-humid Region, North China

NASA Astrophysics Data System (ADS)

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

2015-04-01

Groundwater flow/recharge variations in time and space are crucial for effective water management especially in semi-arid and semi-humid regions. In order to reveal comprehensive groundwater flow/recharge processes in a catchment with a large topographical relief and seasonal hydrological variations, intensive field surveys were undertaken at 4 times in different seasons (June 2011, August 2012, November 2012, February 2014) in the Wangkuai watershed, Taihang mountains, which is a main groundwater recharge area of the North China Plain. The groundwater, spring, stream water and reservoir water were taken, and inorganic solute constituents and stable isotopes of oxygen-18 and deuterium were determined on all water samples. Also, the stream flow rate and the depth of groundwater table were observed. The stable isotopic compositions and inorganic solute constituents in the groundwater are depleted and shown similar values as those of the surface water at the mountain-plain transitional area. Additionally, the groundwater in the vicinity of the Wangkuai Reservoir presents clearly higher stable isotopic compositions and lower d-excess than those of the stream water, indicating the groundwater around the reservoir is affected by evaporation same as the Wangkuai Reservoir itself. Hence, the surface water in the mountain-plain transitional area and Wangkuai Reservoir are principal groundwater recharge sources. An inversion analysis and simple mixing model were applied in the Wangkuai watershed using stable isotopes of oxygen-18 and deuterium to construct a groundwater flow model. The model shows that multi-originated groundwater flows from upstream to downstream along topography with certain mixing. In addition, the groundwater recharge occurs dominantly at the altitude from 421 m to 953 m, and the groundwater recharge rate by the Wangkuai Reservoir is estimated to be 2.4 % of the total groundwater recharge in the Wangkuai watershed. Therefore, the stream water and reservoir water in the mountain-plain transitional area plays an important role of groundwater recharge in semi-arid and semi-humid regions.

Sediment source detection by stable isotope analysis, carbon and nitrogen content and CSSI in a small river of the Swiss Plateau

NASA Astrophysics Data System (ADS)

SchindlerWildhaber, Yael; Alewell, Christine; Birkholz, Axel

2014-05-01

Suspended sediment (SS) and organic matter in rivers can harm the fauna by affecting health and fitness of free swimming fish and by causing siltation of the riverbed. The temporal and spatial dynamics of sediment, carbon (C) and nitrogen (N) during the brown trout spawning season in a small river of the Swiss Plateau were assessed and C isotopes as well as the C/N atomic ratio were used to distinguish autochthonous and allochthonous sources of organic matter in SS loads. The visual basic program IsoSource with 13Ctot and 15N as input isotopes was used to quantify the temporal and spatial sources of SS. We determined compound specific stable carbon isotopes (CSSI) in fatty acids of possible sediment source areas to the stream in addition and compared them to SS from selected high flow and low flow events. Organic matter concentrations in the infiltrated and suspended sediment were highest during low flow periods with small sediment loads and lowest during high flow periods with high sediment loads. Peak values in nitrate and dissolved organic C were measured during high flow and high rainfall, probably due to leaching from pasture and arable land. The organic matter was of allochthonous sources as indicated by the C/N atomic ratio and δ13Corg. Organic matter in SS increased from up- to downstream due to an increase in sediment delivery from pasture and arable land downstream of the river. While the major sources of SS are pasture and arable land during base flow conditions, SS from forest soils increased during heavy rain events and warmer winter periods most likely due to snow melt which triggered erosion. Preliminary results of CSSI analysis of sediment source areas and comparison to SS of selected events indicate that differences in d13C values of individual fatty acids are too small to differentiate unambiguously between sediment sources.

Water exchange, mixing and transient storage between a saturated karstic conduit and the surrounding aquifer: Groundwater flow modeling and inputs from stable water isotopes

NASA Astrophysics Data System (ADS)

Binet, S.; Joigneaux, E.; Pauwels, H.; Albéric, P.; Fléhoc, Ch.; Bruand, A.

2017-01-01

Water exchanges between a karstic conduit and the surrounding aquifer are driven by hydraulic head gradient at the interface between these two domains. The case-study presented in this paper investigates the impact of the geometry and interface conditions around a conduit on the spatial distribution of these exchanges. Isotopic (δ18O and δD), discharge and water head measurements were conducted at the resurgences of a karst system with a strong allogenic recharge component (Val d'Orléans, France), to estimate the amounts of water exchanged and the mixings between a saturated karstic conduit and the surrounding aquifer. The spatio-temporal variability of the observed exchanges was explored using a 2D coupled continuum-conduit flow model under saturated conditions (Feflow®). The inputs from the water heads and stable water isotopes in the groundwater flow model suggest that the amounts of water flowing from the aquifer are significant if the conduit flow discharges are less than the conduit flow capacity. This condition creates a spatial distribution of exchanges from upstream where the aquifer feeds the conduit (recharge area) to downstream where the conduit reaches its maximum discharge capacity and can feed the aquifer (discharge area). In the intermediate transport zone no exchange between the two domains takes place that brings a new criterion to delineate the vulnerable zones to surface water. On average, 4% of the water comes from the local recharge, 80% is recent river water and 16% is old river water. During the November 2008 flood, both isotopic signatures and model suggest that exchanges fluctuate around this steady state, limited when the river water level increases and intensified when the river water level decreases. The existence of old water from the river suggests a transient storage at the aquifer/conduit interface that can be considered as an underground hyporheic zone.

Isotope effect of mercury diffusion in air

PubMed Central

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

2014-01-01

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

Isotope effect of mercury diffusion in air.

PubMed

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

2014-01-01

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

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.

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.

The two-dimensional pattern of metamorphic fluid flow at Mary Kathleen, Australia: Fluid focusing, transverse dispersion, and implications for modeling fluid flow

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

Cartwright, I.

The pattern of [delta][sup 18]O values in layered Corella calc-silicate rocks adjacent to a scapolitized metadolerite dike at Timberu in the Mary Kathleen fold belt illustrates some of the complexities of two-dimensional metamorphic fluid flow. Fluids flowing from the dike ([delta][sup 18]O = 9-10%) into the calc-silicate rocks lowered calcite [delta][sup 18]O values form 19-20% to as low as 10.3%. Time-integrate advectite fluid fluxes varied from 0.72 to > 8.1 m[sup 3]/m[sup 2] over a 4.5-m lateral distance, and there are two distinct channels of higher fluid flux. If the duration of fluid flow was similar across the outcrop, intrinsicmore » permeabilities varied laterally by at least an order of magnitude. Fluid flow was largely focused across lithological layering, with rare excursions parallel to layering, suggesting that (up to 1 m) to those at the isotopic front ([approximately]1.2 m), indicating that the coefficients of transverse and longitudinal dispersion are of similar orders of magnitude. Localities in other terrains probably show similar complex patterns of isotopic resetting that in two dimensions correspond to the predictions of the advective-dispersive transport models, but which are difficult to interpret using a one-dimensional analysis. Transverse dispersion during channeled fluid flow will potentially reset O-isotope ratios adjacent to the channels and cause decoupling of geochemical parameters during advective and dispersive transport. 43 refs., 5 figs., 2 tabs.« less

Evaluation of diffuse and preferential flow pathways of infiltrated precipitation and irrigation using oxygen and hydrogen isotopes

NASA Astrophysics Data System (ADS)

Ma, Bin; Liang, Xing; Liu, Shaohua; Jin, Menggui; Nimmo, John R.; Li, Jing

2017-05-01

Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (18O) and hydrogen (2H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10-40 cm depth in the grassland and arable land, and 10-60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ18O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ18O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ18O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ18O spikes at 20-50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

A quarter-million years of paleoenvironmental change at Bear Lake, Utah and Idaho

USGS Publications Warehouse

Kaufman, D.S.; Bright, Jordon; Dean, W.E.; Rosenbaum, J.G.; Moser, K.; Anderson, R. Scott; Colman, Steven M.; Heil, C.W.; Jiménez-Moreno, Gonzalo; Reheis, M.C.; Simmons, K.R.

2009-01-01

A continuous, 120-m-long core (BL00-1) from Bear Lake, Utah and Idaho, contains evidence of hydrologic and environmental change over the last two glacial-interglacial cycles. The core was taken at 41.95??N, 111.31??W, near the depocenter of the 60-m-deep, spring-fed, alkaline lake, where carbonate-bearing sediment has accumulated continuously. Chronological control is poor but indicates an average sedimentation rate of 0.54 mm yr-1. Analyses have been completed at multi-centennial to millennial scales, including (in order of decreasing temporal resolution) sediment magnetic properties, oxygen and carbon isotopes on bulk-sediment carbonate, organic- and inorganiccarbon contents, palynology; mineralogy (X-ray diffraction), strontium isotopes on bulk carbonate, ostracode taxonomy, oxygen and carbon isotopes on ostracodes, and diatom assemblages. Massive silty clay and marl constitute most of the core, with variable carbonate content (average = 31 ?? 19%) and oxygen-isotopic values (??18O ranging from -18??? to -5??? in bulk carbonate). These variations, as well as fluctuations of biological indicators, reflect changes in the water and sediment discharged from the glaciated headwaters of the dominant tributary, Bear River, and the processes that influenced sediment delivery to the core site, including lake-level changes. Although its influence has varied, Bear River has remained a tributary to Bear Lake during most of the last quarter-million years. The lake disconnected from the river and, except for a few brief excursions, retracted into a topographically closed basin during global interglaciations (during parts of marine isotope stages 7, 5, and 1). These intervals contain up to 80% endogenic aragonite with high ??18O values (average = -5.8 ?? 1.7???), indicative of strongly evaporitic conditions. Interglacial intervals also are dominated by small, benthic/tychoplanktic fragilarioid species indicative of reduced habitat availability associated with low lake levels, and they contain increased high-desert shrub and Juniperus pollen and decreased forest and forest-woodland pollen. The 87Sr 86Sr values (>0.7100) also increase, and the ratio of quartz to dolomite decreases, as expected in the absence of Bear River in flow. The changing paleoenvironments inferred from BL00-1 generally are consistent with other regional and global records of glacialinterglacial fluctuations; the diversity of paleoenvironmental conditions inferred from BL00-1 also reflects the influence of catchment-scale processes. Copyright ?? 2009 The Geological Society of America.

Development of metal hydride composites

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

Congdon, J.W.

1992-12-01

Most of current hydride technology at Savannah River Site is based on beds of metal hydride powders; the expansion upon hydridation and the cycling results in continued breakdown into finer particles. Goal is to develop a composite which will contain the fines in a dimensionally stable matrix, for use in processes which require a stable gas flow through a hydride bed. Metal hydride composites would benefit the advanced Thermal Cycling Absorption process (hydrogen isotope separation), and the Replacement Tritium Facility (storage, pumping, compression, purification of hydrogen isotopes). These composites were fabricated by cold compaction of a mixture of metal hydridemore » granules and coarse copper powder; the porosity in the granules was introduced by means of ammonium carbonate. The composite pellets were cycled 138 times in hydrogen with the loss of LANA0.75 (LaNi{sub 4.25}Al{sub 0.75}) limited to the surface. Vacuum sintering can provide additional strength at the edges. Without a coating, the metal hydride particles exposed at the pellet surface can be removed by cycling several times in hydrogen.« less

In situ sulfur isotopes (δ(34)S and δ(33)S) analyses in sulfides and elemental sulfur using high sensitivity cones combined with the addition of nitrogen by laser ablation MC-ICP-MS.

PubMed

Fu, Jiali; Hu, Zhaochu; Zhang, Wen; Yang, Lu; Liu, Yongsheng; Li, Ming; Zong, Keqing; Gao, Shan; Hu, Shenghong

2016-03-10

The sulfur isotope is an important geochemical tracer in diverse fields of geosciences. In this study, the effects of three different cone combinations with the addition of N2 on the performance of in situ S isotope analyses were investigated in detail. The signal intensities of S isotopes were improved by a factor of 2.3 and 3.6 using the X skimmer cone combined with the standard sample cone or the Jet sample cone, respectively, compared with the standard arrangement (H skimmer cone combined with the standard sample cone). This signal enhancement is important for the improvement of the precision and accuracy of in situ S isotope analysis at high spatial resolution. Different cone combinations have a significant effect on the mass bias and mass bias stability for S isotopes. Poor precisions of S isotope ratios were obtained using the Jet and X cones combination at their corresponding optimum makeup gas flow when using Ar plasma only. The addition of 4-8 ml min(-1) nitrogen to the central gas flow in laser ablation MC-ICP-MS was found to significantly enlarge the mass bias stability zone at their corresponding optimum makeup gas flow in these three different cone combinations. The polyatomic interferences of OO, SH, OOH were also significantly reduced, and the interference free plateaus of sulfur isotopes became broader and flatter in the nitrogen mode (N2 = 4 ml min(-1)). However, the signal intensity of S was not increased by the addition of nitrogen in this study. The laser fluence and ablation mode had significant effects on sulfur isotope fractionation during the analysis of sulfides and elemental sulfur by laser ablation MC-ICP-MS. The matrix effect among different sulfides and elemental sulfur was observed, but could be significantly reduced by line scan ablation in preference to single spot ablation under the optimized fluence. It is recommended that the d90 values of the particles in pressed powder pellets for accurate and precise S isotope analysis should be less than 10 μm. Under the selected optimized analytical conditions, excellent agreements between the determined values and the reference values were achieved for the IAEA-S series standard reference materials and a set of six well-characterized, isotopic homogeneous sulfide standards (PPP-1, MoS2, MASS-1, P-GBW07267, P-GBW07268, P-GBW07270), validating the capability of the developed method for providing high-quality in situ S isotope data in sulfides and elemental sulfur. Copyright © 2016. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Noble gases, stable isotopes, and radiocarbon as tracers of flow in the Dakota aquifer, Colorado and Kansas

USGS Publications Warehouse

Clark, J.F.; Davisson, M.L.; Hudson, G.B.; Macfarlane, P.A.

1998-01-01

A suite of chemical and isotope tracers (dissolved noble gases, stable isotopes of water, radiocarbon, and CI) have been analyzed along a flow path in the Dakota aquifer system to determine likely recharge sources, ground water residence times, and the extent of mixing between local and intermediate flow systems, presumably caused by large well screens. Three water types were distinguished with the tracers, each having a very different history. Two of the water types were found in south-eastern Colorado where the Dakota is poorly confined. The tracer data suggest that the first group recharged locally during the last few thousand years and the second group was composed of ground water that recharged earlier during a cooler climate, presumably during the last glacial period (LGP) and mixed aged water. The paleotemperature record archived in this groundwater system indicates that south-eastern Colorado was about 5??C cooler during the LGP than during the late Holocene. Similar temperature changes derived from dissolved noble gases in other aquifer systems have been reported earlier for the south-western United States. The third water type was located down gradient of the first two in the confined Dakota in western and central Kansas. Groundwater residence time of this water mass is on the order of 104-105 yrs and its recharge location is near the Colorado and Kansas border down gradient of the other water types. The study shows the importance of using multiple tracers when investigating ground water systems.A suite of chemical and isotope tracers (dissolved noble gases, stable isotopes of water, radiocarbon, and CL) were analyzed along a flow path in the Dakota aquifer system to determine likely recharge sources, ground water residence times, and the extent of mixing between local and intermediate flow systems. Three water types were distinguished with the tracers, each having a very different history. Two of the water types were located in south-eastern Colorado where the Dakota is poorly confined. The third water type was located down gradient of the first two in the confined Dakota in western and central Kansas.

A multidisciplinary investigation of groundwater fluctuations and their control on river chemistry - Insights from river dissolved concentrations and Li isotopes during flood events

NASA Astrophysics Data System (ADS)

Kuessner, M.; Bouchez, J.; Dangeard, M.; Bodet, L.; Thiesson, J.; Didon-Lescot, J. F.; Frick, D. A.; Grard, N.; Guérin, R.; Domergue, J. M.; Gaillardet, J.

2017-12-01

Water flow exerts a strong control on weathering reactions in the Critical Zone (CZ). The relationships between hydrology and river chemistry have been widely studied for the past decades [1]. Solute export responds strongly to storm events [2] and investigating the concentration and isotope composition of trace elements in river catchments can advance our understanding of the processes governing water-rock interactions and provide information on the water flow paths during these "hot moments". Especially, lithium (Li) and its isotopes are sensitive to the balance between mineral dissolution and precipitation in the subsurface and therefore, a powerful tool to characterize the response of chemical weathering to hydrology [3]. Hence, high-frequency stream chemistry yields valuable insight into the hydrological processes within the catchment during "hot moments". This study focuses on a CZ Observatory (OHMCV, part of French Research Infrastructure OZCAR). The granitic catchment Sapine (0.54 km2, southern France) is afflicted by big rain events and therefore, it is an appropriate location to study stormflows. Here we combine results from high-frequency stream water sampling during rain events with time-lapse seismic imaging to monitor the changes in aquifer properties [4]. The relationships between concentrations and discharge indicate differential responses of dissolved elements to the hydrological forcing. Especially, systematic changes are observed for Li and its isotopes as a function of water discharge, suggesting maximum secondary mineral formation at intermediate discharge. We suggest that Li dynamics are chiefly influenced by the depth at which water is flowing with, e.g. dissolution of primary minerals in deeper groundwater flows, and water-secondary mineral interaction at shallower depths. The combination of elemental concentrations and Li isotopes in river dissolved load tracing chemical weathering, with hydrogeophysical methods mapping water flows and pools, provides us with a time-resolved image of the CZ, improving our knowledge of the impact of hydrological changes on the chemical mass budgets in catchments. [1] Maher et al. (2011), Earth Planet. Sci. Lett. [2] Kirchner et al. (2010), Hydrol. Processes. [3] Liu et al. (2015), Earth Planet. Sci. Lett. [4] see poster by M. Dangeard et al.

Non-linear isotope and fast ions effects: routes for low turbulence in DT plasmas

NASA Astrophysics Data System (ADS)

Garcia, Jeronimo

2017-10-01

The isotope effect, i.e. the fact that heat and particle fluxes do not follow the expected Gyro-Bohm estimate for turbulent transport when the plasma mass is changed, is one of the main challenges in plasma theory. Of particular interest is the isotope exchange between the fusion of deuterium (DD) and deuterium-tritium (DT) nuclei as there are no clear indications of what kind of transport difference can be expected in burning plasmas. The GENE code is therefore used for computing DD vs DT linear and nonlinear microturbulence characteristics in the core plasma region of a previously ITER hybrid scenario at high beta obtained in the framework of simplified integrated modelling. Scans on common turbulence related quantitates as external ExB flow shear, Parallel Velocity Gradient (PVG), plasma beta, colisionality or the number of ion species have been performed. Additionally, the role of energetic particles, known to reduce Ion Temperature Gradient (ITG) turbulence has been also addressed. It is obtained that the ITER operational point will be close to threshold and in these conditions turbulence is dominated by ITG modes. A purely weak non-linear isotope effect, absent in linear scans, can be found when separately adding moderate ExB flow shear or electromagnetic effects, whereas collisionality just modulates the intensity. The isotope effect, on the other hand, becomes very strong in conditions with simultaneously moderate ExB flow shear, beta and low q profile with significant reductions of ion heat transport from DD to DT. By analyzing the radial structure of the two point electrostatic potential correlation function it has been found that the inherent Gyro-Bohm scaling for plasma microturbulence, which increases the radial correlation length at short scales form DD to DT, is counteracted by the concomitant appearance of a complex nonlinear multiscale space interaction involving external ExB flow shear, zonal flow activity, magnetic geometry and electromagnetic effects. The number of ion species and the fast ion population is also found to play a role in this non-linear process whereas a symmetry breaking between D and T, with systematic reduced heat and particle transport for T, is always obtained.

Modeling of sorption processes on solid-phase ion-exchangers

NASA Astrophysics Data System (ADS)

Dorofeeva, Ludmila; Kuan, Nguyen Anh

2018-03-01

Research of alkaline elements separation on solid-phase ion-exchangers is carried out to define the selectivity coefficients and height of an equivalent theoretical stage for both continuous and stepwise filling of column by ionite. On inorganic selective sorbents the increase in isotope enrichment factor up to 0.0127 is received. Also, parametrical models that are adequately describing dependence of the pressure difference and the magnitude expansion in the ion-exchange layer from the flow rate and temperature have been obtained. The concentration rate value under the optimum realization conditions of process and depending on type of a selective material changes in a range 1.021÷1.092. Calculated results show agreement with experimental data.

Uranium isotopes (U-234/U-238) in rivers of the Yukon Basin (Alaska and Canada) as an aid in identifying water sources, with implications for monitoring hydrologic change in arctic regions

USGS Publications Warehouse

Kraemer, Thomas F.; Brabets, Timothy P.

2012-01-01

The ability to detect hydrologic variation in large arctic river systems is of major importance in understanding and predicting effects of climate change in high-latitude environments. Monitoring uranium isotopes (234U and 238U) in river water of the Yukon River Basin of Alaska and northwestern Canada (2001–2005) has enhanced the ability to identify water sources to rivers, as well as detect flow changes that have occurred over the 5-year study. Uranium isotopic data for the Yukon River and major tributaries (the Porcupine and Tanana rivers) identify several sources that contribute to river flow, including: deep groundwater, seasonally frozen river-valley alluvium groundwater, and high-elevation glacial melt water. The main-stem Yukon River exhibits patterns of uranium isotopic variation at several locations that reflect input from ice melt and shallow groundwater in the spring, as well as a multi-year pattern of increased variability in timing and relative amount of water supplied from higher elevations within the basin. Results of this study demonstrate both the utility of uranium isotopes in revealing sources of water in large river systems and of incorporating uranium isotope analysis in long-term monitoring of arctic river systems that attempt to assess the effects of climate change.

Energy flow and trophic partitioning of contrasting Cold Water Coral ecosystems of the NE Atlantic.

NASA Astrophysics Data System (ADS)

Kiriakoulakis, K.; Smith, E. L.; Dempster, N. M.; Roberts, M.; Hennige, S. J.; Wolff, G. A.

2016-02-01

This study investigates the energy flow, trophic positioning and nutritional quality of suspended particulate organic matter (sPOM) that reaches cold-water coral (CWC) ecosystems from two contrasting oceanographic settings of the N. E. Atlantic using molecular (lipid) and stable isotopic analysis. Study sites are the shallow ( 150m) Mingulay Reef on the NW Scotland shelf vs the deeper ( 700m) Logachev Mounds on the eastern slope of the Rockall Bank. Cold water corals are now being realised as abundant, cosmopolitan and biodiverse hotspots of the global ocean. Recent research has shown links between high levels of surface primary productivity and sPOM flux; which when combined with hydrodynamic processes facilitates an almost continuous supply of nutrient rich sPOM to these deep-ocean ecosystems. However, little is understood regarding the exact nutritional requirements of these ecosystems. Fresh marine sPOM is usually rich in proteins and lipids; however during transport into the ocean interior its chemical composition is influenced by a variety of complex transformation, remineralisation and repackaging processes; thus altering its `freshness' and nutritional quality. The study of the bioavailable and nutritional fractions of sPOM in relation to specific oceanographic transport regimes can help further understand the processes, nutritional requirements and energy flow of these ecosystems. Isotopic ratios of carbon and nitrogen were analysed using EA-IR-MS and lipids via GC-MS. Initial results show significant differences in δ15N and δ13C values of sPOM between the two areas, indicating differences in trophic dynamics and sPOM re-working between locations. In addition lipid results highlight differences in trophic contributions to the energy flows of the two locations, yet similarities in molecular nutritional component contributions; thus supporting previous studies regarding the importance of certain lipid classes in the development of these deep and fragile ecosystems. This multi-disciplinary approach to biogeochemical analysis may also be used to detect chemosynthetic energy pathway contributions to sPOM.

Reactive Fluid Flow and Applications to Diagenesis, Mineral Deposits, and Crustal Rocks

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

Rye, Danny M.; Bolton, Edward W.

2002-11-04

The objective is to initiate new: modeling of coupled fluid flow and chemical reactions of geologic environments; experimental and theoretical studies of water-rock reactions; collection and interpretation of stable isotopic and geochemical field data at many spatial scales of systems involving fluid flow and reaction in environments ranging from soils to metamorphic rocks. Theoretical modeling of coupled fluid flow and chemical reactions, involving kinetics, has been employed to understand the differences between equilibrium, steady-state, and non-steady-state behavior of the chemical evolution of open fluid-rock systems. The numerical codes developed in this project treat multi-component, finite-rate reactions combined with advective andmore » dispersive transport in multi-dimensions. The codes incorporate heat, mass, and isotopic transfer in both porous and fractured media. Experimental work has obtained the kinetic rate laws of pertinent silicate-water reactions and the rates of Sr release during chemical weathering. Ab-initio quantum mechanical techniques have been applied to obtain the kinetics and mechanisms of silicate surface reactions and isotopic exchange between water and dissolved species. Geochemical field-based studies were carried out on the Wepawaug metamorphic schist, on the Irish base-metal sediment-hosted ore system, in the Dalradian metamorphic complex in Scotland, and on weathering in the Columbia River flood basalts. The geochemical and isotopic field data, and the experimental and theoretical rate data, were used as constraints on the numerical models and to determine the length and time scales relevant to each of the field areas.« less

Method and apparatus for separation of heavy and tritiated water

DOEpatents

Lee, Myung W.

2001-01-01

The present invention is a bi-thermal membrane process for separating and recovering hydrogen isotopes from a fluid containing hydrogen isotopes, such as water and hydrogen gas. The process in accordance with the present invention provides counter-current cold and hot streams of the fluid separated with a thermally insulating and chemically transparent proton exchange membrane (PEM). The two streams exchange hydrogen isotopes through the membrane: the heavier isotopes migrate into the cold stream, while the lighter isotopes migrate into the hot stream. The heavy and light isotopes are continuously withdrawn from the cold and hot streams respectively.

The Practical Application of Aqueous Geochemistry in Mapping Groundwater Flow Systems in Fractured Rock Masses

NASA Astrophysics Data System (ADS)

Bursey, G.; Seok, E.; Gale, J. E.

2017-12-01

Flow to underground mines and open pits takes place through an interconnected network of regular joints/fractures and intermediate to large scale structural features such as faults and fracture zones. Large scale features can serve either as high permeability pathways or as barriers to flow, depending on the internal characteristics of the structure. Predicting long term water quality in barrier-well systems and long-term mine water inflows over a mine life, as a mine expands, requires the use of a 3D numerical flow and transport code. The code is used to integrate the physical geometry of the fractured-rock mass with porosity, permeability, hydraulic heads, storativity and recharge data and construct a model of the flow system. Once that model has been calibrated using hydraulic head and permeability/inflow data, aqueous geochemical and isotopic data provide useful tools for validating flow-system properties, when one is able to recognize and account for the non-ideal or imperfect aspects of the sampling methods used in different mining environments. If groundwater samples are collected from discrete depths within open boreholes, water in those boreholes have the opportunity to move up or down in response to the forces that drive groundwater flow, whether they be hydraulic gradients, gas pressures, or density differences associated with variations in salinity. The use of Br/Cl ratios, for example, can be used to determine if there is active flow into, or out of, the boreholes through open discontinuities in the rock mass (i.e., short-circuiting). Natural groundwater quality can also be affected to varying degrees by mixing with drilling fluids. The combined use of inorganic chemistry and stable isotopes can be used effectively to identify dilution signals and map the dilution patterns through a range of fresh, brackish and saline water types. The stable isotopes of oxygen and hydrogen are nearly ideal natural tracers of water, but situations occur when deep groundwater samples can plot to the left of the meteoric water line as a result of isotopic exchange between meteoric water and silicate rock in near-surface environments at low temperatures. These and other examples are considered in the practical application of aqueous geochemistry in helping to map flow systems in fractured-rock systems.

Stable isotope reactive transport modeling in water-rock interactions during CO2 injection

NASA Astrophysics Data System (ADS)

Hidalgo, Juan J.; Lagneau, Vincent; Agrinier, Pierre

2010-05-01

Stable isotopes can be of great usefulness in the characterization and monitoring of CO2 sequestration sites. Stable isotopes can be used to track the migration of the CO2 plume and identify leakage sources. Moreover, they provide unique information about the chemical reactions that take place on the CO2-water-rock system. However, there is a lack of appropriate tools that help modelers to incorporate stable isotope information into the flow and transport models used in CO2 sequestration problems. In this work, we present a numerical tool for modeling the transport of stable isotopes in groundwater reactive systems. The code is an extension of the groundwater single-phase flow and reactive transport code HYTEC [2]. HYTEC's transport module was modified to include element isotopes as separate species. This way, it is able to track isotope composition of the system by computing the mixing between the background water and the injected solution accounting for the dependency of diffusion on the isotope mass. The chemical module and database have been expanded to included isotopic exchange with minerals and the isotope fractionation associated with chemical reactions and mineral dissolution or precipitation. The performance of the code is illustrated through a series of column synthetic models. The code is also used to model the aqueous phase CO2 injection test carried out at the Lamont-Doherty Earth Observatory site (Palisades, New York, USA) [1]. References [1] N. Assayag, J. Matter, M. Ader, D. Goldberg, and P. Agrinier. Water-rock interactions during a CO2 injection field-test: Implications on host rock dissolution and alteration effects. Chemical Geology, 265(1-2):227-235, July 2009. [2] Jan van der Lee, Laurent De Windt, Vincent Lagneau, and Patrick Goblet. Module-oriented modeling of reactive transport with HYTEC. Computers & Geosciences, 29(3):265-275, April 2003.

Using Sap Flow Monitoring for Improved Process-based Ecohydrologic Understanding 2022

USDA-ARS?s Scientific Manuscript database

Sap flow measurements can be an important tool for unraveling the complex web of ecosystem fluxes, especially when it is combined with other measurements like eddy covariance, isotopes, remote sensing, etc. In this talk, we will demonstrate how sap flow measurements have improved our process-level u...

Modeling radium distribution in coastal aquifers during sea level changes: The Dead Sea case

USGS Publications Warehouse

Kiro, Yael; Yechieli, Yoseph; Voss, Clifford I.; Starinsky, Abraham; Weinstein, Yishai

2012-01-01

We present a new approach to studying the behavior of radium isotopes in a coastal aquifer. In order to simulate radium isotope distributions in the dynamic flow field of the Dead Sea aquifer, a multi-species density dependent flow model (SUTRA-MS) was used. Field data show that the activity of 226Ra decreases from 140 to 60 dpm/L upon entering the aquifer from the Dead Sea, and then further decreases linearly due to mixing with Ra-poor fresh water. On the other hand, an increase is observed in the activity of the shorter-lived isotopes (up to 52 dpm/L 224Ra and 31 dpm/L 223Ra), which are relatively low in Dead Sea water (up to 2.5 dpm/L 224Ra and 0.5 dpm/L 223Ra). The activities of the short lived radium isotopes also decrease with decreasing salinity, which is due to the effect of salinity on the adsorption of radium. The relationship between 224Ra and salinity suggests that the adsorption partition coefficient (K) is linearly related to salinity. Simulations of the steady-state conditions, show that the distance where equilibrium activity is attained for each radium isotope is affected by the isotope half-life, K and the groundwater velocity, resulting in a longer distance for the long-lived radium isotopes. K affects the radium distribution in transient conditions, especially that of the long-lived radium isotopes. The transient conditions in the Dead Sea system, with a 1 m/yr lake level drop, together with the radium field data, constrains K to be relatively low (226Ra cannot be explained by adsorption, and it is better explained by removal via coprecipitation, probably with barite or celestine.

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).

Models for coupled fluid flow, mineral reaction, and isotopic alteration during contact metamorphism: The Notch Peak aureole, Utah

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

Ferry, J.M.; Dipple, G.M.

Three different models were developed to simulate the effect of contact metamorphism and fluid-rock interaction on the prograde mineralogical and O isotopic evolution of calcareous argillites from the Notch Peak aureole, Utah. All models assume local mineral-fluid equilibrium, a steady-state temperature profile corresponding to peak metamorphic values, and the thermodynamic data for minerals and fluid of Berman (1988). The preferred model, metamorphism with flow of a time-integrated fluid flux of 2 {plus minus} 0.5 {center dot} 10{sup 4} mol/cm{sup 2} in the direction of increasing temperature, successfully reproduces the principal petrologic and isotopic features of the aureole: (1) occurrence andmore » positions (in map view) of diopside-in, tremolite-out, grossular-in, wollastonite-in, and quartz-out isograds; (2) stable coexistence of tremolite + calcite + quartz + diopside over an {approx}1 km distance between the diopside-in and tremolite-out isograds; (3) variable whole-rock {sup 18}O depletions of {approx}6-9{per thousand} adjacent to the contact; and (4) a gradual and irregular increase in {delta}{sup 18}O with increasing distance from the pluton. Results demonstrate how isotopic and petrologic data for contact aureoles can be integrated to provide quantitative constraints on the magnitude and geometry of metamorphic fluid flow.« less

Calculation of gas-flow in plasma reactor for carbon partial oxidation

NASA Astrophysics Data System (ADS)

Bespala, Evgeny; Myshkin, Vyacheslav; Novoselov, Ivan; Pavliuk, Alexander; Makarevich, Semen; Bespala, Yuliya

2018-03-01

The paper discusses isotopic effects at carbon oxidation in low temperature non-equilibrium plasma at constant magnetic field. There is described routine of experiment and defined optimal parameters ensuring maximum enrichment factor at given electrophysical, gas-dynamic, and thermodymanical parameters. It has been demonstrated that at high-frequency generator capacity of 4 kW, supply frequency of 27 MHz and field density of 44 mT the concentration of paramagnetic heavy nuclei 13C in gaseous phase increases up to 1.78 % compared to 1.11 % for natural concentration. Authors explain isotopic effect decrease during plasmachemical separation induced by mixing gas flows enriched in different isotopes at the lack of product quench. With the help of modeling the motion of gas flows inside the plasma-chemical reactor based on numerical calculation of Navier-Stokes equation authors determine zones of gas mixing and cooling speed. To increase isotopic effects and proportion of 13C in gaseous phase it has been proposed to use quench in the form of Laval nozzle of refractory steel. The article represents results on calculation of optimal Laval Nozzle parameters for plasma-chemical reactor of chosen geometry of. There are also given dependences of quench time of products on pressure at the diffuser output and on critical section diameter. Authors determine the location of quench inside the plasma-chemical reactor in the paper.

The use of natural isotopes for identifying the origins of groundwater flows: Drentsche Aa Brook Valley, The Netherlands.

NASA Astrophysics Data System (ADS)

Elshehawi, Samer; Grootjans, Ab; Bregman, Enno

2017-04-01

This paper investigates the origin of various groundwater flows in a small brook valley reserve Drentsche Aa Valley in the northern part of the Netherlands. The aim was also to validate a hydrological model that simulated coupled particle flow in this area and also incorporated different scenarios for groundwater abstraction in order to predict future implications of groundwater abstraction on ecological values. Water samples from various sites and depths were analysed for macro-ionic composition, stable isotopes (2H and 18O) and also 14C. Three sites have 14C activities over 100%, indicating very recent water. The main groundwater discharge areas showed inflow of old groundwater up to 5000 years. Inflow of different groundwater flows of various ages could be detected most clearly from the 14C data. Downstream area that were affected by groundwater abstraction showed distinct infiltration characteristics, both in macro-ionic composition and contents of natural isotopes, to a depth of 6m below surface In the main exfiltration areas, we found that at 95 meters below the surface, the groundwater was characterized by a NaCl type groundwater facies. But the absolute concentrations were not high enough to conclude that double diffusive convection (DDC) near a salt diapir was responsible for this effect.

Discovering complex groundwater dynamics of a multiple aquifer system on the base of stable and radio-isotope patterns

NASA Astrophysics Data System (ADS)

Wilske, Cornelia; Rödiger, Tino; Suckow, Axel; Geyer, Stefan; Weise, Stephan; Merchel, Silke; Rugel, Georg; Pavetich, Stefan; Merkel, Broder; Siebert, Christian

2017-04-01

The water supply in semi-arid Israel and Palestine, predominantly relies on groundwater as freshwater resource, stressed by increasing demand and low recharge rates. Sustainable management of such resources requires a sound understanding of its groundwater migration through space and time, particularly in structurally complex multi-aquifer systems as the Eastern Mountain Aquifer, affected by salting. To differentiate between the flow paths of the different water bodies and their respective residence times, a multi-tracer approach, combining age dating isotopes (36Cl/Cl; 3H) with rock specific isotopes like 87Sr/86Sr and δ34S-SO4 was applied. As a result, the investigated groundwaters from the two Cretaceous aquifers and their respective flow paths are differentiable by e.g. their 87Sr/86Sr signatures, resembling the intensity of the rock-water interaction and hence indirectly residence times. In the discharge areas within the Jordan Valley and along the Dead Sea shore, δ34S-SO4 ratios reveal the different sources of salinity (ascending brines, interstitial brines and dissolved salts). Based on 36Cl and 3H and the atmospheric input functions, very heterogeneous infiltration times and effective flow velocities, respectively, indicate an at least dual porosity system, resulting in distinctly different regimes of matrix and pipe flow.

Sources and fate of nitrate in the Illinois River Basin, Illinois

USGS Publications Warehouse

Panno, S.V.; Kelly, W.R.; Hackley, Keith C.; Hwang, H.-H.; Martinsek, A.T.

2008-01-01

We conducted a two-year investigation into the sources and fate of nitrate (NO3-) in the Illinois River from the Chicago area to the river's confluence with the Mississippi River. Samples from waterways in the Chicago area (Des Plaines River and the Sanitary and Ship Canal) had relatively high concentrations of nitrogen (N) species and NO3- isotopic compositions indicative of treated wastewater (TWW). Downstream of the Brandon Road Lock and Dam, NO3- in tributaries discharging to the Illinois River primarily comes from tiles draining row crops. Nitrate isotopic signatures from these tributaries as well as drain tiles were indicative of synthetic fertilizer and/or soil organic matter (SOM) at various stages of denitrification. Nitrate-N concentrations generally decreased in the Illinois River with distance from the Chicago area primarily due to dilution. The decrease in NO3-N concentrations was especially conspicuous during the summer, when there is minimal discharge from drain tiles and NO3-N concentrations in the tributaries were low. In August 2005, when conditions were very dry, NO3-N concentrations decreased from 7.4 mg/L in the Chicago area to less than 1 mg/L near where the Illinois River discharges to the Mississippi River. The isotopic composition of NO3- in water samples from the Illinois River were a mixture of three end members: (1) fertilizer and/or SOM in drain tile water, typically showing the least amount of denitrification, (2) fertilizer and/or SOM in deeper ground water, showing the highest degree of denitrification, and (3) TWW. There was seasonal variability, depending on the volume of water flowing in the Illinois River. During high flow periods, river water samples plotted closest to those of tile drain samples; during low flow periods, a greater influence of TWW was observed in the isotopic composition. A subset of summer samples from the Chicago waterways had isotopic values plotting near and within the domain that characterizes manure and sewage. Nitrate in the Chicago area is primarily derived from TWW, with its isotopic signature evident downstream at least as far as Pekin during most of the year and all the way to the Mississippi River during periods of low flow. Denitrification occurs predominantly in groundwater between and away from drain tiles, although there is evidence that in-stream denitrification and/or biological uptake of NO3- occurs in the Peoria Lake reach of the Illinois River, at least during periods of low flow in the summer. We calculated that the river was losing about half of its NO3-N load in Peoria Lake in August 2005 (a period of very low flow), at a rate of about 7500 kg/day.

Heart-cutting two-dimensional gas chromatography in combination with isotope ratio mass spectrometry for the characterization of the wax fraction in plant material.

PubMed

Dumont, Emmie; Tienpont, Bart; Higashi, Nobukazu; Mitsui, Kazuhisa; Ochiai, Nobuo; Kanda, Hirooki; David, Frank; Sandra, Pat

2013-11-22

Gas chromatography coupled to isotope ratio mass spectrometry after on-line combustion (GC-C-IRMS) and high temperature conversion (GC-HTC-IRMS) is used for compound specific isotope ratio determination. This determination can only be performed successfully if the target solutes are fully resolved from other compounds. A new instrumental set-up consisting of heart-cutting two-dimensional GC based on capillary flow technology and a low thermal mass GC oven in combination with an isotope ratio mass spectrometer is presented. Capillary flow technology was also used in all column and interface connections for robust and leak-free operation. The new configuration was applied to the characterization of wax compounds in tobacco leaf and corresponding smoke samples. It is demonstrated that high accuracy is obtained, both in the determination of δ(13)C and δ(2)H values, allowing the study of biosynthesis and delivery mechanisms of naturally occurring compounds in tobacco. Copyright © 2013 Elsevier B.V. All rights reserved.

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

PubMed

Graney, Joseph R; Landis, Matthew S

2013-03-15

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

Geologic, hydrologic, and geochemical identification of flow paths in the Edwards Aquifer, northeastern Bexar and southern Comal Counties, Texas

USGS Publications Warehouse

Otero, Cassi L.

2007-01-01

The U.S. Geological Survey, in cooperation with the San Antonio Water System, conducted a 4-year study during 2002?06 to identify major flow paths in the Edwards aquifer in northeastern Bexar and southern Comal Counties (study area). In the study area, faulting directs ground water into three hypothesized flow paths that move water, generally, from the southwest to the northeast. These flow paths are identified as the southern Comal flow path, the central Comal flow path, and the northern Comal flow path. Statistical correlations between water levels for six observation wells and between the water levels and discharges from Comal Springs and Hueco Springs yielded evidence for the hypothesized flow paths. Strong linear correlations were evident between the datasets from wells and springs within the same flow path and the datasets from wells in areas where flow between flow paths was suspected. Geochemical data (major ions, stable isotopes, sulfur hexafluoride, and tritium and helium) were used in graphical analyses to obtain evidence of the flow path from which wells or springs derive water. Major-ion geochemistry in samples from selected wells and springs showed relatively little variation. Samples from the southern Comal flow path were characterized by relatively high sulfate and chloride concentrations, possibly indicating that the water in the flow path was mixing with small amounts of saline water from the freshwater/saline-water transition zone. Samples from the central Comal flow path yielded the most varied major-ion geochemistry of the three hypothesized flow paths. Central Comal flow path samples were characterized, in general, by high calcium concentrations and low magnesium concentrations. Samples from the northern Comal flow path were characterized by relatively low sulfate and chloride concentrations and high magnesium concentrations. The high magnesium concentrations characteristic of northern Comal flow path samples from the recharge zone in Comal County might indicate that water from the Trinity aquifer is entering the Edwards aquifer in the subsurface. A graph of the relation between the stable isotopes deuterium and delta-18 oxygen showed that, except for samples collected following an unusually intense rain storm, there was not much variation in stable isotope values among the flow paths. In the study area deuterium ranged from -36.00 to -20.89 per mil and delta-18 oxygen ranged from -6.03 to -3.70 per mil. Excluding samples collected following the intense rain storm, the deuterium range in the study area was -33.00 to -20.89 per mil and the delta-18 oxygen range was -4.60 to -3.70 per mil. Two ground-water age-dating techniques, sulfur hexafluoride concentrations and tritium/helium-3 isotope ratios, were used to compute apparent ages (time since recharge occurred) of water samples collected in the study area. In general, the apparent ages computed by the two methods do not seem to indicate direction of flow. Apparent ages computed for water samples in northeastern Bexar and southern Comal Counties do not vary greatly except for some very young water in the recharge zone in central Comal County.

An ion microprobe study of individual zircon phenocrysts from voluminous post-caldera rhyolites of the Yellowstone caldera

NASA Astrophysics Data System (ADS)

Watts, K. E.; Bindeman, I. N.; Schmitt, A. K.

2010-12-01

Following the formation of the Yellowstone caldera from the 640 ka supereruption of the Lava Creek Tuff (LCT), a voluminous episode of post-caldera volcanism filled the caldera with >600 km3 of low-δ18O rhyolite. Such low-δ18O signatures require remelting of 100s of km3 of hydrothermally altered (18O-depleted) rock in the shallow crust. We present a high resolution oxygen isotope and geochronology (U-Th and U-Pb) study of individual zircon crystals from seven of these voluminous post-caldera rhyolites in order to elucidate their genesis. Oxygen isotope and geochronology analyses of zircon were performed with an ion microprobe that enabled us to doubly fingerprint 25-30 µm diameter spots. Host groundmass glasses and coexisting quartz were analyzed in bulk for oxygen isotopes by laser fluorination. We find that zircons from the youngest (200-80 ka) post-caldera rhyolites have oxygen isotopic compositions that are in equilibrium with low-δ18O host groundmass glasses and quartz and are unzoned in oxygen and U-Th age. This finding is in contrast to prior work on older (500-250 ka) post-caldera rhyolites, which exhibit isotopic disequilibria and age zoning, including the presence of clearly inherited zircon cores. Average U-Th crystallization ages and δ18O zircon values for Pitchstone Plateau flow (81±7 ka, 2.8±0.2‰), West Yellowstone flow (118±8 ka, 2.8±0.1‰), Elephant Back flow (175±22 ka, 2.7±0.2‰) and Tuff of Bluff Point (176±20 ka, 2.7±0.1‰) are overlapping or nearly overlapping in age and identical in oxygen isotope composition within uncertainty (2 SE). New U-Pb geochronology and oxygen isotope data for the North Biscuit Basin flow establish that it has an age (188±33 ka) and δ18O signature (2.8±0.2‰) that is distinctive of the youngest post-caldera rhyolites. Conversely, the South Biscuit Basin flow has a heterogeneous zircon population with ages that range from 550-250 ka. In this unit, older and larger (200-400 µm) zircons have more disparity in δ18O signatures (-0.2-3.6‰) while the younger and smaller (<100-200 µm) zircons have δ18O signatures (2.6±0.3‰) that are identical to the youngest post-caldera rhyolites. Our results are consistent with derivation of the youngest post-caldera rhyolites from a common magma reservoir that was assembled from heterogeneous pockets of low-δ18O melt. The magma was homogenized prior to eruption, erasing evidence of batch assembly in all but the oldest South Biscuit Basin unit. An important new finding of this study is that the newly defined post-LCT East Biscuit Basin flow is the oldest (U-Pb age of 761±66 ka) and most primitive (70 wt% SiO2) rhyolite to erupt from within the Yellowstone caldera. Unlike the youngest post-caldera rhyolites, the average δ18O composition of East Biscuit Basin zircons (4.4±0.3‰) is significantly higher and out of equilibrium with the host groundmass glass (δ18O=1.0‰). Its formation requires remelting of hydrothermally altered LCT and pre-LCT subcaldera rocks that retain oxygen isotopic evidence of inherited zircon phenocrysts.

Evaluation of diffuse and preferential flow pathways of infiltratedprecipitation and irrigation using oxygen and hydrogen isotopes

USGS Publications Warehouse

Ma, Bin; Liang, Xing; Liu, Shaohua; Jin, Menggui; Nimmo, John R.; Li, Jingxin

2017-01-01

Subsurface-water flow pathways in three different land-use areas (non-irrigated grassland, poplar forest, and irrigated arable land) in the central North China Plain were investigated using oxygen (18O) and hydrogen (2H) isotopes in samples of precipitation, soils, and groundwater. Soil water in the top 10 cm was significantly affected by both evaporation and infiltration. Water at 10–40 cm depth in the grassland and arable land, and 10–60 cm in poplar forest, showed a relatively short residence time, as a substantial proportion of antecedent soil water was mixed with a 92-mm storm infiltration event, whereas below those depths (down to 150 cm), depleted δ18O spikes suggested that some storm water bypassed the shallow soil layers. Significant differences, in soil-water content and δ18O values, within a small area, suggested that the proportion of immobile soil water and water flowing in subsurface pathways varies depending on local vegetation cover, soil characteristics and irrigation applications. Soil-water δ18O values revealed that preferential flow and diffuse flow coexist. Preferential flow was active within the root zone, independent of antecedent soil-water content, in both poplar forest and arable land, whereas diffuse flow was observed in grassland. The depleted δ18O spikes at 20–50 cm depth in the arable land suggested the infiltration of irrigation water during the dry season. Temporal isotopic variations in precipitation were subdued in the shallow groundwater, suggesting more complete mixing of different input waters in the unsaturated zone before reaching the shallow groundwater.

Ecohydrological and subsurface controls on drought-induced contraction and disconnection of stream networks

NASA Astrophysics Data System (ADS)

Godsey, S.; Kirchner, J. W.; Whiting, J. A.

2016-12-01

Temporary headwater streams - both intermittent and ephemeral waterways - supply water to approximately 1/3 of the US population, and 60% of streams used for drinking water are temporary. Stream ecologists increasingly recognize that a gradient of processes across the drying continuum affect ecosystems at dynamic terrestrial-aquatic interfaces. Understanding the hydrological controls across that gradient of drying may improve management of these sensitive systems. One possible control on surface flows includes transpiration losses from either the riparian zone or the entire watershed. We mapped several stream networks under extreme low flow conditions brought on by severe drought in central Idaho and California in 2015. Compared to previous low-flow stream length estimates, the active drainage network had generally decreased by a very small amount across these sites, perhaps because stored water buffered the precipitation decrease, or because flowing channel heads are fixed by focused groundwater flow emerging at springs. We also examined the apparent sources of water for both riparian and hillslope trees using isotopic techniques. During drought conditions, we hypothesized that riparian trees - but not those far from flowing streams - would be sustained by streamflow recharging riparian aquifers, and thus would transpire water that was isotopically similar to streamflow because little soil water would remain available below the wilting point and stream water would be sustain those trees. We found a more complex pattern, but in most places stream water and water transpired by trees were isotopically distinct regardless of flow intermittency or tree location. We also found that hillslope trees outside of the riparian zone appeared to be using different waters from those used by riparian trees. Finally, we explore subsurface controls on network extent, showing that bedrock characteristics can influence network stability and contraction patterns.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Quaternary Sedimentary Processes and Budgets in Orphan Basin, Southwestern Labrador Sea

NASA Astrophysics Data System (ADS)

Hiscott, Richard N.; Aksu, Ali E.

1996-03-01

The continental slope in Orphan Basin, northeast of Newfoundland, is underlain by several seaward-thinning debris-flow wedges alternating with acoustically stratified, regionally extensive, mainly hemipelagic sediments. δ 18O stratigraphy and volcanic ash layers in a 11.67-m core indicate that the uppermost debris-flow wedge formed during the last of several sea-level lowstands in isotopic stages 2-4. Similarly, seismic reflection correlation of dated levels at DSDP Site 111 with the Orphan Basin succession suggests that two deeper debris-flow wedges were deposited during oxygen isotopic stages 6 and 8. The oldest of the debris-flow deposits in at least three of the wedges formed well into the corresponding glacial cycle, after ice sheets had reached the edge of the continental shelf. Slower deposition by hemipelagic processes and ice rafting formed the acoustically stratified units, including Heinrich layers. The youngest three debris-flow wedges each have volumes of 1300-1650 km 3. Approximately two-thirds of this material is attributed to glacial erosion of Mesozoic and Tertiary strata beneath the Northeast Newfoundland Shelf. The remainder is believed to have been derived by glacial erosion of older bedrock that now forms the island of Newfoundland. The observed sediment volumes and the inferred basal and upper ages of the debris-flow wedges imply an average glacial denudation rate of about 0.13 mm/yr for this older bedrock, and an average of about 60 m of glacial bedrock erosion since oxygen isotope stage 22. This denudation rate is similar to estimates from the Barents Sea region off Norway.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Sources and Residence Times of Groundwater in Shasta County, CA Determined by Isotopic Tracers

NASA Astrophysics Data System (ADS)

Peters, E.; Moran, J. E.; Deinhart, A.; Roberts, S. K.; Esser, B.; Visser, A.

2015-12-01

Large-volume springs are a significant source of water to communities in Shasta County. Aquifers in this region are developed in young volcanic formations and the age and flow of groundwater is not well characterized, making predicting the impact of drought and climate change on spring flow difficult. To better understand the water resources and the hydrogeology of the region and to better constrain the age of water produced by springs, we have sampled water from wells, springs, and streams for a suite of geochemical and isotopic tracers. We are using isotopic tracers because of the limited number of sampling points over a large area, leaving traditional hydrogeologic methods such as water levels and pump tests inadequate for a regional study. We analyzed samples for sulfur-35 (87.4 day half-life) and found detections in two springs, confirming the presence of a fraction of recently (1-2 years) recharged groundwater. Tritium (12.3 year half-life) activities show that some wells produce water recharged more than 5 decades ago, but most produce more recently recharged water. We will also report results for sodium-22 (2.6 year half-life), krypton-85 (10.8 year half-life), carbon-14 (5,730 year half-life), dissolved noble gases, stable isotopes of water, and helium isotopic composition. These isotopes are applied to determine the age (residence time) of groundwater over a broad age distribution, from less than one year to tens of thousands of years. These tracers should also provide information on aquifer volumes, help delineate groundwater flow, and help to identify recharge areas. A collection of groundwater ages from springs at high elevations to wells in the upper Sacramento Valley will help delineate groundwater flowpaths. Finally, groundwater residence times will help determine groundwater volume and recharge rates, and resolve questions related to drought vulnerability and effective adjustments in water resource management.

Segregation of isotopes of heavy metals due to light-induced drift: results and problems

NASA Astrophysics Data System (ADS)

Sapar, A.; Aret, A.; Poolamäe, R.; Sapar, L.

2008-04-01

Atutov and Shalagin (1988) proposed light-induced drift (LID) as a physically well understandable mechanism to explain the formation of isotopic anomalies observed in CP stars. We have generalized the theory of LID and applied it to diffusion of heavy elements and their isotopes in quiescent atmospheres of CP stars. Diffusional segregation of isotopes of chemical elements is described by the equations of continuity and diffusion velocity. Computations of evolutionary sequences for the abundances of mercury isotopes in several model atmospheres have been made, using the Fortran 90 program SMART composed by the authors. Results confirm predominant role of LID in separation of isotopes.

A lab in the field: high-frequency analysis of water quality and stable isotopes in stream water and precipitation

NASA Astrophysics Data System (ADS)

von Freyberg, Jana; Studer, Bjørn; Kirchner, James W.

2017-03-01

High-frequency measurements of solutes and isotopes (18O and 2H) in rainfall and streamflow can shed important light on catchment flow pathways and travel times, but the workload and sample storage artifacts involved in collecting, transporting, and analyzing thousands of bottled samples severely constrain catchment studies in which conventional sampling methods are employed. However, recent developments towards more compact and robust analyzers have now made it possible to measure chemistry and water isotopes in the field at sub-hourly frequencies over extended periods. Here, we present laboratory and field tests of a membrane-vaporization continuous water sampler coupled to a cavity ring-down spectrometer for real-time measurements of δ18O and δ2H combined with a dual-channel ion chromatograph (IC) for the synchronous analysis of major cations and anions. The precision of the isotope analyzer was typically better than 0.03 ‰ for δ18O and 0.17 ‰ for δ2H in 10 min average readings taken at intervals of 30 min. Carryover effects were less than 1.2 % between isotopically contrasting water samples for 30 min sampling intervals, and instrument drift could be corrected through periodic analysis of secondary reference standards. The precision of the ion chromatograph was typically ˜ 0.1-1 ppm or better, with relative standard deviations of ˜ 1 % or better for most major ions in stream water, which is sufficient to detect subtle biogeochemical signals in catchment runoff. We installed the coupled isotope analyzer/IC system in an uninsulated hut next to a stream of a small catchment and analyzed stream water and precipitation samples every 30 min over 28 days. These high-frequency measurements facilitated a detailed comparison of event-water fractions via endmember mixing analysis with both chemical and isotope tracers. For two events with relatively dry antecedent moisture conditions, the event-water fractions were < 21 % based on isotope tracers but were significantly overestimated (40 to 82 %) by the chemical tracers. These observations, coupled with the storm-to-storm patterns in precipitation isotope inputs and the associated stream water isotope response, led to a conceptual hypothesis for runoff generation in the catchment. Under this hypothesis, the pre-event water that is mobilized by precipitation events may, depending on antecedent moisture conditions, be significantly shallower, younger, and less mineralized than the deeper, older water that feeds baseflow and thus defines the pre-event endmember used in hydrograph separation. This proof-of-concept study illustrates the potential advantages of capturing isotopic and hydrochemical behavior at a high frequency over extended periods that span multiple hydrologic events.

Use of oxygen-18 and deuterium to assess the hydrology of groundwater-lake systems: Chapter 3: Advances in chemistry

USGS Publications Warehouse

Krabbenhoft, David P.; Bowser, Carl J.; Kendall, Carol; Gat, Joel

2009-01-01

A thorough understanding of a lake's hydrology is essential for many lake studies. In some situations the interactions between groundwater systems and lakes are complex; in other cases the hydrology of a multilake system needs to be quantified. In such places, stable isotopes offer an alternative to the more traditional piezometer networks, which are costly to install and time-consuming to maintain. The stable-isotope mass-balance relations presented here can be used to estimate groundwater exchange rates for individual lakes and geographically clustered lakes. These relations also can be used to estimate other hydrological factors, such as average relative humidity. In places where the groundwater system is unstable (e.g., where flow reversals occur), natural solute tracers may provide a better alternative than stable isotopes for estimating rates of groundwater flow to and from lakes.

Application of a new model for groundwater age distributions: Modeling and isotopic analysis of artificial recharge in the Rialto-Colton basin, California

USGS Publications Warehouse

Ginn, T.R.; Woolfenden, L.

2002-01-01

A project for modeling and isotopic analysis of artificial recharge in the Rialto-Colton basin aquifer in California, is discussed. The Rialto-Colton aquifer has been divided into four primary and significant flowpaths following the general direction of groundwater flow from NW to SE. The introductory investigation include sophisticated chemical reaction modeling, with highly simplified flow path simulation. A comprehensive reactive transport model with the established set of geochemical reactions over the whole aquifer will also be developed for treating both reactions and transport realistically. This will be completed by making use of HBGC123D implemented with isotopic calculation step to compute Carbon-14 (C14) and stable Carbon-13 (C13) contents of the water. Computed carbon contents will also be calibrated with the measured carbon contents for assessment of the amount of imported recharge into the Linden pond.

Axi-symmetrical flow reactor for .sup.196 Hg photochemical enrichment

DOEpatents

Grossman, Mark W.

1991-01-01

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, .sup.196 Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired .sup.196 Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith.

Using stable isotopes of carbon to investigate the seasonal variation of carbon transfer in a northwestern Arkansas cave

USGS Publications Warehouse

Knierim, Katherine J.; Pollock, Erik; Hays, Phillip D.; Khojasteh, Jam

2015-01-01

Stable-isotope analyses are valuable in karst settings, where characterizing biogeochemical cycling of carbon along groundwater flow paths is critical for understanding and protecting sensitive cave and karst water resources. This study quantified the seasonal changes in concentration and isotopic composition (δ13C) of aqueous and gaseous carbon species—dissolved inorganic carbon (DIC) and gaseous carbon dioxide (CO2)—to characterize sources and transfer of these species along a karst flow path, with emphasis on a cave environment. Gas and water samples were collected from the soil and a cave in northwestern Arkansas approximately once a month for one year to characterize carbon cycling along a conceptual groundwater flow path. In the soil, as the DIC concentration increased, the isotopic composition of the DIC became relatively lighter, indicating an organic carbon source for a component of the DIC and corroborating soil DIC as a proxy for soil respiration. In the cave, a positive correlation between DIC and surface temperature was due to increased soil respiration as the organic carbon signal from the soil was transferred to the cave environment via the aqueous phase. CO2 concentration was lowest in the cave during colder months and increased exponentially with increasing surface temperature, presumably due to higher rates of soil respiration during warmer periods and changing ventilation patterns between the surface and cave atmosphere. Isotopic disequilibrium between CO2 and DIC in the cave was greatest when CO2 concentration was changing during November/ December and March/April, presumably due to the rapid addition or removal of gaseous CO2. The isotopic disequilibrium between DIC and CO2 provided evidence that cave CO2 was a mixture of carbon from several sources, which was mostly constrained by mixture between atmospheric CO2 and soil CO2. The concentration and isotopic composition of gaseous and aqueous carbon species were controlled by month-to-month variations in temperature and precipitation and provided insight into the sources of carbon in the cave. Stable carbon isotope ratios provided an effective tool to explore carbon transfer from the soil zone and into the cave, identify carbon sources in the cave, and investigate how seasonality affected the transfer of carbon in a shallow karst system.

Determination of the δ34S of Total Sulfur in Solids: RSIL Lab Code 1800

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler B.

2006-01-01

The purpose of Reston Stable Isotope Laboratory Lab (RSIL) Code 1800 is to determine the δ(34S/32S), abbreviated as δ34S, of total sulfur in a solid sample. A Carlo Erba NC 2500 elemental analyzer (EA) is used to convert total sulfur in a solid sample into SO2 gas. The EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines the relative difference in stable sulfur isotope-amount ratio (34S/32S) of the product SO2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in tin capsules and loaded into a Costech Zero-Blank Autosampler on the EA. Under computer control, samples are dropped into a heated tube reaction tube that combines both the oxidation and the reduction reactions. The combustion takes place in a He atmosphere that contains an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a He carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO2, N2, and SO2, are separated by a gas chromatograph (GC). The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Thermo-Finnigan ConFlo II interface, which also is used to inject SO2 reference gas and He for sample dilution. The IRMS is a Thermo-Finnigan DeltaPlus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge (m/z) 64 and 66 simultaneously. The ion beams from SO2 are as follows: m/z 64 = SO2 = 32S16O16O; and m/z 66 = SO2 = 34S16O16O primarily.

Carbon and oxygen isotope ratios of ecosystem respiration along an Oregon conifer transect: preliminary observations based on small-flask sampling.

PubMed

Ehleringer, J. R.; Cook, C. S.

1998-01-01

Isotope ratio analyses of atmospheric CO(2) at natural abundance have significant potential for contributing to our understanding of photosynthetic and respiration processes in forest ecosystems. Recent advances in isotope ratio mass spectrometry allow for rapid, on-line analysis of small volumes of CO(2) in air, and open new research opportunities at the ecophysiological, whole-organism, and atmospheric levels. Among the immediate applications are the carbon and oxygen isotope ratio analyses of carbon dioxide in atmospheric air. Routine analysis of carbon dioxide in air volumes of approximately 50-300 &mgr;l is accomplished by linking a commercially available, trace gas condenser and gas chromatograph to an isotope ratio mass spectrometer operated in continuous-flow mode. Samples collected in the field are stored in either gas-tight syringes or 100-ml flasks. The small sample volume required makes it possible to subsample the air in flasks for CO(2) and then to sample the remaining air volume for the analysis of the isotopic composition of either methane or nitrous oxide. Reliable delta(13)C and delta(18)O values can be obtained from samples collected and stored for 1-3 days. Longer-term storage, on the order of weeks, is possible for delta(13)C measurements without drift in the isotope ratio signal, and should also be possible for delta(18)O measurements. When linked with an infrared gas analyzer, pump and flask sampling system, it is feasible to sample CO(2) extensively in remote forest locations. The air-sampling system was used to measure the isotope ratios of atmospheric CO(2) and to conduct a regression analysis of the relationship between these two parameters. From the regression, we calculated the delta(13)C of ecosystem respiration of four coniferous ecosystems along a precipitation gradient in central Oregon. The ecosystems along the coast-to-interior Oregon (OTTER) gradient are dominated by spruce-hemlock forests at the wet, coastal sites (> 200 cm precipitation annually) to juniper woodlands (20 cm precipitation) at the interior, dry end of the transect. The delta(13)C values of ecosystem respiration along this transect differed by only 1.3 per thousand (range of -25.2 to -23.9 per thousand ) during August at the peak of the summer drought. Following autumn rains in September, the delta(13)C of ecosystem respiration in the four stands decreased; overall the difference in the carbon isotope ratio of ecosystem respiration among sites increased to 3.9 per thousand (-26.8 to -22.9 per thousand ).

Using stable isotopes to associate migratory shorebirds with their wintering locations in Argentina

USGS Publications Warehouse

Farmer, A.H.; Abril, M.; Fernandez, M.; Torres, J.; Kester, C.; Bern, C.

2004-01-01

We are evaluating the use of stable isotopes to identify the wintering areas of Neotropical migratory shorebirds in Argentina. Our goal is to associate individual birds, captured on the breeding grounds or in migration with specific winter sites, thereby helping to identify distinct areas used by different subpopulations. In January and February 2002 and 2003, we collected flight feathers from shorebirds at 23 wintering sites distributed across seven province s in Argentina (n = 170). Feathers samples were pre- pared and analyzed for δ13C, δ15N, δ34S, δ18O and δD by continuous flow methods. A discriminant function based on deuterium alone was not an accurate predictor of a shorebird’s province of origin, ranging from 8% correct (Santiago del Estero) to 80% correct (San ta Cruz). When other isotopes were included, the prediction accuracy increased substantially (from 56% in Buenos Aires to 100% in Tucumán). The improvement in accuracy was due to C/N, which separated D-depleted sites in the Andes from those in the south, and the inclusion of S separated sites with respect to their distance from the Atlantic. We also were able to correctly discriminate shorebirds from among two closely spaced sites within the province of Tierra del Fuego. These results suggest the feasibility of identifying the origin of a shorebird at a provincial level of accuracy, as well as uniquely identifying birds from some closely spaced sites. There is a high degree of intra- and inter-bird variability, especially in the Pampas region, where there is wide variety of wetland/water conditions. In that important shorebird region, the variability itself may in fact be the “signature.” Future addition of trace elements to the analyses may improve predictions based solely on stable isotopes.

Competition influence in the segregation of the trophic niche of otariids: a case study using isotopic Bayesian mixing models in Galapagos pinnipeds.

PubMed

Páez-Rosas, Diego; Rodríguez-Pérez, Mónica; Riofrío-Lazo, Marjorie

2014-12-15

The feeding success of predators is associated with the competition level for resources, and, thus, sympatric species are exposed to a potential trophic overlap. Isotopic Bayesian mixing models should provide a better understanding of the contribution of preys to the diet of predators and the feeding behavior of a species over time. The carbon and nitrogen isotopic signatures from pup hair samples of 93 Galapagos sea lions and 48 Galapagos fur seals collected between 2003 and 2009 in different regions (east and west) of the archipelago were analyzed. A PDZ Europa ANCA-GSL elemental analyzer interfaced with a PDZ Europa 20-20 continuous flow gas source mass spectrometer was employed. Bayesian models, SIAR and SIBER, were used to estimate the contribution of prey to the diet of predators, the niche breadth, and the trophic overlap level between the populations. Statistical differences in the isotopic values of both predators were observed over the time. The mixing model determined that Galapagos fur seals had a primarily teutophagous diet, whereas the Galapagos sea lions fed exclusively on fish in both regions of the archipelago. The SIBER analysis showed differences in the trophic niche between the two sea lion populations, with the western rookery of the Galapagos sea lion being the population with the largest trophic niche area. A trophic niche partitioning between Galapagos fur seals and Galapagos sea lions in the west of the archipelago is suggested by our results. At intraspecific level, the western population of the Galapagos sea lion (ZwW) showed higher trophic breadth than the eastern population, a strategy adopted by the ZwW to decrease the interspecific competition levels in the western region. Copyright © 2014 John Wiley & Sons, Ltd.

Evidence for Dietary Time Series in Layers of Cetacean Skin Using Stable Carbon and Nitrogen Isotope Ratios.

PubMed

Wild, Lauren A; Chenoweth, Ellen M; Mueter, Franz J; Straley, Janice M

2018-05-18

Stable isotope analysis integrates diet information over a time period specific to the type of tissue sampled. For metabolically active skin of free-ranging cetaceans, cells are generated at the basal layer of the skin and migrate outward until they eventually slough off, suggesting potential for a dietary time series. Skin samples from cetaceans were analyzed using continuous-flow elemental analyzer isotope ratio mass spectrometery (EA-IRMS). We used ANOVAs to compare the variability of δ 13 C and δ 15 N values within and among layers and columns ("cores") of the skin of a fin, humpback, and sperm whale. We then used mixed-effects models to analyze isotopic variability among layers of 28 sperm whale skin samples, over the course of a season and among years. We found layer to be a significant predictor of δ 13 C values in the sperm whale's skin, and δ 15 N values the humpback whale's skin. There was no evidence for significant differences in δ 15 N or δ 13 C values among cores for any species. Mixed effects models selected layer and day of the year as significant predictors of δ 13 C and δ 15 N values in sperm whale skin across individuals sampled during the summer months in the Gulf of Alaska. These results suggest that skin samples from cetaceans may be subsampled to reflect diet during a narrower time period; specifically different layers of skin may contain a dietary time series. This underscores the importance of selecting an appropriate portion of skin to analyze based on the species and objectives of the study. This article is protected by copyright. All rights reserved.

Ground based mobile isotopic methane measurements in the Front Range, Colorado

NASA Astrophysics Data System (ADS)

Vaughn, B. H.; Rella, C.; Petron, G.; Sherwood, O.; Mielke-Maday, I.; Schwietzke, S.

2014-12-01

Increased development of unconventional oil and gas resources in North America has given rise to attempts to monitor and quantify fugitive emissions of methane from the industry. Emission estimates of methane from oil and gas basins can vary significantly from one study to another as well as from EPA or State estimates. New efforts are aimed at reconciling bottom-up, or inventory-based, emission estimates of methane with top-down estimates based on atmospheric measurements from aircraft, towers, mobile ground-based vehicles, and atmospheric models. Attributing airborne measurements of regional methane fluxes to specific sources is informed by ground-based measurements of methane. Stable isotopic measurements (δ13C) of methane help distinguish between emissions from the O&G industry, Confined Animal Feed Operations (CAFO), and landfills, but analytical challenges typically limit meaningful isotopic measurements to individual point sampling. We are developing a toolbox to use δ13CH4 measurements to assess the partitioning of methane emissions for regions with multiple methane sources. The method was applied to the Denver-Julesberg Basin. Here we present data from continuous isotopic measurements obtained over a wide geographic area by using MegaCore, a 1500 ft. tube that is constantly filled with sample air while driving, then subsequently analyzed at slower rates using cavity ring down spectroscopy (CRDS). Pressure, flow and calibration are tightly controlled allowing precise attribution of methane enhancements to their point of collection. Comparisons with point measurements are needed to confirm regional values and further constrain flux estimates and models. This effort was made in conjunction with several major field campaigns in the Colorado Front Range in July-August 2014, including FRAPPÉ (Front Range Air Pollution and Photochemistry Experiment), DISCOVER-AQ, and the Air Water Gas NSF Sustainability Research Network at the University of Colorado.

Very high precision and accuracy analysis of triple isotopic ratios of water. A critical instrumentation comparison study.

NASA Astrophysics Data System (ADS)

Gkinis, Vasileios; Holme, Christian; Morris, Valerie; Thayer, Abigail Grace; Vaughn, Bruce; Kjaer, Helle Astrid; Vallelonga, Paul; Simonsen, Marius; Jensen, Camilla Marie; Svensson, Anders; Maffrezzoli, Niccolo; Vinther, Bo; Dallmayr, Remi

2017-04-01

We present a performance comparison study between two state of the art Cavity Ring Down Spectrometers (Picarro L2310-i, L2140-i). The comparison took place during the Continuous Flow Analysis (CFA) campaign for the measurement of the Renland ice core, over a period of three months. Instant and complete vaporisation of the ice core melt stream, as well as of in-house water reference materials is achieved by accurate control of microflows of liquid into a homemade calibration system by following simple principles of the Hagen-Poiseuille law. Both instruments share the same vaporisation unit in a configuration that minimises sample preparation discrepancies between the two analyses. We describe our SMOW-SLAP calibration and measurement protocols for such a CFA application and present quality control metrics acquired during the full period of the campaign on a daily basis. The results indicate an unprecedented performance for all 3 isotopic ratios (δ2H, δ17O, δ18O ) in terms of precision, accuracy and resolution. We also comment on the precision and accuracy of the second order excess parameters of HD16O and H217O over H218O (Dxs, Δ17O ). To our knowledge these are the first reported CFA measurements at this level of precision and accuracy for all three isotopic ratios. Differences on the performance of the two instruments are carefully assessed during the measurement and reported here. Our quality control protocols extend to the area of low water mixing ratios, a regime in which often atmospheric vapour measurements take place and Cavity Ring Down Analysers show a poorer performance due to the lower signal to noise ratios. We address such issues and propose calibration protocols from which water vapour isotopic analyses can benefit from.

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

PubMed

Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

2017-12-01

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

An Ice Core Melter System for Continuous Major and Trace Chemical Analyses of a New Mt. Logan Summit Ice Core

NASA Astrophysics Data System (ADS)

Osterberg, E. C.; Handley, M. J.; Sneed, S. D.; Mayewski, P. A.; Kreutz, K. J.; Fisher, D. A.

2004-12-01

The ice core melter system at the University of Maine Climate Change Institute has been recently modified and updated to allow high-resolution (<1-2 cm ice/sample), continuous and coregistered sampling of ice cores, most notably the 2001 Mt. Logan summit ice core (187 m to bedrock), for analyses of 34 trace elements (Sr, Cd, Sb, Cs, Ba, Pb, Bi, U, As, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, REE suite) by inductively coupled plasma mass spectrometry (ICP-MS), 8 major ions (Na+, Ca2+, Mg2+, K+, Cl-, SO42-, NO3-, MSA) by ion chromatography (IC), stable water isotopes (δ 18O, δ D, d) and volcanic tephra. The UMaine continuous melter (UMCoM) system is housed in a dedicated clean room with HEPA filtered air. Standard clean room procedures are employed during melting. A Wagenbach-style continuous melter system has been modified to include a pure Nickel melthead that can be easily dismantled for thorough cleaning. The system allows melting of both ice and firn without wicking of the meltwater into unmelted core. Contrary to ice core melter systems in which the meltwater is directly channeled to online instruments for continuous flow analyses, the UMCoM system collects discrete samples for each chemical analysis under ultraclean conditions. Meltwater from the pristine innermost section of the ice core is split between one fraction collector that accumulates ICP-MS samples in acid pre-cleaned polypropylene vials under a class-100 HEPA clean bench, and a second fraction collector that accumulates IC samples. A third fraction collector accumulates isotope and tephra samples from the potentially contaminated outer portion of the core. This method is advantageous because an archive of each sample remains for subsequent analyses (including trace element isotope ratios), and ICP-MS analytes are scanned for longer intervals and in replicate. Method detection limits, calculated from de-ionized water blanks passed through the entire UMCoM system, are below 10% of average Mt. Logan values. A strong correlation (R2>0.9) between Ca and S concentrations measured on different fractions of the same sample by IC and ICP-MS validates sample coregistration. Preliminary analyses of data from the 2001 Mt. Logan summit ice core confirm subannual resolution sampling and annual scale variability of major and trace elements. Accumulation rate models and isotope data suggest that annual resolution will be possible to 1000-2000 y.b.p., with multi-annual to centennial resolution for the remainder of the Holocene and possibly including the last deglaciation. Dust proxy elements, including REEs, strongly co-vary in time-series and reveal concentration ratio fluctuations interpreted as source region changes. Volcanic eruptions are characterized by elevated concentrations of S, SO42-, Cu, Sb, Zn and other trace elements. Concentrations of potential anthropogenic contaminants are also discussed.

A high precision gas flow cell for performing in situ neutron studies of local atomic structure in catalytic materials

DOE PAGES

Olds, Daniel; Page, Katharine; Paecklar, Arnold A.; ...

2017-03-17

Gas-solid interfaces enable a multitude of industrial processes, including heterogeneous catalysis; however, there are few methods available for studying the structure of this interface under operating conditions. Here, we present a new sample environment for interrogating materials under gas-flow conditions using time-of-flight neutron scattering under both constant and pulse probe gas flow. Outlined are descriptions of the gas flow cell and a commissioning example using the adsorption of N 2 by Ca-exchanged zeolite-X (Na 78–2xCa xAl 78Si 144O 384,x ≈ 38). We demonstrate sensitivities to lattice contraction and N 2 adsorption sites in the structure, with both static gas loadingmore » and gas flow. A steady-state isotope transient kinetic analysis of N 2 adsorption measured simultaneously with mass spectrometry is also demonstrated. In the experiment, the gas flow through a plugged-flow gas-solid contactor is switched between 15N 2 and 14N 2 isotopes at a temperature of 300 K and a constant pressure of 1 atm; the gas flow and mass spectrum are correlated with the structure factor determined from event-based neutron total scattering. As a result, available flow conditions, sample considerations, and future applications are discussed.« less

Tracing seasonal groundwater contributions to stream flow using a suite of environmental isotopes

NASA Astrophysics Data System (ADS)

Pritchard, J. L.; Herczeg, A. L.; Lamontagne, S.

2003-04-01

Groundwater discharge to streams is important for delivering essential solutes to maintain ecosystem health and flow throughout dry seasons. However, managing the groundwater components of stream flow is difficult because several sources of water can contribute, including delayed drainage from bank storage and regional groundwater. In this study we assessed the potential for a variety of environmental tracers to discriminate between different sources of water to stream flow. A case study comparing Cl-, delta O-18 &delta H-2, Rn-222 and 87Sr/86Sr to investigate the spatial and temporal variability of groundwater inputs to stream flow was conducted in the Wollombi Brook Catchment (SE Australia). The objectives were to characterise the three potential sources of water to stream flow (surface water, groundwater from the near-stream sandy alluvial aquifer system, and groundwater from the regional sandstone aquifer system) and estimate their relative contributions to stream discharge at flood recession and baseflow. Surface water was sampled at various locations along the Wollombi Brook and from its tributaries during flood recession (Mar-01) and under baseflow conditions (Oct-01). Alluvial groundwater was sampled from a piezometer network and regional groundwater from deeper bores in the lower to mid-catchment biannually over two years to characterise these potential sources of water to stream flow. Chloride identified specific reaches of the catchment that were either subjected to evaporation or received regional groundwater contributions to stream flow. The water isotopes verified which of these reaches were dominated by evaporation versus groundwater contributions. They also revealed that the predominant sources of water to stream flow during flood recession were either rainfall and storm runoff or regional groundwater, and that during baseflow the predominant source of water to stream flow was alluvial groundwater. Radon showed that there was a greater proportion of groundwater contributing to stream flow in the upper part of the catchment than the lower catchment during both flood recession and baseflow. Strontium isotopes showed that regional groundwater contributed less than 10% to stream flow in all parts of the catchment under baseflow conditions.

Impacts of 3 years of elevated atmospheric CO2 on rhizosphere carbon flow and microbial community dynamics.

PubMed

Drigo, Barbara; Kowalchuk, George A; Knapp, Brigitte A; Pijl, Agata S; Boschker, Henricus T S; van Veen, Johannes A

2013-02-01

Carbon (C) uptake by terrestrial ecosystems represents an important option for partially mitigating anthropogenic CO2 emissions. Short-term atmospheric elevated CO2 exposure has been shown to create major shifts in C flow routes and diversity of the active soil-borne microbial community. Long-term increases in CO2 have been hypothesized to have subtle effects due to the potential adaptation of soil microorganism to the increased flow of organic C. Here, we studied the effects of prolonged elevated atmospheric CO2 exposure on microbial C flow and microbial communities in the rhizosphere. Carex arenaria (a nonmycorrhizal plant species) and Festuca rubra (a mycorrhizal plant species) were grown at defined atmospheric conditions differing in CO2 concentration (350 and 700 ppm) for 3 years. During this period, C flow was assessed repeatedly (after 6 months, 1, 2, and 3 years) by (13) C pulse-chase experiments, and label was tracked through the rhizosphere bacterial, general fungal, and arbuscular mycorrhizal fungal (AMF) communities. Fatty acid biomarker analyses and RNA-stable isotope probing (RNA-SIP), in combination with real-time PCR and PCR-DGGE, were used to examine microbial community dynamics and abundance. Throughout the experiment the influence of elevated CO2 was highly plant dependent, with the mycorrhizal plant exerting a greater influence on both bacterial and fungal communities. Biomarker data confirmed that rhizodeposited C was first processed by AMF and subsequently transferred to bacterial and fungal communities in the rhizosphere soil. Over the course of 3 years, elevated CO2 caused a continuous increase in the (13) C enrichment retained in AMF and an increasing delay in the transfer of C to the bacterial community. These results show that, not only do elevated atmospheric CO2 conditions induce changes in rhizosphere C flow and dynamics but also continue to develop over multiple seasons, thereby affecting terrestrial ecosystems C utilization processes. © 2012 Blackwell Publishing Ltd.

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2010 CFR

2010-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2012 CFR

2012-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2011 CFR

2011-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2013 CFR

2013-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

10 CFR 50.62 - Requirements for reduction of risk from anticipated transients without scram (ATWS) events for...

Code of Federal Regulations, 2014 CFR

2014-01-01

... into the reactor pressure vessel a borated water solution at such a flow rate, level of boron concentration and boron-10 isotope enrichment, and accounting for reactor pressure vessel volume, that the... minute of 13 weight percent sodium pentaborate decahydrate solution at the natural boron-10 isotope...

Melt migration and mantle chromatography, 2: a time-series Os isotope study of Mauna Loa volcano, Hawaii

NASA Astrophysics Data System (ADS)

Hauri, Erik H.; Kurz, Mark D.

1997-12-01

We have determined the major element, trace element, and Os isotopic compositions of a stratigraphic suite of tholeiitic basalts spanning >30,000 years of the eruptive history of Mauna Loa volcano. Good correlations are observed between Os isotopes and the isotopes of Sr, Nd, Pb and He. In addition, the isotopes correlate with fractionation-corrected major element abundances within this single volcano, and provide a record of increased melting of mafic material with time at Mauna Loa. Chromatographic element fractionation during melt transport is shown to be negligible based on the good correlations of the isotopes of the compatible element Os with the other incompatible element tracers. The temporal variation at Mauna Loa is best described by the translation of the volcano over a Hawaiian plume which is radially zoned in composition. The radial zonation is a predicted consequence of thermal entrainment during flow in a mantle plume conduit.

Temporal variation of chemical and isotopic signals in major discharges of an alpine karst aquifer in Turkey: implications with respect to response of karst aquifers to recharge

NASA Astrophysics Data System (ADS)

Ozyurt, N. Nur; Bayari, C. Serdar

2008-03-01

Proper management of karst aquifers requires a better understanding of flow and transport mechanisms in these systems. Flow in karst aquifers is inherently very complex due to the non-linear and non-stationary relationship between recharge and discharge. Information on this relationship has been acquired for a large (1,000 km2), mountainous (>3,500 m asl) karst aquifer with a deep unsaturated zone (>2,000 m) in the Aladaglar mountain range of south-central Turkey. All major discharges from the aquifer, which drain almost all the recharge, have been observed periodically for specific electrical conductivity, tritium and oxygen-18 variations during a period of 12 months. Observations reveal that the system’s response to recharge depends strongly on the competition between the infiltration and drainage velocities. These velocities, which are controlled by variables such as the time of precipitation, time of infiltration, intensity, and continuity of recharge, determine the degree of dominance of different types of flow mechanisms in the aquifer. Bypass, well-mixed and piston flow mechanisms are used to explain the response of the aquifer to the spatio-temporal variations in recharge. It appears that the aquifer switches among these flow mechanisms depending on the prevailing recharge mode and the competition between infiltration and drainage velocities.

Water-level, borehole geophysical log, and water-quality data from wells transecting the freshwater/saline-water interface of the San Antonio segment of the Edwards Aquifer, South-Central Texas, 1999-2007

USGS Publications Warehouse

Lambert, Rebecca B.; Hunt, Andrew G.; Stanton, Gregory P.; Nyman, Michael B.

2009-01-01

As a part of a 9-year (1999-2007) study done by the U.S. Geological Survey in cooperation with the San Antonio Water System to improve understanding of the San Antonio segment of the Edwards aquifer, south-central Texas, in and near the freshwater/saline-water transition zone of the aquifer, the U.S. Geological Survey collected water-level, borehole geophysical, and water-quality data during 1999-2007 from 37 wells arranged in nine transects (except for two wells) across the freshwater/saline-water interface of the aquifer. This report presents the data collected and also describes the data-collection, analytical, and quality-assurance methods used. The wells, constructed with casing from land surface into the upper part of the aquifer and completed as open hole in the aquifer, are in Uvalde County (East Uvalde transect), in Medina County (South Medina and Devine wells), in Bexar County (Pitluk, Mission, and San Antonio transects), in Comal and Guadalupe Counties (Tri-County transect), in Comal County (New Braunfels transect), and in Hays County (Fish Hatchery, San Marcos, and Kyle transects). Data collected included continuous water level at 18 wells; fluid electrical conductivity and temperature with depth (fluid profiles) obtained by borehole geophysical logging of 15 wells; discrete (periodic) samples for major ions and trace elements at 36 wells; stable isotopes or stable isotopes and tritium at 27 wells; dissolved gases obtained by pumping (or collecting flow) of 19 wells; and continuous specific conductance and temperature at three of the wells equipped with continuous water-level sensors.

A fully automated meltwater monitoring and collection system for spatially distributed isotope analysis in snowmelt-dominated catchments

NASA Astrophysics Data System (ADS)

Rücker, Andrea; Boss, Stefan; Von Freyberg, Jana; Zappa, Massimiliano; Kirchner, James

2016-04-01

In many mountainous catchments the seasonal snowpack stores a significant volume of water, which is released as streamflow during the melting period. The predicted change in future climate will bring new challenges in water resource management in snow-dominated headwater catchments and their receiving lowlands. To improve predictions of hydrologic extreme events, particularly summer droughts, it is important characterize the relationship between winter snowpack and summer (low) flows in such areas (e.g., Godsey et al., 2014). In this context, stable water isotopes (18O, 2H) are a powerful tool for fingerprinting the sources of streamflow and tracing water flow pathways. For this reason, we have established an isotope sampling network in the Alptal catchment (46.4 km2) in Central-Switzerland as part of the SREP-Drought project (Snow Resources and the Early Prediction of hydrological DROUGHT in mountainous streams). Samples of precipitation (daily), snow cores (weekly) and runoff (daily) are analyzed for their isotopic signature in a regular cycle. Precipitation is also sampled along a horizontal transect at the valley bottom, and along an elevational transect. Additionally, the analysis of snow meltwater is of importance. As the sample collection of snow meltwater in mountainous terrain is often impractical, we have developed a fully automatic snow lysimeter system, which measures meltwater volume and collects samples for isotope analysis at daily intervals. The system consists of three lysimeters built from Decagon-ECRN-100 High Resolution Rain Gauges as standard component that allows monitoring of meltwater flow. Each lysimeter leads the meltwater into a 10-liter container that is automatically sampled and then emptied daily. These water samples are replaced regularly and analyzed afterwards on their isotopic composition in the lab. Snow melt events as well as system status can be monitored in real time. In our presentation we describe the automatic snow lysimeter system and present initial results from field tests in winter 2015/2016 under natural conditions at an experimental field site. Fully functional deployment in a forested and an open field location in the Erlenbach subcatchment (0.7 km2) is envisaged for winter 2016/2017. Godsey, S.E.,* J.W. Kirchner and C.L. Tague, Effects of changes in winter snowpacks on summer low flows: case studies in the Sierra Nevada, California, USA, Hydrological Processes, 28, 5048-5064, doi: 10.1002/hyp.9943, 2014.

Tracing groundwater recharge sources in the northwestern Indian alluvial aquifer using water isotopes (δ18O, δ2H and 3H)

NASA Astrophysics Data System (ADS)

Joshi, Suneel Kumar; Rai, Shive Prakash; Sinha, Rajiv; Gupta, Sanjeev; Densmore, Alexander Logan; Rawat, Yadhvir Singh; Shekhar, Shashank

2018-04-01

Rapid groundwater depletion from the northwestern Indian aquifer system in the western Indo-Gangetic basin has raised serious concerns over the sustainability of groundwater and the livelihoods that depend on it. Sustainable management of this aquifer system requires that we understand the sources and rates of groundwater recharge, however, both these parameters are poorly constrained in this region. Here we analyse the isotopic (δ18O, δ2H and tritium) compositions of groundwater, precipitation, river and canal water to identify the recharge sources, zones of recharge, and groundwater flow in the Ghaggar River basin, which lies between the Himalayan-fed Yamuna and Sutlej River systems in northwestern India. Our results reveal that local precipitation is the main source of groundwater recharge. However, depleted δ18O and δ2H signatures at some sites indicate recharge from canal seepage and irrigation return flow. The spatial variability of δ18O, δ2H, d-excess, and tritium reflects limited lateral connectivity due to the heterogeneous and anisotropic nature of the aquifer system in the study area. The variation of tritium concentration with depth suggests that groundwater above c. 80 mbgl is generally modern water. In contrast, water from below c. 80 mbgl is a mixture of modern and old waters, and indicates longer residence time in comparison to groundwater above c. 80 mbgl. Isotopic signatures of δ18O, δ2H and tritium suggest significant vertical recharge down to a depth of 320 mbgl. The spatial and vertical variations of isotopic signature of groundwater reveal two distinct flow patterns in the aquifer system: (i) local flow (above c. 80 mbgl) throughout the study area, and (ii) intermediate and regional flow (below c. 80 mbgl), where water recharges aquifers through large-scale lateral flow as well as vertical infiltration. The understanding of spatial and vertical recharge processes of groundwater in the study area provides important base-line knowledge for developing a sustainable groundwater management plan for the northwestern Indian aquifer system.

Continuous field measurements of δD in water vapor by open-path Fourier transform infrared spectrometry

NASA Astrophysics Data System (ADS)

Wang, Wei; Liu, Wenqing; Zhang, Tianshu

2012-12-01

The stable isotopes in atmospheric water vapor contain rich information on the hydrologic cycles and gaseous exchange processes between biosphere and atmosphere. About one-week field experiment was conducted to continuously measure the isotope composition of water vapor in ambient air using an open-path FTIR system. Mixing ratios of H2 16O and HD16O were measured simultaneously. Analysis of water vapor isotopes revealed that the variations of H2 16O and HD16O were highly related. Mixing ratios of both isotopes varied considerably on a daily timescale or between days, with no obvious diurnal cycle, whereas the deuterium isotopic [delta]D showed clear diel cycle. The results illustrated that the correlation between [delta]D and H2O mixing ratio was relatively weak, which was also demonstrated by the Keeling plot analysis with the whole data. Yet the further Keeling analysis on a daily timescale displayed more obvious linear relationship between [delta]D and the total H2O concentration. All daily isotopic values of evapotranspiration source were obtained, with the range between -113.93±10.25‰ and -245.63±17.61‰ over the observation period.

Back arc basalts from Patagonia: sediment input in a distal subduction domain

NASA Astrophysics Data System (ADS)

Hesse, A.; Mandeville, C.; Varekamp, J. C.

2007-12-01

Cinder cones and lava flows from the Loncopue graben in N Patagonia (37 S) were sampled over a 180 km N-S transect. These mainly basaltic and trachybasaltic lava flows carry olivine with Cr-Al-rich spinel inclusions, while some more evolved flows carry clinopyroxene and plagioclase. Most of these rocks have between 5-8 percent MgO, and show highly variable K and LIL trace element concentrations. The rocks have up to 180 ppm Ni and 250 ppm Cr. Relative trace element abundance diagrams show negative Ta-Nb anomalies in most rocks, although their depths vary strongly. The REE patterns show LREE enrichment and most rocks have no Eu anomalies, indicating the absence of significant plagioclase fractionation. The basalts have constant U/Th values (~0.25) that are similar to those found in the nearby Copahue-Caviahue arc volcanics. Microprobe analyses of the main phases show olivine with Mg # of 80-87 and up to 2600 ppm Ni. Simulations with the Melts-pMelts programs and application of mineral-melt geothermometers suggest that most olivine phenocrysts crystallized at ~8-10 kbar pressure at temperatures of 1170-1220 oC and with 1-3 percent H2O in the melt. The Sr isotope compositions of 9 samples show a range from 0.7033 - 0.7043, which are negatively correlated with Nd isotope ratios (0.51273- 0.51292). Surprisingly, the most MgO-rich basalt has the most radiogenic Sr isotope ratio. The Pb isotope ratios, well outside the DMM range, correlate very poorly with either Sr isotope ratios or in Pb-Pb isotope graphs. The lack of correlation between degree of evolution and Sr isotope ratios as well as the primitive nature of the rocks and crystals suggest that crustal assimilation was not a major process impacting the composition of these small magma volumes. Incompatible trace element patterns of several samples resemble those of detrital sediment samples from the Pacific, which together with the isotopic data suggest that these magmas may carry a subducted sediment component. Trace element concentrations and ratios do not correlate with radiogenic isotope ratios, suggesting that more than one contaminant source impacted the mantle domain, e.g., fluids as well as sediment melts. Isotope and trace element ratios vary considerably between cinder cones that are only 10-15 km apart, suggesting that the underlying mantle is highly heterogeneous, enriched in subducted components in thin veins and patches. The Loncopue basalts seem to be transitional in composition between the very voluminous S-Patagonia back-arc basalts and the Copahue-Caviahue arc rocks to the north.

Simultaneous determination of the intravenous and oral pharmacokinetic parameters of D,L-verapamil using stable isotope-labelled verapamil.

PubMed

Eichelbaum, M; Somogyi, A; von Unruh, G E; Dengler, H J

1981-01-01

Following i.v. administration, the plasma concentration-time curve of verapamil could best be described by either a mono- or biexponential equation. Total plasma clearance (1.26 1/min) approached liver blood flow (1.51/min), so it can be concluded that its clearance is liver blood flow-dependent. Although absorption was almost complete after oral administration, absolute bioavailability (20%) was low, due to extensive hepatic first-pass metabolism. The approach using stable isotope-labelled and unlabelled drug permits simultaneous administration by the intravascular and extravascular routes, thus allowing determination of absolute bioavailability in a single experiment.

Further Insight into the Reaction FeO+ + H2 Yields Fe+ + H2O: Temperature Dependent Kinetics, Isotope Effects, and Statistical Modeling (Postprint)

DTIC Science & Technology

2014-07-31

a laminar flow tube via a Venturi inlet, where ∼104 to 105 collisions with a He buffer gas act to thermalize the ions and carry them downstream...ISOTOPE EFFECTS , AND STATISTICAL MODELING (POSTPRINT) Shaun G. Ard, et al. 31 July 2014 Journal Article AIR FORCE RESEARCH LABORATORY Space Vehicles...Kinetics, Isotope Effects , and Statistical Modeling (Postprint) 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 61102F 6

The Physical and Petrologic Evolution of a Multi-vent Volcanic Field Associated With Yellowstone-Newberry Volcanism

NASA Astrophysics Data System (ADS)

Brueseke, M. E.; Hart, W. K.

2004-12-01

The Santa Rosa-Calico volcanic field (SC) of northern Nevada is perhaps the most chemically and physically diverse of all volcanic fields associated with mid-Miocene northwestern USA volcanism. SC volcanism occurred from 16.5 to 14 Ma and was characterized by the eruption of a complete compositional spectrum from basalt through high-Si rhyolite. Locally derived tholeiitic lava flows and shallow intrusive bodies are chemically and isotopically identical to the Steens Basalt (87/86Sri=<0.7040), the Oregon Plateau-wide mid-Miocene flood basalt. Andesite-dacite lava flows are exposed as at least four geographically and chemically distinct packages representing products of multiple, discrete magmatic systems. The most voluminous of these is calc-alkaline and characterized by abundant granitoid and mafic xenoliths/xenocrysts and radiogenic Sr isotopic ratios. Subalkaline silicic lava flows, domes, and shallow intrusive bodies define three diffuse north-south trending zones. Textural, chemical, and isotopic variability within the silicic units is linked to their spatial and temporal distribution, again necessitating the existence of multiple magmatic systems. The youngest locally derived silicic units are ash flows exposed in the central portion of the SC that erupted in actively forming sedimentary basins at ˜15.4 Ma. Underlying the 400-1500m thick package of SC volcanic rocks are temporally ( ˜103 and ˜85 Ma), chemically, and isotopically (87/86Sr at 16 Ma= 0.7045 to 0.7058 and 0.7061 to >0.7070) heterogeneous granitoid plutons and a package of ˜20-23 Ma calc-alkaline, arc-related intermediate lava flows. The observed disequilibrium textures, xenoliths, and chemical/isotopic diversity suggests that upwelling Steens magma interacted with local crust, siliceous crustal melts, and the mafic plutonic roots of early Miocene arc volcanism in multiple magmatic systems characterized by heterogeneous open system processes. The formation of these systems is tectonically controlled as evidenced by magma eruption/ascent along active zones of lithospheric extension. Thus, the observed physical and chemical diversity in this volcanic field is attributed to a combination of factors; tectonic setting, availability of upwelling mafic magma(s), nature of pre-Miocene crustal addition and lithospheric modification, and the resulting array of magma sources and petrogenetic processes.

Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

NASA Astrophysics Data System (ADS)

Noone, D.; Galewsky, J.; Sharp, Z.; Worden, J.

2008-12-01

The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link the water sources to regional sinks, and thus proves useful in understanding the large scale humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and monitored as climate changes.

Water vapor isotopes measurements at Mauna Loa, Hawaii: Comparison of laser spectroscopy and remote sensing with traditional methods, and the need for ongoing monitoring

NASA Astrophysics Data System (ADS)

Galewsky, J.; Noone, D.; Sharp, Z.; Worden, J.

2009-04-01

The isotopic composition of water vapor (2H/1H and 18O/16 ratios) provides unique information on the transport pathways that link water sources to regional sinks, and thus proves useful in understanding large scale atmospheric humidity budgets. Recent advances in measurement technology allow the monitoring of water vapor isotope composition in ways which has can revolutionize investigations of atmospheric hydrology. Traditional measurement of isotopic composition requires trapping of samples with either large volume vacuum flasks or by trapping liquid samples with cryogens for later analyses using mass spectrometry, and are laborious and seldom span more than just short dedicated observational periods. On the other hand, laser absorption spectroscopy can provide almost continuous and autonomous in situ measurements of isotope abundances with precision almost that of traditional mass spectrometry, and observations from spacecraft can make almost daily maps of the global isotope distributions. In October of 2008 three laser based spectrometers were deployed at the Mauna Loa Laboratory in Hawaii to make continuous measurement of the 2H and 18O abundance of free tropospheric water vapor. These results are compared with traditional measurements and with measurements from two satellite platforms. While providing field validation of the new methodologies, the data show variability which captures the transport processes in the region. The data are used to characterize the role of large scale mixing of dry air, the influence of the boundary layer and the importance of moist convection in controlling the low humidity of subtropical air near Hawaii. Although the record is short, it demonstrates the usefulness of using robust isotope measurements to understand the budgets of the most important greenhouse gas. This work motivates establishing a continuous record of isotopes measurement at baseline sites, like Mauna Loa, such that the changes in water cycle can be understood and monitored as climate changes.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Isotopic evolution of Mauna Loa volcano

NASA Astrophysics Data System (ADS)

Kurz, Mark D.; Kammer, David P.

1991-04-01

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

Defining a stable water isotope framework for isotope hydrology application in a large trans-boundary watershed (Russian Federation/Ukraine).

PubMed

Vystavna, Yuliya; Diadin, Dmytro; Huneau, Frédéric

2018-05-01

Stable isotopes of hydrogen ( 2 H) and oxygen ( 18 O) of the water molecule were used to assess the relationship between precipitation, surface water and groundwater in a large Russia/Ukraine trans-boundary river basin. Precipitation was sampled from November 2013 to February 2015, and surface water and groundwater were sampled during high and low flow in 2014. A local meteoric water line was defined for the Ukrainian part of the basin. The isotopic seasonality in precipitation was evident with depletion in heavy isotopes in November-March and an enrichment in April-October, indicating continental and temperature effects. Surface water was enriched in stable water isotopes from upstream to downstream sites due to progressive evaporation. Stable water isotopes in groundwater indicated that recharge occurs mainly during winter and spring. A one-year data set is probably not sufficient to report the seasonality of groundwater recharge, but this survey can be used to identify the stable water isotopes framework in a weakly gauged basin for further hydrological and geochemical studies.

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

Method and apparatus to measure vapor pressure in a flow system

DOEpatents

Grossman, Mark W.; Biblarz, Oscar

1991-01-01

The present invention is directed to a method for determining, by a condensation method, the vapor pressure of a material with a known vapor pressure versus temperature characteristic, in a flow system particularly in a mercury isotope enrichment process.

Late Oligocene to early Miocene geochronology and paleoceanography from the subantarctic South Atlantic

NASA Astrophysics Data System (ADS)

Billups, K.; Channell, J. E. T.; Zachos, J.

2002-01-01

At Ocean Drilling Program (ODP) Site 1090 on the Agulhas Ridge (subantarctic South Atlantic) benthic foraminiferal stable isotope records span the late Oligocene through the early Miocene (25-16 Ma) at a temporal resolution of ~10 kyr. In the same time interval a magnetic polarity stratigraphy can be unequivocally correlated to the geomagnetic polarity timescale (GPTS), thereby providing secure correlation of the isotope record to the GPTS. On the basis of the isotope-magnetostratigraphic correlation we provide refined age calibration of established oxygen isotope events Mi1 through Mi2 as well as several other distinctive isotope events. Our data suggest that the δ18O maximum commonly associated with the Oligocene/Miocene (O/M) boundary falls within C6Cn.2r (23.86 Ma). The δ13C maximum coincides, within the temporal resolution of our record, with C6Cn.2n/r boundary and hence to the O/M boundary. Comparison of the stable isotope record from ODP Site 1090 to the orbitally tuned stable isotope record from ODP Site 929 across the O/M boundary shows that variability in the two records is very similar and can be correlated at and below the O/M boundary. Site 1090 stable isotope records also provide the first deep Southern Ocean end-member for reconstructions of circulation patterns and late Oligocene to early Miocene climate change. Comparison to previously published records suggests that basin to basin carbon isotope gradients were small or nonexistent and are inconclusive with respect to the direction of deep water flow. Oxygen isotope gradients between sites suggest that the deep Southern Ocean was cold in comparison to the North Atlantic, Indian, and the Pacific Oceans. Dominance of cold Southern Component Deep Water at Site 1090, at least until 17 Ma, suggests that relatively cold circumpolar climatic conditions prevailed during the late Oligocene and early Miocene. We believe that a relatively cold Southern Ocean reflects unrestricted circumpolar flow through the Drake Passage in agreement with bathymetric reconstructions.

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

NASA Astrophysics Data System (ADS)

Hu, R.

2015-12-01

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

Fractionation of Sulfur Isotopes by Desulfovibrio vulgaris Mutants Lacking Periplasmic Hydrogenases or the Type I Tetraheme Cytochrome c3

NASA Astrophysics Data System (ADS)

Sim, M.; Ono, S.; Bosak, T.

2012-12-01

A large fraction of anaerobic mineralization of organic compounds relies on microbial sulfate reduction. Sulfur isotope fractionation by these microbes has been widely used to trace the biogeochemical cycling of sulfur and carbon, but intracellular mechanisms behind the wide range of fractionations observed in nature and cultures are not fully understood. In this study, we investigated the influence of electron transport chain components on the fractionation of sulfur isotopes by culturing Desulfovibrio vulgaris Hildenborough mutants lacking hydrogenases or type I tetraheme cytochrome c3 (Tp1-c3). The mutants were grown both in batch and continuous cultures. All tested mutants grew on lactate or pyruvate as the sole carbon and energy sources, generating sulfide. Mutants lacking cytoplasmic and periplasmic hydrogenases exhibited similar growth physiologies and sulfur isotope fractionations to their parent strains. On the other hand, a mutant lacking Tp1-c3 (ΔcycA) fractionated the 34S/32S ratio more than the wild type, evolving H2 in the headspace and exhibiting a lower specific respiration rate. In the presence of high concentrations of pyruvate, the growth of ΔcycA relied largely on fermentation rather than sulfate reduction, even when sulfate was abundant, producing the largest sulfur isotope effect observed in this study. Differences between sulfur isotope fractionation by ΔcycA and the wild type highlight the effect of electron transfer chains on the magnitude of sulfur isotope fractionation. Because Tp1-c3 is known to exclusively shuttle electrons from periplasmic hydrogenases to transmembrane complexes, electron transfers in the absence of Tp1-c3 should bypass the periplasmic hydrogen cycling, and the loss of reducing equivalents in the form of H2 can impair the flow of electrons from organic acids to sulfur, increasing isotope fractionation. Larger fractionation by ΔcycA can inform interpretations of sulfur isotope data at an environmental scale as well, because intracellular concentrations of electron transport components can be altered by environmental factors such as iron availability. Simultaneous sulfate reduction and fermentation, and their corresponding sulfur isotope effects, also generate a hypothesis that links sulfur isotope fractionation to the cellular energy budget. Theoretically, the largest fractionation during microbial sulfate reduction occurs when the backward fluxes equal the forward fluxes in sulfate reduction pathway. However, when the generation of ATP depends exclusively on sulfate respiration, a minimum respiration rate is required to fulfill the maintenance energy requirement. In contrast, when sulfate reduction occurs simultaneously with fermentation, the latter process may contribute toward maintenance energy, enabling slower and more reversible sulfate reduction, and leading to larger fractionation. Given that many sulfate-reducing microbes are also facultative fermenters, fermentation by sulfate reducing microbes in natural habitats and sulfur isotope signatures produced by such communities deserve further exploration.

The role of interbasin groundwater transfers in geologically complex terranes, demonstrated by the Great Basin in the western United States

NASA Astrophysics Data System (ADS)

Nelson, Stephen T.; Mayo, Alan L.

2014-06-01

In the Great Basin, USA, bedrock interbasin flow is conceptualized as the mechanism by which large groundwater fluxes flow through multiple basins and intervening mountains. Interbasin flow is propounded based on: (1) water budget imbalances, (2) potential differences between basins, (3) stable isotope evidence, and (4) modeling studies. However, water budgets are too imprecise to discern interbasin transfers and potential differences may exist with or without interbasin fluxes. Potentiometric maps are dependent on conceptual underpinnings, leading to possible false inferences regarding interbasin transfers. Isotopic evidence is prone to non-unique interpretation and may be confounded by the effects of climate change. Structural and stratigraphic considerations in a geologically complex region like the Great Basin should produce compartmentalization, where increasing aquifer size increases the odds of segmentation along a given flow path. Initial conceptual hypotheses should explain flow with local recharge and short flow paths. Where bedrock interbasin flow is suspected, it is most likely controlled by diversion of water into the damage zones of normal faults, where fault cores act as barriers. Large-scale bedrock interbasin flow where fluxes must transect multiple basins, ranges, and faults at high angles should be the conceptual model of last resort.

Monthly Atmospheric 13C/12C Isotopic Ratios for 11 SIO Stations (1977-2008)

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

Keeling, R. F.; Piper, S. C.; Bollenbacher, A. F.

Stable isotopic measurements for atmospheric 13C/12C and 18O/16O at global sampling sites were initiated by Dr. C.D. Keeling and co-workers at Scripps Institution of Oceanography (SIO) in 1977. These isotopic measurements complement the continuing global atmospheric and oceanic CO2 measurements initiated by Keeling in 1957. This work is currently being continued under the direction of R.F. Keeling, who also runs a parallel program at SIO to measure changes in atmospheric O2 and Ar abundances (Scripps O2 Program). A more complete set of 13CO2 data is found online at http://scrippsco2.ucsd.edu/data/atmospheric_co2.html

Long-term nitrogen additions and the intrinsic water-use efficiency of boreal Scots pine.

NASA Astrophysics Data System (ADS)

Marshall, John; Wallin, Göran; Linder, Sune; Lundmark, Tomas; Näsholm, Torgny

2015-04-01

Nitrogen fertilization nearly always increases productivity in boreal forests, at least in terms of wood production, but it is unclear how. In a mature (80 yrs. old) Scots pine forest in northern Sweden, we tested the extent to which nitrogen fertilization increased intrinsic photosynthetic water-use efficiency. We measured δ13C both discretely, in biweekly phloem sampling, and continuously, by monitoring of bole respiration. The original experiment was designed as a test of eddy covariance methods and is not therefore strictly replicated. Nonetheless, we compared phloem contents among fifteen trees from each plot and stem respiration from four per plot. The treatments included addition of 100 kg N/ha for eight years and a control. Phloem contents have the advantage of integrating over the whole canopy and undergoing complete and rapid turnover. Their disadvantage is that some have observed isotopic drift with transport down the length of the stem, presumably as a result of preferential export and/or reloading. We also measured the isotopic composition of stem respiration from four trees on each plot using a Picarro G1101-I CRDS attached to the vent flow from a continuous gas-exchange system. We detected consistent differences in δ13C between the treatments in phloem contents. Within each treatment, the phloem δ13C was negatively correlated with antecedent temperature (R2= 0.65) and no other measured climate variable. The isotopic composition of stem CO2 efflux will be compared to that of phloem contents. However, when converted to intrinsic water-use efficiency, the increase amounted to only about 4%. This is a small relative to the near doubling in wood production. Although we were able to detect a clear and consistent increase in water-use efficiency with N-fertilization, it constitutes but a minor cause of the observed increase in wood production.

Organic matter dynamics and stable isotopes for tracing sources of suspended sediment

NASA Astrophysics Data System (ADS)

Schindler Wildhaber, Y.; Liechti, R.; Alewell, C.

2012-01-01

Suspended sediment (SS) and organic matter in rivers can harm brown trout Salmo trutta by impact on health and fitness of free swimming fish and siltation of the riverbed. The later results in a decrease of hydraulic conductivity and therefore smaller oxygen supply to the salmonid embryos. Additionally, oxygen demand within riverbeds will increase as the pool of organic matter increases. We assessed the temporal and spatial dynamics of sediment, carbon (C) and nitrogen (N) during the brown trout spawning season and used C isotopes as well as the C/N atomic ratio to distinguish autochthonous and allochthonous sources of organic matter in SS loads. The visual basic program IsoSource with 13Ctot and 15N as input isotopes was used to quantify the sources of SS in respect of time and space. Organic matter fractions in the infiltrated and suspended sediment were highest during low flow periods with small sediment loads and lowest during high flow periods with high sediment loads. Peak values in nitrate and dissolved organic C were measured during high flow and precipitation probably due to leaching from pasture and arable land. The organic matter was of allochthonous sources as indicated by the C/N atomic ratio and δ13Corg. Organic matter in SS increased from up- to downstream due to pasture and arable land. The fraction of SS originating from upper watershed riverbed sediment increased at all sites during high flow. Its mean fraction decreased from up- to downstream. During base flow conditions, the major sources of SS are pasture and arable land. The later increased during rainy and warmer periods probably due to snow melting and erosion processes. These modeling results support the measured increased DOC and NO3 concentrations during high flow.

Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

NASA Astrophysics Data System (ADS)

Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

2015-12-01

Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

A Metal Stable Isotope Approach to Understanding Uranium Mobility Across Roll Front Redox Boundaries

NASA Astrophysics Data System (ADS)

Brown, S. T.; Basu, A.; Christensen, J. N.; DePaolo, D. J.; Heikoop, J. M.; Reimus, P. W.; Maher, K.; Weaver, K. L.

2015-12-01

Sedimentary roll-front uranium (U) ore deposits are the principal source of U for nuclear fuel in the USA and an important part of the current all-of-the-above energy strategy. Mining of roll-front U ore in the USA is primarily by in situ alkaline oxidative dissolution of U minerals. There are significant environmental benefits to in situ mining including no mine tailings or radioactive dust, however, the long-term immobilization of U in the aquifer after the completion of mining remains uncertain. We have utilized the metal stable isotopes U, Se and Mo in groundwater from roll-front mines in Texas and Wyoming to quantify the aquifer redox conditions and predict the onset of U reduction after post mining aquifer restoration. Supporting information from the geochemistry of groundwater and aquifer sediments are used to understand the transport of U prior to and after in situ mining. Groundwater was collected across 4 mining units at the Rosita mine in the Texas coastal plain and 2 mining units at the Smith Ranch mine in the Powder River Basin, Wyoming. In general, the sampled waters are moderately reducing and ore zone wells contain the highest aqueous U concentrations. The lowest U concentrations occur in monitoring wells downgradient of the ore zone. 238U/235U is lowest in downgradient wells and is correlated with aqueous U concentrations. Rayleigh distillation models of the 238U/235U are consistent with U isotope fractionation factors of 1.0004-1.001, similar to lab-based studies. Based on these results we conclude that redox reactions continue to affect U distribution in the ore zone and downgradient regions. We also measured aqueous selenium isotope (δ82Se) and molybdenum isotope (δ98Mo) compositions in the Rosita groundwater. Se(VI) primarily occurs in the upgradient wells and is absent in most ore zone and downgradient wells. Rayleigh distillation models suggest reduction of Se(VI) along the groundwater flow path and when superimposed on the U isotope data Se reduction is favored over U reduction. The δ98Mo of Rosita groundwater is significantly elevated compared to the U ore and is negatively correlated with the groundwater Eh, which suggests localized strong reducing conditions capable of Mo reduction. Ongoing work will determine the Mo isotope systematics of U ores and groundwater from roll-front deposits.

Inadequacy, Impurity and Infidelity; Modifying the Modified Brendel Alpha-Cellulose Extraction Method for Resinous Woods in Stable Isotope Dendroclimatology

NASA Astrophysics Data System (ADS)

Brookman, T. H.; Whittaker, T. E.; King, P. L.; Horton, T. W.

2011-12-01

Stable isotope dendroclimatology is a burgeoning field in palaeoclimate science due to its unique potential to contribute (sub)annually resolved climate records, over millennial timescales, to the terrestrial palaeoclimate record. Until recently the time intensive methods precluded long-term climate reconstructions. Advances in continuous-flow mass spectrometry and isolation methods for α-cellulose (ideal for palaeoclimate studies as, unlike other wood components, it retains its initial isotopic composition) have made long-term, calendar dated palaeoclimate reconstructions a viable proposition. The Modified Brendel (mBrendel) α-cellulose extraction method is a fast, cost-effective way of preparing whole-wood samples for stable oxygen and carbon isotope analysis. However, resinous woods often yield incompletely processed α-cellulose using the standard mBrendel approach. As climate signals may be recorded by small (<1%) isotopic shifts it is important to investigate if incomplete processing affects the accuracy and precision of tree-ring isotopic records. In an effort to address this methodological issue, we investigated three highly resinous woods: kauri (Agathis australis), ponderosa pine (Pinus ponderosa) and huon pine (Lagarastrobus franklinii). Samples of each species were treated with 16 iterations of the mBrendel, varying reaction temperature, time and reagent volumes. Products were investigated using microscopic and bulk transmission Fourier Transform infrared spectroscopy (FITR) to reveal variations in the level of processing; poorly-digested fibres display a peak at 1520cm-1 suggesting residual lignin and a peak at ~1600cm-1 in some samples suggests retained resin. Despite the different levels of purity, replicate analyses of samples processed by high temperature digestion yielded consistent δ18O within and between experiments. All α-cellulose samples were 5-7% enriched compared to the whole-wood, suggesting that even incomplete processing at high temperature can provide acceptable δ18O analytical external precision. For kauri, short, lower temperature extractions produced α-cellulose with δ18O consistently ~1% lower than longer, higher temperature kauri experiments. These findings suggest that temperature and time are significant variables that influence the analytical precision of α-cellulose stable isotope analysis and that resinous hardwoods (e.g. kauri) may require longer and/or hotter digestions than softwoods. The effects of mBrendel variants on the carbon isotope ratio precision of α-cellulose extracts will also be presented. Our findings indicate that the standard mBrendel α-cellulose extraction method may not fully remove lignins and resins depending on the type of wood being analysed. Residual impurities can decrease analytical precision and accuracy. Fortunately, FTIR analysis prior to isotopic analysis is a relatively fast and cost effective way to determine α-cellulose extract purity, ultimately improving the data quality, accuracy and utility of tree-ring based stable isotopic climate records.

New biotite and muscovite isotopic reference materials, USGS57 and USGS58, for δ2H measurements–A replacement for NBS 30

USGS Publications Warehouse

Qi, Haiping; Coplen, Tyler B.; Gehre, Matthias; Vennemann, Torsten W.; Brand, Willi A.; Geilmann, Heike; Olack, Gerard; Bindeman, Ilya N.; Palandri, Jim; Huang, Li; Longstaffe, Fred J.

2017-01-01

The advent of continuous-flow isotope-ratio mass spectrometry (CF-IRMS) coupled with a high temperature conversion (HTC) system enabled faster, more cost effective, and more precise δ2H analysis of hydrogen-bearing solids. Accurate hydrogen isotopic analysis by on-line or off-line techniques requires appropriate isotopic reference materials (RMs). A strategy of two-point calibrations spanning δ2H range of the unknowns using two RMs is recommended. Unfortunately, the supply of the previously widely used isotopic RM, NBS 30 biotite, is exhausted. In addition, recent measurements have shown that the determination of δ2H values of NBS 30 biotite on the VSMOW-SLAP isotope-delta scale by on-line HTC systems with CF-IRMS may be unreliable because hydrogen in this biotite may not be converted quantitatively to molecular hydrogen. The δ2HVSMOW-SLAP values of NBS 30 biotite analyzed by on-line HTC systems can be as much as 21 mUr (or ‰) too positive compared to the accepted value of − 65.7 mUr, determined by only a few conventional off-line measurements. To ensure accurate and traceable on-line hydrogen isotope-ratio determinations in mineral samples, we here propose two isotopically homogeneous, hydrous mineral RMs with well-characterized isotope-ratio values, which are urgently needed. The U.S. Geological Survey (USGS) has prepared two such RMs, USGS57 biotite and USGS58 muscovite. The δ2H values were determined by both glassy carbon-based on-line conversion and chromium-based on-line conversion, and results were confirmed by off-line conversion. The quantitative conversion of hydrogen from the two RMs using the on-line HTC method was carefully evaluated in this study. The isotopic compositions of these new RMs with 1-σ uncertainties and mass fractions of hydrogen are:USGS57 (biotite)δ2HVSMOW-SLAP = − 91.5 ± 2.4 mUr (n = 24)Mass fraction hydrogen = 0.416 ± 0.002% (n = 4)Mass fraction water = 3.74 ± 0.02% (n = 4)USGS58 (muscovite)δ2HVSMOW-SLAP = − 28.4 ± 1.6 mUr (n = 24)Mass fraction hydrogen = 0.448 ± 0.002% (n = 4)Mass fraction water = 4.03 ± 0.02% (n = 4).These δ2HVSMOW-SLAP values encompass typical ranges for solid unknowns of crustal and mantle origin and are available to users for recommended two-point calibration.

Geochemistry of Woranso-Mille Pliocene basalts from west-central Afar, Ethiopia: Implications for mantle source characteristics and rift evolution

NASA Astrophysics Data System (ADS)

Alene, Mulugeta; Hart, William K.; Saylor, Beverly Z.; Deino, Alan; Mertzman, Stanley; Haile-Selassie, Yohannes; Gibert, Luis B.

2017-06-01

The Woranso-Mille (WORMIL) area in the west-central Afar, Ethiopia, contains several Pliocene basalt flows, tuffs, and fossiliferous volcaniclastic beds. We present whole-rock major- and trace-element data including REE, and Sr-Nd-Pb isotope ratios from these basalts to characterize the geochemistry, constrain petrogenetic processes, and infer mantle sources. Six basalt groups are distinguished stratigraphically and geochemically within the interval from 3.8 to 3 Ma. The elemental and isotopic data show intra- and inter-group variations derived primarily from source heterogeneity and polybaric crystallization ± crustal inputs. The combined Sr-Nd-Pb isotope data indicate the involvement of three main reservoirs: the Afar plume, depleted mantle, and enriched continental lithosphere (mantle ± crust). Trace element patterns and ratios further indicate the basalts were generated from spinel-dominated shallow melting, consistent with significantly thinned Pliocene lithosphere in western Afar. The on-land continuation of the Aden rift into western Afar during the Pliocene is reexamined in the context of the new geochemistry and age constraints of the WORMIL basalts. The new data reinforce previous interpretations that progressive rifting and transformation of the continental lithosphere to oceanic lithosphere allows for increasing asthenospheric inputs through time as the continental lithosphere is thinned. Accepted trace element values for BHVO-2 are those recently recommended by Jochum et al. (2016) rounded to provide the same significant figures as the data. Ternary model after Schilling et al. (1992); Endmembers from Rooney et al. (2012).

Modeling of water isotopes in polar regions and application to ice core studies

NASA Astrophysics Data System (ADS)

Jouzel, J.

2012-04-01

Willi Dansgaard spear-headed the use of the stable isotopes of water in climatology and palaeoclimatology especially as applied to deep ice cores for which measurements of the oxygen and hydrogen isotope ratios remain the key tools for reconstructing continuous palaeotemperature records. In the line of his pioneering work on "Stable isotopes in precipitation" published in Tellus in 1964, I will review how isotopic models, either Rayleigh type or based on the implementation of water isotopes in General Circulation Models, have developed and been used for applications in polar ice core studies. This will include a discussion of the conventional approach for interpreting water isotopes in ice cores and of additional information provided by measurements of the deuterium excess and more recently of the 17O-excess.

Axi-symmetrical flow reactor for [sup 196]Hg photochemical enrichment

DOEpatents

Grossman, M.W.

1991-04-30

The present invention is directed to an improved photochemical reactor useful for the isotopic enrichment of a predetermined isotope of mercury, especially, [sup 196]Hg. Specifically, two axi-symmetrical flow reactors were constructed according to the teachings of the present invention. These reactors improve the mixing of the reactants during the photochemical enrichment process, affording higher yields of the desired [sup 196]Hg product. Measurements of the variation of yield (Y) and enrichment factor (E) along the flow axis of these reactors indicates very substantial improvement in process uniformity compared to previously used photochemical reactor systems. In one preferred embodiment of the present invention, the photoreactor system was built such that the reactor chamber was removable from the system without disturbing the location of either the photochemical lamp or the filter employed therewith. 10 figures.

Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Hansen, Maximilian; Scholz, Denis

2016-02-01

We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3- dissolved in a thin water film covering the surface of a speleothem. The result is τex = τredex · [HCO3-]/ (KH · pCO2cave) , where τredex depends on the depth, a, of the water film and on temperature. [HCO3-] is the concentration of bicarbonate, pCO2cave the partial pressure of CO2, and KH is Henry's constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of pCO2 500, 12,500, or 25,000 ppmV and defined isotope composition. The δ13C and δ18O values of the DIC in the solution were measured as a function of the exposure time. For stagnant films with depths between 0.06 and 0.2 cm the δ13C values exhibit an exponential approach towards isotope equilibrium with the atmospheric CO2 with exchange time, τex. The δ18O values first evolve towards isotopic equilibrium with atmospheric CO2, reach a minimum value and then drift away from the isotopic equilibrium with atmospheric CO2 approaching a steady state caused by isotopic exchange of oxygen with water. The experimental findings are in satisfactory agreement with the theoretical predictions. To further investigate isotope evolution in cave analogue conditions, a water film containing 5 mmol/L of NaHCO3 with a depth of 0.013 cm flowing down an inclined borosilicate glass plate was exposed to an atmosphere with pCO2 = 500 ppmV at a temperature of 20 °C. The δ13C and δ18O values were measured as a function of flow (exposure) time, t. The isotope compositions in the DIC of the water film decrease linear in time by δDIC (t) =δDIC (0) - (δDIC (0) -δDIC (∞)) · t /τex where δDIC (0) is the initial isotope composition of dissolved inorganic carbon (DIC) in the water film and δDIC (∞) its final value. From these data an exchange time τex of ca. 7000 s was obtained, in satisfactory agreement with the theoretical predictions. The exchange times can be calculated by τex = τredex · [HCO3-]/ (KH · pCO2cave), where τredex is given by the theory as function of temperature and the depth, a, of the water film. This way it is possible to obtain exchange times for various conditions of stalagmite growth as they occur in caves.

Lead isotopes reveal bilateral asymmetry and vertical continuity in the Hawaiian mantle plume.

PubMed

Abouchami, W; Hofmann, A W; Galer, S J G; Frey, F A; Eisele, J; Feigenson, M

2005-04-14

The two parallel chains of Hawaiian volcanoes ('Loa' and 'Kea') are known to have statistically different but overlapping radiogenic isotope characteristics. This has been explained by a model of a concentrically zoned mantle plume, where the Kea chain preferentially samples a more peripheral portion of the plume. Using high-precision lead isotope data for both centrally and peripherally located volcanoes, we show here that the two trends have very little compositional overlap and instead reveal bilateral, non-concentric plume zones, probably derived from the plume source in the mantle. On a smaller scale, along the Kea chain, there are isotopic differences between the youngest lavas from the Mauna Kea and Kilauea volcanoes, but the 550-thousand-year-old Mauna Kea lavas are isotopically identical to Kilauea lavas, consistent with Mauna Kea's position relative to the plume, which was then similar to that of present-day Kilauea. We therefore conclude that narrow (less than 50 kilometres wide) compositional streaks, as well as the larger-scale bilateral zonation, are vertically continuous over tens to hundreds of kilometres within the plume.

Method and apparatus to measure vapor pressure in a flow system

DOEpatents

Grossman, M.W.; Biblarz, O.

1991-10-15

The present invention is directed to a method for determining, by a condensation method, the vapor pressure of a material with a known vapor pressure versus temperature characteristic, in a flow system particularly in a mercury isotope enrichment process. 2 figures.

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.

Spatial and Temporal Patterns In Ecohydrological Separation

NASA Astrophysics Data System (ADS)

Jarvis, S. K.; Barnard, H. R.; Singha, K.; Harmon, R. E.; Szutu, D.

2017-12-01

The model of ecohydrological separation suggests that trees source water from a different subsurface pool than what is contributing to stream flow during dry periods, however diel fluctuations in stream flow and transpiration are tightly coupled. To better understand the mechanism of this coupling, this study examines spatiotemporal patterns in water isotopic relationships between tree, soil, and stream water. Preliminary analysis of data collected in 2015 show a trend in δ18O enrichment in xylem water, suggesting an increased reliance on enriched soil water not flowing to the stream as the growing season progresses, while xylem samples from 2016, a particularly wet year, do not have this trend. Variations in these temporal trends are explored with regard to distance from stream, aspect of hillslope, position in the watershed, size of the tree, and soil depth. Additionally, a near-stream site is examined at high resolution using water isotope data, sap flow, and electrical resistivity surveying to examine soil moisture and water use patterns across the riparian-hillslope transition.

Influence of Locally Derived Recharge on the Water Quality and Temperature of Springs in Hot Springs National Park, Arkansas

USGS Publications Warehouse

Bell, Richard W.; Hays, Phillip D.

2007-01-01

The hot springs of Hot Springs National Park consist of a mixture of water from two recharge components: a primary hot-water component and a secondary cold-water component. Widespread distribution of fractures enables mixing of the hot- and cold-water components of flow near the discharge area for the springs. Urbanization in the area near the hot springs of Hot Springs National Park has increased the potential for degradation of the quality of surface-water runoff and locally derived ground-water recharge to the hot springs. Previous studies by the U.S. Geological Survey have indicated that water from some cold-water springs and wells in the vicinity of Hot Springs, Arkansas, showed evidence of contamination and that water from locally derived cold-water recharge might contribute 25 percent of the total flow to the hot springs after storms. Water samples were collected during base-flow conditions at nine hot springs and two cold-water springs in September 2000. Nine hot springs and one cold-water spring were resampled in October 2001 after a storm that resulted in a measurable decrease in water temperature in selected hot springs. Water samples were analyzed for a variety of dissolved chemical constituents (nutrients, major ions, trace elements, pesticides, semivolatile compounds, isotopes, and radiochemicals), physical properties, field measurements, and bacteria. Comparison of analyses of samples collected during base-flow conditions from the springs in 2000 and during a storm event in 2001 with the results from earlier studies dating back to the late 1800's indicates that little change in major, minor, and trace constituent chemistry has occurred and that the water continues to be of excellent quality. Water-quality data show distinguishable differences in water chemistry of the springs during base-flow and stormflow conditions, indicating changing input of cold-water recharge relative to hot-water recharge. Silica, total dissolved solids, strontium, barium, and sulfate show statistically significant differences between the median values of base-flow and stormflow samples. While variations in these constituents do not degrade water quality, the differences do provide evidence of variability in the factors controlling water quality of the hot springs and show that water quality is influenced by the locally derived, cold-water component of flow to the springs. Water temperature was measured continuously (3-minute intervals) between August 2000 and October 2002 at four hot springs. Continuous water-temperature data at the springs provide no indication of persistent long-term change in water temperature through time. Short time-scale water-temperature decreases occur in response to mixing of hot-springs water with locally derived recharge after storm events; the magnitude of these decreases varied inversely with the amount of rainfall. Maximum decreases in water temperature for specific storms had a non-linear relation with the amount of precipitation measured for the events. Response time for water temperature to begin decreasing from baseline temperature as a result of storm recharge was highly variable. Some springs began decreasing from baseline temperature as quickly as 1 hour after the beginning of a storm; one spring had an 8-hour minimum response time to show a storm-related temperature decrease. Water-quality, water-temperature, isotopic, and radiochemical data provide multiple lines of evidence supporting the importance of the contribution of cold-water recharge to hot springs. All the springs sampled indicated some measure of influence from local recharge. Binary mixing models using silica and total dissolved solids indicate that cold-water recharge from stormflow contributes an estimated 10 to 31 percent of the flow of hot springs. Models using water temperature indicate that cold-water recharge from stormflow contributes an estimated 1 to 35 percent of the flow of the various hot springs. Alth

Lead and strontium isotopic evidence for crustal interaction and compositional zonation in the source regions of Pleistocene basaltic and rhyolitic magmas of the Coso volcanic field, California

USGS Publications Warehouse

Bacon, C.R.; Kurasawa, H.; Delevaux, M.H.; Kistler, R.W.; Doe, B.R.

1984-01-01

The isotopic compositions of Pb and Sr in Pleistocene basalt, high-silica rhyolite, and andesitic inclusions in rhyolite of the Coso volcanic field indicate that these rocks were derived from different levels of compositionally zoned magmatic systems. The 2 earliest rhyolites probably were tapped from short-lived silicic reservoirs, in contrast to the other 36 rhyolite domes and lava flows which the isotopic data suggest may have been leaked from the top of a single, long-lived magmatic system. Most Coso basalts show isotopic, geochemical, and mineralogic evidence of interaction with crustal rocks, but one analyzed flow has isotopic ratios that may represent mantle values (87Sr/86Sr=0.7036,206Pb/204Pb=19.05,207Pb/204Pb=15.62,208Pb/204Pb= 38.63). The (initial) isotopic composition of typical rhyolite (87Sr/86Sr=0.7053,206Pb/204Pb=19.29,207Pb/204Pb= 15.68,208Pb/204Pb=39.00) is representative of the middle or upper crust. Andesitic inclusions in the rhyolites are evidently samples of hybrid magmas from the silicic/mafic interface in vertically zoned magma reservoirs. Silicic end-member compositions inferred for these mixed magmas, however, are not those of erupted rhyolite but reflect the zonation within the silicic part of the magma reservoir. The compositional contrast at the interface between mafic and silicic parts of these systems apparently was greater for the earlier, smaller reservoirs. ?? 1984 Springer-Verlag.

Temporal dynamics of catchment transit times from stable isotope data

NASA Astrophysics Data System (ADS)

Klaus, Julian; Chun, Kwok P.; McGuire, Kevin J.; McDonnell, Jeffrey J.

2015-06-01

Time variant catchment transit time distributions are fundamental descriptors of catchment function but yet not fully understood, characterized, and modeled. Here we present a new approach for use with standard runoff and tracer data sets that is based on tracking of tracer and age information and time variant catchment mixing. Our new approach is able to deal with nonstationarity of flow paths and catchment mixing, and an irregular shape of the transit time distribution. The approach extracts information on catchment mixing from the stable isotope time series instead of prior assumptions of mixing or the shape of transit time distribution. We first demonstrate proof of concept of the approach with artificial data; the Nash-Sutcliffe efficiencies in tracer and instantaneous transit times were >0.9. The model provides very accurate estimates of time variant transit times when the boundary conditions and fluxes are fully known. We then tested the model with real rainfall-runoff flow and isotope tracer time series from the H.J. Andrews Watershed 10 (WS10) in Oregon. Model efficiencies were 0.37 for the 18O modeling for a 2 year time series; the efficiencies increased to 0.86 for the second year underlying the need of long time tracer time series with a long overlap of tracer input and output. The approach was able to determine time variant transit time of WS10 with field data and showed how it follows the storage dynamics and related changes in flow paths where wet periods with high flows resulted in clearly shorter transit times compared to dry low flow periods.

Nd, Sr, and O isotopic variations in metaluminous ash-flow tuffs and related volcanic rocks at the Timber Mountain/Oasis Valley Caldera, Complex, SW Nevada: implications for the origin and evolution of large-volume silicic magma bodies

USGS Publications Warehouse

Farmer, G.L.; Broxton, D.E.; Warren, R.G.; Pickthorn, W.

1991-01-01

Nd, Sr and O isotopic data were obtained from silicic ash-flow tuffs and lavas at the Tertiary age (16-9 Ma) Timber (Mountain/Oasis Valley volcanic center (TMOV) in southern Nevada, to assess models for the origin and evolution of the large-volume silicic magma bodies generated in this region. The large-volume (>900 km3), chemically-zoned, Topopah Spring (TS) and Tiva Canyon (TC) members of the Paintbrush Tuff, and the Rainier Mesa (RM) and Ammonia Tanks (AT) members of the younger Timber Mountain Tuff all have internal Nd and Sr isotopic zonations. In each tuff, high-silica rhyolites have lower initial e{open}Nd values (???1 e{open}Nd unit), higher87Sr/86Sr, and lower Nd and Sr contents, than cocrupted trachytes. The TS, TC, and RM members have similar e{open}Nd values for high-silica rhyolites (-11.7 to -11.2) and trachytes (-10.5 to -10.7), but the younger AT member has a higher e{open}Nd for both compositional types (-10.3 and -9.4). Oxygen isotope data confirm that the TC and AT members were derived from low e{open}Nd magmas. The internal Sr and Nd isotopic variations in each tuff are interpreted to be the result of the incorporation of 20-40% (by mass) wall-rock into magmas that were injected into the upper crust. The low e{open}Nd magmas most likely formed via the incorporation of low ??18O, hydrothermally-altered, wall-rock. Small-volume rhyolite lavas and ash-flow tuffs have similar isotopic characteristics to the large-volume ash-flow tuffs, but lavas erupted from extracaldera vents may have interacted with higher ??18O crustal rocks peripheral to the main magma chamber(s). Andesitic lavas from the 13-14 Ma Wahmonie/Salyer volcanic center southeast of the TMOV have low e{open}Nd (-13.2 to -13.8) and are considered on the basis of textural evidence to be mixtures of basaltic composition magmas and large proportions (70-80%) of anatectic crustal melts. A similar process may have occurred early in the magmatic history of the TMOV. The large-volume rhyolites may represent a mature stage of magmatism after repeated injection of basaltic magmas, crustal melting, and volcanism cleared sufficient space in the upper crust for large magma bodies to accumulate and differentiate. The TMOV rhyolites and 0-10 Ma old basalts that erupted in southern Nevada all have similar Nd and Sr isotopic compositions, which suggests that silicic and mafic magmatism at the TMOV were genetically related. The distinctive isotopic compositions of the AT member may reflect temporal changes in the isotopic compositions of basaltic magmas entering the upper crust, possibly as a result of increasing "basification" of a lower crustal magma source by repeated injection of mantle-derived mafic magmas. ?? 1991 Springer-Verlag.

Modelingofwaterisotopesinpolarregionsandapplicationtoicecorestudies

NASA Astrophysics Data System (ADS)

Jouzel, J.

2012-04-01

Willi Dansgaard spear-headed the use of the stable isotopes of water in climatology and palaeoclimatology especially as applied to deep ice cores for which measurements of the oxygen and hydrogen isotope ratios remain the key tools for reconstructing continuous palaeotemperature records. In the line of his pioneering work on "Stable isotopes in precipitation" published in Tellus in 1964, I will review how isotopic models, either Rayleigh type or based on the implementation of water isotopes in General Circulation Models, have developed and been used for applications in polar ice core studies. This will include a discussion of the conventional approach for interpreting water isotopes in ice cores and of additional information provided by measurements of the deuterium excess and more recently of the 17O-excess.

Circulation Plasma Centrifuge with Product Flow

NASA Astrophysics Data System (ADS)

Borisevich, V. D.; Potanin, E. P.

2018-05-01

We have analyzed the isotope separation in a high-frequency plasma circulating centrifuge operating with a product flow. The rotation of a weakly ionized plasma is ensured by a rotating magnetic field, while the countercurrent flow (circulation) is produced by a traveling magnetic field. We have calculated the dependences of the enrichment factor and the separative power of the centrifuge on a product flow. The optimal characteristics of the separation unit have been determined.

Development and deployment of a passive sampling system in groundwater to characterize the critical zone through isotope tracing

NASA Astrophysics Data System (ADS)

Gal, Frédérick; Négrel, Philippe; Chagué, Bryan

2017-04-01

The Critical Zone (CZ) is the evolving boundary layer where rock, soil, water, air, and living organisms interact, zone controlling the transfer and storage of water and chemical elements. For investigating the CZ, we have developed an integrative sampling system to concentrate the chemical elements in groundwater (CRITEX project). Aims are to measure concentrations and isotopic ratios in groundwater through integrative sampling. In the frame of the groundwater analysis, particularly those located in the critical zone (0-100 m depth), this system makes it possible to create a water flow in a support of passive samplers using Diffusive Gradient in Thin type (DGT) and thus to pre-concentrate the chemical species on a chelating resin by diffusion through a membrane and over a given period in order to facilitate subsequent laboratory measurements. Because DGTs are generally used in surface waters with a high flow rate, the current objective is to create a sufficient flow of water in the sampler to optimize the trapping of elements. Different options and geometries have been modelled by simulation of the flow (agitation of water supplied by a motor and a propeller, pumping ...). The economic model of the device is based on an assembly of commercially available equipment, the novation is based on the support, fully designed in house (patent pending). The device aims to recreate sufficient water flow to avoid the creation of a too large Diffusion Boundary Layer (DBL) on the DGT surface and then to mimic the uptake conditions that prevail in surface waters. The simulations made it possible to optimize the position of the DGT and the velocity of the fluid in order to obtain the maximum flow at its surface and avoid the creation of the DBL. Conditions equivalent to those of a circulation of weakly agitated surface water are thus recreated. The first tests were carried out at lab, in a column simulating a piezometer, including pump, DGT holder and flow meter. Initial functional tests were carried out with tap water to observe the flow of water in the device, to determine the technical characteristics of the system (current, voltage, flow...) and to perform blank measurements to ensure that the device brings no contamination. We then carried out 6 days of immersion of the system on a piezometer of the BRGM site. In parallel, daily sampling was performed using conventional pumping method. Finally, we carried out tests on drillings in the Coët Dan experimental basin (Naizin, Morbihan, France). We established a screening of chemical elements on which isotopic measurements can be done by comparing the accumulated mass in the DGT with respect to the concentration of the elements in water. This suggests that the isotopic determination is possible for U, Sr, Nd and Ni with the exception of Cu and Zn at the moment. Possible contamination of DGTs themselves and/or during field investigations should be further studied in order to rule if Cu or Zn isotope analyses can be foreseen in the future.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Tracing of the Rhône River within Lake Geneva using stable isotope composition of water

NASA Astrophysics Data System (ADS)

Cotte, Gabriel; Vennemann, Torsten

2017-04-01

Determining the hydrodynamics of lake water is essential for a better understanding of nutrient transport but also of the distribution of potential pollutants through water reservoirs. The objective of this study is to understand the mixing of Rhône River water within Lake Geneva. During summer and autumn, when the lake thermally well stratified, the Rhône River water can potentially flow more or less directly towards and finally out of the "Petit Lac" (small lake basin close to Geneva) more than 55 km from its mouth. During winter, when stratification is weakened, the water from the Rhône River mixes more diffusively with the water of Lake Geneva. The aim of this study is to determine the path of the Rhône River through the lake more precisely and identify the thermal and meteorologic conditions favourable for different types of flows as suggested by physical circulation models of the Rhône River interflows. Waters are sampled from different North-South transects across the lake. Bathymetric profiles are measured for temperature, pH, conductivity and oxygen concentrations. In addition, the H- and O-isotope compositions of water, the C-isotope composition of dissolved inorganic carbon and the major ions are analysed. Sampling campaigns are carried out every two months to study the hydrodynamics of the lake at varying thermal conditions. The isotopic composition of water was already proven to be a powerful tool to trace the Rhône River interflow within the lake (Halder et al., 2013) but the details of this interflow remain debatable. It is the aim of the present study to use the isotopic tracer method in much more detailed cross-sections as a tool to both test and verify interflow models based on wind patterns and thermal dispersion of the waters. The chosen cross-sections, to be sampled regularly and "event-based", that is after extended periods of similar meteorological conditions, should allow for more precise estimates of the path of the Rhône water interflow and the control of different wind conditions on the formation of resultant gyres of circulation within Lake Geneva. For example, an anticlockwise gyre forces Rhône River water to flow at intermediate depths towards the northern shore of the lake and a return interflow close to the southern shore of the lake. Isotopic mixing models coupled to physical hydrodynamic models of the lake will help constrain the flow paths of the Rhône. References Halder J., Decrouy L. & Vennemann T. 2013 : Mixing of Rhône River water in Lake Geneva (Switzerland-France) inferred from stable hydrogen and oxygen isotope profiles, Journal of Hydrology 477:152-164

Evolution model of δ³⁴S and δ¹⁸O in dissolved sulfate in volcanic fan aquifers from recharge to coastal zone and through the Jakarta urban area, Indonesia.

PubMed

Hosono, Takahiro; Delinom, Robert; Nakano, Takanori; Kagabu, Makoto; Shimada, Jun

2011-06-01

The sources of sulfate in an aquifer system, and its formation/degradation via biogeochemical reactions, were investigated by determining sulfate isotope ratios (δ³⁴S(SO₄) and δ¹⁸O(SO₄) in dissolved sulfate in groundwater from the Jakarta Basin. The groundwater flow paths, water ages, and geochemical features are well known from previous studies, providing a framework for the groundwater chemical and isotopic data, which is supplemented with data for spring water, river water, hot spring water, seawater, detergents, and fertilizers within the basin. The sulfate isotope composition of groundwater samples varied widely from -2.9‰ to +33.4‰ for δ³⁴S(SO₄) and +4.9‰ to +17.8‰ for δ¹⁸O(SO₄) and changed systematically along its flow direction from the mountains north to the coastal area. The groundwater samples were classified into three groups showing (1) relatively low and narrow δ(34)S(SO₄) (+2.3‰ to +7.6‰) with low and varied δ¹⁸O(SO₄) (+4.9‰ to +12.9‰) compositions, (2) high and varied δ³⁴S(SO₄) (+10.2‰ to +33.4‰) with high δ¹⁸O(SO₄) (+12.4‰ to +17.3‰) compositions, and (3) low δ³⁴S(SO₄) (< +6.1‰) with high δ¹⁸O(SO₄) (up to +17.8‰) compositions. These three types of groundwater were observed in the terrestrial unconfined aquifer, the coastal unconfined and confined aquifers, and the terrestrial confined aquifer, respectively. A combination of field measurements, concentrations, and previously determined δ¹⁵N(NO₃) data, showed that the observed isotopic heterogeneity was mainly the result of contributions of pollutants from domestic sewage in the rural area, mixing of seawater sulfate that had experienced previous bacterial sulfate reduction in the coastal area, and isotopic fractionation during the formation of sulfate through bacterial disproportionation of elemental sulfur. Our results clearly support the hypothesis that human impacts are important factors in understanding the sulfur cycle in present-day subsurface environments. A general model of sulfate isotopic evolution along with groundwater flow has rarely been proposed, due to the complicated hydrogeological research setting that causes varied isotope ratios, although its understanding has recently received great attention. This pioneer study on a simple volcanic fan aquifer system with a well-understood groundwater flow mechanism provides a useful model for future studies. Copyright © 2011 Elsevier B.V. All rights reserved.

Determination of the components of stormflow using water chemistry and environmental isotopes, Mattole River basin, California

USGS Publications Warehouse

Kennedy, V.C.; Kendall, C.; Zellweger, G.W.; Wyerman, T.A.; Avanzino, R.J.

1986-01-01

The chemical and isotopic composition of rainfall and stream water was monitored during a storm in the Mattole River basin of northwestern California. About 250 mm of rain fell during 6 days (???80% within a 42 h period) in late January, 1972, following 24 days of little or no precipitation. River discharge near Petrolia increased from 22 m3 s-1 to a maximum of 1300 m3 s-1 while chloride and silica concentrations decreased only from 3.2 to 2.1 and 11.5 to 8.6 mgl-1, respectively. Meanwhile, the isotopic composition of the river changed from ??D = - 42???, ??180 = - 6.8??? and 40 tritium units (T.U.) to extreme values at highest flow of ??D = - 35???, ??180 = - 5.9??? and 25 T.U. in response to volume-weighted rainfall averaging ??D = - 19.5???, ??180 = - 3.1??? and 18 T.U. Despite much rainfall of a composition quite different from that of the prestorm river water, "buffering" processes in the watershed greatly restricted changes in the chemical and isotopic content of the river during storm runoff. Because of the physical and hydrologic characteristics of the watershed, major contributions of groundwater to stormflow are very unlikely. The large increase in dissolved chemical load observed at maximum river discharge required that extensive interaction with, and presumably penetration of, soils occurred within a few hours time. Such a large increase in chemical load also required subsurface stormflow throughout a high proportion of the watershed. Chemical and isotopic stabilization of stormflow is believed to be due mainly to displacement of prestorm soil water, with some effects on river chemistry due to rapid rain-soil interactions. The isotopic and chemical composition of prestorm soil moisture cannot readily be predicted a priori because of possible variability in rainfall composition, evaporation, and exchange with atmospheric moisture, nor can it be assumed that baseflow has a predictable relation to the chemical or isotopic composition of water displaced from soils during storms. Therefore, it seems inappropriate to draw conclusions as to the relative proportions of groundwater and rainfall in runoff from a particular storm based only on the average compositions of rainfall, stormflow, and prestorm river water, as has been done in most previous isotope hydrograph studies. Given the great variation in hydrology, topography, soil characteristics, rainfall intensity and quantity, etc. from place to place, the relative amount of overland flow, subsurface flow from the unsaturated zone and of groundwater in stormflow can vary greatly in time and space. ?? 1986.

Water isotope ratio (δ2H and δ18O) measurements in atmospheric moisture using an optical feedback cavity enhanced absorption laser spectrometer

NASA Astrophysics Data System (ADS)

Iannone, Rosario Q.; Romanini, Daniele; Cattani, Olivier; Meijer, Harro A. J.; Kerstel, Erik R. Th.

2010-05-01

Water vapor isotopes represent an innovative and excellent tool for understanding complex mechanisms in the atmospheric water cycle over different time scales, and they can be used for a variety of applications in the fields of paleoclimatology, hydrology, oceanography, and ecology. We use an ultrasensitive near-infrared spectrometer, originally designed for use on airborne platforms in the upper troposphere and lower stratosphere, to measure the water deuterium and oxygen-18 isotope ratios in situ, in ground-level tropospheric moisture, with a high temporal resolution (from 300 s down to less than 1 s). We present some examples of continuous monitoring of near-surface atmospheric moisture, demonstrating that our infrared laser spectrometer could be used successfully to record high-concentration atmospheric water vapor mixing ratios in continuous time series, with a data coverage of ˜90%, interrupted only for daily calibration to two isotope ratio mass spectrometry-calibrated local water standards. The atmospheric data show that the water vapor isotopic composition exhibits a high variability that can be related to weather conditions, especially to changes in relative humidity. Besides, the results suggest that observed spatial and temporal variations of the stable isotope content of atmospheric water vapor are strongly related to water vapor transport in the atmosphere.

Laser photochemical lead isotopes separation for harmless nuclear power engineering

NASA Astrophysics Data System (ADS)

Bokhan, P. A.; Fateev, N. V.; Kim, V. A.; Zakrevsky, D. E.

2016-09-01

The collisional quenching of the metastable 3 P 1,2 and 1 D 2 lead atoms is studied experimentally in the gas flow of the lead atoms, reagent-molecules and a carrier gas Ar. The experimental parameters were similar to the conditions that are required in the operation of the experimental setup for photochemical isotope separation. Excited atoms are generated under electron impact conditions created by a gas glow discharge through the mixture of gases and monitored photoelectrically by attenuation of atomic resonance radiation from hollow cathode 208Pb lamp. The decay of the excited atoms has been studied in the presence various molecules and total cross section data are reported. The flow tube measurements has allowed to separate the physical and chemical quenching channels and measure the rates of the chemical reaction excited lead with N2O, CH2Cl2, SF6 and CuBr molecules. These results are discussed in the prospects of the obtaining isotopically modified lead as a promising coolant in the reactors on the fast-neutron.

New insights on ecosystem mercury cycling revealed by stable isotopes of mercury in water flowing from a headwater peatland catchment

Treesearch

Glenn E. Woerndle; Martin Tsz-Ki Tsui; Stephen D. Sebestyen; Joel D. Blum; Xiangping Nie; Randall K. Kolka

2018-01-01

Stable isotope compositions of mercury (Hg) were measured in the outlet stream and in soil cores at different landscape positions in a 9.7-ha boreal upland-peatland catchment. An acidic permanganate/persulfate digestion procedure was validated for water samples with high dissolved organic matter (DOM) concentrations through Hg spike addition analysis. We report a...

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.

Production waters associated with the Ferron coalbed methane fields, central Utah: Chemical and isotopic composition and volumes

USGS Publications Warehouse

Rice, C.A.

2003-01-01

This study investigated the composition of water co-produced with coalbed methane (CBM) from the Upper Cretaceous Ferron Sandstone Member of the Mancos Shale in east-central Utah to better understand coalbed methane reservoirs. The Ferron coalbed methane play currently has more than 600 wells producing an average of 240 bbl/day/well water. Water samples collected from 28 wellheads in three fields (Buzzards Bench, Drunkards Wash, and Helper State) of the northeast-southwest trending play were analyzed for chemical and stable isotopic composition.Water produced from coalbed methane wells is a Na-Cl-HCO3 type. Water from the Drunkards Wash field has the lowest total dissolved solids (TDS) (6300 mg/l) increasing in value to the southeast and northeast. In the Helper State field, about 6 miles northeast, water has the highest total dissolved solids (43,000 mg/l), and major ion abundance indicates the possible influence of evaporite dissolution or mixing with a saline brine. In the southern Buzzards Bench field, water has variable total dissolved solids that are not correlated with depth or spatial distance. Significant differences in the relative compositions are present between the three fields implying varying origins of solutes and/or different water-rock interactions along multiple flow paths.Stable isotopic values of water from the Ferron range from +0.9??? to -11.4??? ?? 18O and -32??? to -90??? ?? 2H and plot below the global meteoric water line (GMWL) on a line near, but above values of present-day meteoric water. Isotopic values of Ferron water are consistent with modification of meteoric water along a flow path by mixing with an evolved seawater brine and/or interaction with carbonate minerals. Analysis of isotopic values versus chloride (conservative element) and total dissolved solids concentrations indicates that recharge water in the Buzzards Bench area is distinct from recharge water in Drunkards Wash and is about 3 ??C warmer. These variations in isotopes along with compositional variations imply that the Ferron reservoir is heterogeneous and compartmentalized, and that multiple flow paths may exist. ?? 2003 Published by Elsevier B.V. All rights reserved.

Relations between well-field pumping and induced canal leakage in east-central Miami-Dade County, Florida, 2010-2011

USGS Publications Warehouse

Nemec, Katherine; Antolino, Dominick J.; Turtora, Michael; Adam Foster,

2015-08-26

Results from the groundwater model and the stable isotope data analysis indicate the importance of considering geologic heterogeneity when investigating the relations between pumping and canal leakage, not only at this site, but also at other sites with similar heterogeneous geology. The model results were consistently sensitive to the hydrogeologic framework and changes in hydraulic conductivities. The model and the isotope data indicate that the majority of the groundwater/surface-water interactions occurred within the shallow flow zone. A relatively lower-permeability geologic layer occurring between the shallowest and deep preferential flow zones lessens the interactions between the production wells and the canal.

Numerical modelling of the flow and isotope separation in centrifuge Iguasu for different lengths of the rotor

NASA Astrophysics Data System (ADS)

Bogovalov, S. V.; Borisevich, V. D.; Borman, V. D.; Tronin, I. V.; Tronin, V. N.

2016-06-01

Numerical modelling and optimization of the gas flow and isotope separation in the Iguasu gas centrifuge (GC) for uranium enrichment have been performed for different lengths of the rotor. The calculations show that the specific separative power of the GC reduces with the length of the rotor. We show that the reduction of the specific separative power is connected with the growth of the pressure in the optimal regime and corresponding growth of temperature to prevent the working gas sublimation. The specific separative power remains constant with the growth of the rotor length provided that the temperature of the gas is taken to be constant.

Numerical modelling of the flow and isotope separation in centrifuge Iguasu for different lengths of the rotor

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

Bogovalov, S. V.; Borisevich, V. D.; Borman, V. D.

Numerical modelling and optimization of the gas flow and isotope separation in the Iguasu gas centrifuge (GC) for uranium enrichment have been performed for different lengths of the rotor. The calculations show that the specific separative power of the GC reduces with the length of the rotor. We show that the reduction of the specific separative power is connected with the growth of the pressure in the optimal regime and corresponding growth of temperature to prevent the working gas sublimation. The specific separative power remains constant with the growth of the rotor length provided that the temperature of the gasmore » is taken to be constant.« less

The flow mechanism in the Chalk based on radio-isotope analyses of groundwater in the London Basin

USGS Publications Warehouse

Downing, R.A.; Pearson, F.J.; Smith, D.B.

1979-01-01

14C analyses of groundwaters from the Chalk of the London Basin are re-interpreted and the age of the groundwater is revised. Radio-isotope analyses are used to examine the flow mechanism in the aquifer. The evidence supports the view that a network of micro-fissures and larger intergranular pores in the matrix provides a significant part of the water pumped from Chalk wells and the major fissures distribute the water to the wells. Most of the matrix is fine-grained and contains a very old water. This diffuses into the micro-fissures and larger pores and is carried to the wells by the major fissures. ?? 1979.

Ultrafiltration by a compacted clay membrane-I. Oxygen and hydrogen isotopic fractionation

USGS Publications Warehouse

Coplen, T.B.; Hanshaw, B.B.

1973-01-01

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01 N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disc compacted to a porosity of 35 per cent by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5%. and in O18 by 0.8%. relative to the residual solution. No additional isotopic fractionation due to a salt filtering mechanism was observed at NaCl concentrations up to 0.01 N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. ?? 1973.

Hydrogen isotope exchange in a metal hydride tube

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

Robinson, David B.

2014-09-01

This report describes a model of the displacement of one hydrogen isotope within a metal hydride tube by a different isotope in the gas phase that is blown through the tube. The model incorporates only the most basic parameters to make a clear connection to the theory of open-tube gas chromatography, and to provide a simple description of how the behavior of the system scales with controllable parameters such as gas velocity and tube radius. A single tube can be seen as a building block for more complex architectures that provide higher molar flow rates or other advanced design goals.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Conservation paleobiology in near time: Isotopic estimates for restoration flows to the estuary of the Colorado River, Mexico

NASA Astrophysics Data System (ADS)

Flessa, Karl; Dettman, David; Cintra-Buenrostro, Carlos; Rowell, Kirsten

2016-04-01

In most years since 1960, the Colorado River has not reached the sea. Upstream dams and diversions in the U.S.A. and Mexico have diverted the river's water for agricultural and municipal use. The river's estuary in the upper Gulf of California, in Mexico, once supported very large populations of Mulinia coloradoensis, a trophically important bivalve mollusk, and Totoaba macdonaldi, a now-endangered scianid fish,. Because Colorado River water is isotopically distinct from Gulf of California seawater, we used the δ18O composition of the pre-dam bivalve shells and fish otoliths to estimate past salinities and river flows. We estimate that five to ten percent of the river's annual flow would be needed to restore M. coloradoensis habitat in the river's mouth and to restore the nursery grounds of T. macdonaldi. The dead can speak to the living.

Stable-isotope geochemistry of the Pierina high-sulfidation Au-Ag deposit, Peru: Influence of hydrodynamics on SO42--H2S sulfur isotopic exchange in magmatic-steam and steam-heated environments

USGS Publications Warehouse

Fifarek, R.H.; Rye, R.O.

2005-01-01

The Pierina high-sulfidation Au-Ag deposit formed 14.5 my ago in rhyolite ash flow tuffs that overlie porphyritic andesite and dacite lavas and are adjacent to a crosscutting and interfingering dacite flow dome complex. The distribution of alteration zones indicates that fluid flow in the lavas was largely confined to structures but was dispersed laterally in the tuffs because of a high primary and alteration-induced permeability. The lithologically controlled hydrodynamics created unusual fluid, temperature, and pH conditions that led to complete SO42--H2S isotopic equilibration during the formation of some magmatic-steam and steam-heated alunite, a phenomenon not previously recognized in similar deposits. Isotopic data for early magmatic hydrothermal and main-stage alunite (??34S=8.5??? to 31.7???; ??18 OSO4=4.9??? to 16.5???; ??18 OOH=2.2??? to 14.4???; ??D=-97??? to -39???), sulfides (??34 S=-3.0??? to 4.3???), sulfur (??34S=-1.0??? to 1.1???), and clay minerals (??18O=4.3??? to 12.5???; ??D=-126??? to -81???) are typical of high-sulfidation epithermal deposits. The data imply the following genetic elements for Pierina alteration-mineralization: (1) fluid and vapor exsolution from an I-type magma, (2) wallrock buffering and cooling of slowing rising vapors to generate a reduced (H2S/SO4???6) highly acidic condensate that mixed with meteoric water but retained a magmatic ??34S???S signature of ???1???, (3) SO2 disproportionation to HSO4- and H2S between 320 and 180 ??C, and (4) progressive neutralization of laterally migrating acid fluids to form a vuggy quartz???alunite-quartz??clay???intermediate argillic???propylitic alteration zoning. Magmatic-steam alunite has higher ??34S (8.5??? to 23.2???) and generally lower ??18OSO4 (1.0 to 11.5???), ??18OOH (-3.4 to 5.9???), and ??D (-93 to -77???) values than predicted on the basis of data from similar occurrences. These data and supporting fluid-inclusion gas chemistry imply that the rate of vapor ascent for this environment was unusually slow, which provided sufficient time for the uptake of groundwater and partial to complete SO42--H2S isotopic exchange. The slow steam velocities were likely related to the dispersal of the steam column as it entered the tuffs and possibly to intermediate exsolution rates from magmatic brine. The low ??D values may also partly reflect continuous degassing of the mineralizing magma. Similarly, data for steam-heated alunite (??34S=12.3??? to 27.2???; ??18OSO4=11.7??? to 13.0???; ??18OOH=6.6??? to 9.4???; ??D=-59??? to -42???) are unusual and indicate a strong magmatic influence, relatively high temperatures (140 to 180 ??C, based on ??18 OSO4-OH fractionations), and partial to complete sulfur isotopic exchange between steam-heated sulfate and H2S. Restricted lithologically controlled fluid flow in the host tuffs allowed magmatic condensate to supplant meteoric groundwater at the water table and create the high-temperature low-pH conditions that permitted unusually rapid SO42--H2S isotopic equilibration (50-300 days) and (or) long sulfate residence times for this environment. Late void-filling barite (??34S=7.4??? to 29.7???; ??18OSO4=-0.4??? to 15.1???) and later void-filling goethite (??18O=-11.8??? to 0.2???) document a transition from magmatic condensate to dominantly meteoric water in steam-heated fluids during cooling and collapse of the hydrothermal system. These steam-heated fluids oxidized the top ???300 m of the deposit by leaching sulfides, redistributing metals, and precipitating barite??acanthite??gold and goethite-hematite ??gold. Steam-heated oxidation, rather than weathering, was critical to forming the orebody in that it not only released encapsulated gold but likely enriched the deposit to ore-grade Au concentrations. ?? 2004 Elsevier B.V. All rights reserved.

Can tree-ring isotopes (δ18O and δ13C) improve our understanding of hydroclimate variability in the Columbia River Basin?

NASA Astrophysics Data System (ADS)

Csank, A. Z.; Wise, E.; McAfee, S. A.

2015-12-01

The trajectory of incoming storms from the Pacific Ocean has a strong impact on hydroclimate in the Pacific Northwest. Shifts between zonal and meridional flow are a key influence on drought and pluvial regimes in both the PNW and the western United States as a whole. Circulation-dependent variability in the isotopic composition of precipitation can be recorded and potentially reconstructed using δ18O records derived from tree-rings. Here we present isotopic records of δ18O and δ13C from ponderosa pine (Pinus ponderosa) for the period 1950-2013 from six sites located in the lee of the Cascades in eastern Washington. Because of the orientation of the Cascades, zonal flow will result in an intensified rain shadow whereas meridional flow allows moisture to penetrate at a lower elevation leading to a lower rainout effect. This means zonal flow results in drier conditions in eastern Washington and the converse for meridional flow. We hypothesized that more depleted precipitation δ18O values will occur with periods of more zonal flow across the PNW and will be recorded by trees at our sites. Results show a strong relationship between our δ18O chronologies and winter precipitation (R = -0.50; p<0.001). δ13C chronologies from the same trees showed a relationship to prior fall/winter (pOct-pDec) precipitation (R = -0.46; p<0.005) suggesting a possible link to antecedent moisture conditions. With a focus on years with clear zonal and meridional flow regimes, we regressed the tree-ring δ18O anomaly against the instrumental record of total precipitation and compared the residual series to records of storm track for the period 1978-2008, and we found a detectable signal where the most depleted δ18O was generally associated with zonal flow and the most enriched δ18O with meridional flow. However, there are still some years where the relationship is unclear. Further work is aimed at understanding these anomalous years and extending our record beyond the instrumental period.

Insights into the Groundwater Salinization Processes in Manas River Basin, Northwest China

NASA Astrophysics Data System (ADS)

Jin, M.; Liu, Y.; Liang, X.

2017-12-01

Manas River Basin (MRB) is a typical mountains-oasis-desert inland basin in northwest China, where groundwater salinization is threatening the local water use and the environment, but the groundwater salinization process is not clear. Based on groundwater flow system analysis by integrating flow fields, hydrochemical and isotopic characteristics, a deuterium excess analytical method was used to quantitatively assess salinization mechanism and calculate the contribution ratios of evapoconcentration effect to the salinities. 73 groundwater samples and 11 surface water samples were collected from the basin. Hydrochemical diagrams and δD and δ18O compositions indicated that evapoconcentration, mineral dissolution and transpiration, increased the groundwater salinities (i.e. total dissolved solids). The results showed that the average contribution ratios of evapoconcentration effect to the increased salinities were 5.8% and 32.7% in groundwater and surface water, respectively. From the piedmont plain to the desert plain, the evapoconcentration effect increased the average groundwater loss from 7% to 29%. However, it only increased slight salinity (0 - 0.27 g/L), as determined from the deuterium excess signals. Minerals dissolution and anthropogenic activities are the major cause of groundwater salinization problem. The results revealed that fresh water in the rivers directly and quickly infiltrated the aquifers in the piedmont area with evapoconcentration affected weakly, and the fresh water interacted with the sediments and dissolved soluble minerals, subsequently increasing the salinities. Combined with the groundwater stable isotopic compositions and hydrochemical evolution, the relationships between δ18O and Cl and salinities reveal the soil evaporites leaching by the vertical recharge (irrigation return flow and channels leakage) mainly affect the groundwater salinization processes in the middle alluvial-diluvial plain and the desert land. The saline water released from aquitards by continuous decline of water level due to over exploitation is an additional factor for groundwater salinization.

Quantity and sources of base flow in the San Pedro River near Tombstone, Arizona

USGS Publications Warehouse

Kennedy, Jeffrey R.; Gungle, Bruce

2010-01-01

Base flow in the upper San Pedro River at the gaging station (USGS station 09471550) near Tombstone, Arizona, is an important factor in the long-term sustainability of the river's riparian ecosystem. Most base flow occurs during the non-summer months (typically, from November to May), because evapotranspiration (ET) is greater than groundwater discharge to the riparian zone during the growing season and typically causes periods of zero flow in the spring and fall. Streamflow during the summer months occurs only as a result of rainfall and runoff. Using a hydrograph separation technique that partitions streamflow into stormflow and base flow, based on the change in runoff from the previous day, median base flow at the Tombstone gage from 1968 to 2009 (1987 to 1996 data absent) is 4,890 acre-ft/yr. Median base flow for the earlier period of record, 1968 to 1986, is 5,830 acre-ft/yr and for the later period, 1997 to 2009, is 2,880 acre-ft/yr. Base flow in the upper San Pedro River is derived from groundwater discharge to the river from the regional and alluvial aquifer. The regional aquifer is defined as having recharge zones away from the river, primarily at mountain fronts and along ephemeral channels. The alluvial aquifer is recharged mainly from stormflow. Based on environmental isotope data, the composition of base flow in the upper San Pedro River at the gaging station near Tombstone is 74 +/- 10 percent regional groundwater and 26 +/- 10 percent summer storm runoff stored as alluvial groundwater for the 2000 to 2009 period. The volume of base flow in a given year is well explained, using multiple regression, by mean daily flow during the previous October and by rainfall during the months of December and January (R2 = 0.9). This does not suggest that streamflow is composed only of these two sources; rather, these two sources control the degree of saturation of the near-stream alluvial aquifer and, therefore, the amount of winter base-flow infiltration that is possible upstream of the Tombstone gaging station. Because of losing conditions upstream of the Tombstone gage, there is no minimum amount of base flow that would be expected in any given year. The regression equation was used to adjust the measured base flow to account for year-to-year variation in precipitation. Adjusted base flows decreased, independent of climate, from the early period of record to the late period of record. In addition to total base flow, other metrics were considered, including the start and end dates of base flow, the number of days of base flow, the 25th percentile mean daily flow, and the number of days of zero flow. Each of these showed a decline in base flow between the early period of record and the late period. The available evidence to evaluate this decrease - hydraulic gradients in the alluvial and regional aquifers and a 10-yr record of streamflow environmental isotope samples - indicates that no reduction in groundwater discharge has occurred over this period of record. Continued regional groundwater pumping will, however, eventually lead to a decline in the contribution of regional groundwater to base flow.

Groundwater and surface water interaction in a basin surrounded by steep mountains, central Japan

NASA Astrophysics Data System (ADS)

Ikeda, Koichi; Tsujimura, Maki; Kaeriyama, Toshiaki; Nakano, Takanori

2015-04-01

Mountainous headwaters and lower stream alluvial plains are important as water recharge and discharge areas from the view point of groundwater flow system. Especially, groundwater and surface water interaction is one of the most important processes to understand the total groundwater flow system from the mountain to the alluvial plain. We performed tracer approach and hydrometric investigations in a basin with an area 948 square km surrounded by steep mountains with an altitude from 250m to 2060m, collected 258 groundwater samples and 112 surface water samples along four streams flowing in the basin. Also, Stable isotopes ratios of oxygen-18 (18O) and deuterium (D) and strontium (Sr) were determined on all water samples. The 18O and D show distinctive values for each sub-basin affected by different average recharge altitudes among four sub-basins. Also, Sr isotope ratio shows the same trend as 18O and D affected by different geological covers in the recharge areas among four sub-basins. The 18O, D and Sr isotope values of groundwater along some rivers in the middle stream region of the basin show close values as the rivers, and suggesting that direct recharge from the river to the shallow groundwater is predominant in that region. Also, a decreasing trend of discharge rate of the stream along the flow supports this idea of the groundwater and surface water interaction in the basin.

Mapping the isotopic signature of methane in South-Eastern Spain: complementing biogeochemical long-term research with short term observations

NASA Astrophysics Data System (ADS)

Àgueda, Alba; Morguí, Josep Anton; Vazquez Garcia, Eusebi; Curcoll, Roger; Lowry, David; Fisher, Rebecca E.; Nisbet, Euan G.

2016-04-01

As a greenhouse gas, methane has a global warming potential of 25 in a 100 year scale. In order to establish mitigation plans it is important to assess its sources and sinks which can be both of geological and biological origin. South-Eastern Spain is a region with many different possible methane sources: i) by seismic activity of many geological faults both inland and in the neighbouring marine region (i.e. the Carboneras fault crossing the Alborán Sea along Málaga coastline); ii) by seepage of methane from hydrates present in the marine regions close to the Gibraltar Strait and the Gulf of Cádiz; iii) by emissions from fossil fuels caused by high traffic of merchant ships and the presence of large harbours (Algeciras, Tetuan and Cádiz), and the Africa - Europe Gas Transport Network in the Gibraltar Strait region; iv) by organic matter decomposition in both highly productive marshlands and eutrophic reservoirs; v) by burning of agricultural debris for energy supply, mainly from olive residues. In this study, a methane mapping survey has been conducted in the area around three atmospheric stations of the ClimaDat Atmospheric Network for Continuous Measurements of Greenhouse Gases (www.climadat.es) located in South-Eastern Spain (Sierra de Grazalema (SGC3), Tarifa (EEC3) and Sierra de Segura (SSC3). A cavity ring down spectrometer (CRDS) (G2301m, Picarro®) installed on a car has been used to measure methane concentrations. Additionally, in selected points, air samples have been collected in Tedlar bags for isotopic signature analysis by CF-GC-IRMS (Continuous Flow Gas Chromatography-Isotope Ratio Mass Spectrometry). In order to obtain a map facilitating the identification of the different methane sources in the background air at regional scale, the mapping of isotopic signature of methane together with its concentration is a useful tool to obtain fast and direct information that will contribute to the knowledge of methane transport at the regional scale and will be helpful in the validation of transport models. *Corresponding author: Josep Anton Morguí - josep-anton.morgui@ic3.cat "The research leading to these results has received funding from the European Community's Seventh Framework Programme (FP7/2007-2013) in the InGOS project under grant agreement n° 284274''

High-accuracy measurements of N2O concentration and site-specific nitrogen isotopes in small or high concentration samples

NASA Astrophysics Data System (ADS)

Palmer, M. R.; Arata, C.; Huang, K.

2014-12-01

Nitrous oxide (N2O) gas is among the major contributors to global warming and ozone depletion in stratosphere. Quantitative estimate of N­2O production in various pathways and N­2O fluxes across different reservoirs is the key to understanding the role of N­2O in the global change. To achieve this goal, accurate and concurrent measurement of both N2O concentration ([N2O]) and its site-specific isotopic composition (SP-δ15N), namely δ15Nα and δ15Nβ, is desired. Recent developments in Cavity Ring-Down Spectroscopy (CRDS) have enabled high precision measurements of [N2O] and SP-δ15N of a continuous gas flow. However, many N­­2O samples are discrete with limited volume (< 500 ml), and/or high [N2O] (> 2 ppm), and are not suitable for direct measurements by CRDS. Here we present results of a Small Sample Isotope Module 2 (SSIM2) which is coupled to and automatically coordinated with a Picarro isotopic N2O CRDS analyzer to handle and measure high concentration and/or small volume samples. The SSIM2 requires 20 ml of sample per analysis, and transfers the sample to the CRDS for high precision measurement. When the sample injection is < 20 ml, a zero gas is optionally filled to make up the volume. We used the SSIM2 to dilute high [N2O] samples and < 20 ml samples, and tested the effect of dilution on the measured SP-δ15N. In addition, we employed and tested a newly developed double injection method for samples adequate for two 20 ml injections. After the SSIM2 and the CRDS cavity was primed with the first injection, the second injection, which has negligible dilution of the sample, can be accurately measured for both [N2O] and SP-δ15N. Results of these experiments indicate that the precision of SSIM2-CRDS is similar to that of the continuous measurements using the CRDS alone, and that dilution has minimal effect on SP-δ15N, as along as the [N2O] is > 300 ppb after dilution. Overall, the precision of SP-δ15N measured using the SSIM2 is < 0.5 ‰.

Seasonal and event variations in δ34S values of stream sulfate in a Vermont forested catchment: Implications for sulfur sources and cycling

USGS Publications Warehouse

Shanley, James B.; Mayer, Bernhard; Mitchell, Myron J.; Bailey, Scott W.

2008-01-01

Stable sulfur (S) isotope ratios can be used to identify the sources of sulfate contributing to streamwater. We collected weekly and high-flow stream samples for S isotopic analysis of sulfate through the entire water year 2003 plus the snowmelt period of 2004. The study area was the 41-ha forested W-9 catchment at Sleepers River Research Watershed, Vermont, a site known to produce sulfate from weathering of sulfide minerals in the bedrock. The δ34S values of streamwater sulfate followed an annual sinusoidal pattern ranging from about 6.5‰ in early spring to about 10‰ in early fall. During high-flow events, δ34S values typically decreased by 1 to 3‰ from the prevailing seasonal value. The isotopic evidence suggests that stream sulfate concentrations are controlled by: (1) an overall dominance of bedrock-derived sulfate (δ34S ~ 6–14‰); (2) contributions of pedogenic sulfate (δ34S ~ 5–6‰) during snowmelt and storms with progressively diminishing contributions during base flow recession; and (3) minor effects of dissimilatory bacterial sulfate reduction and subsequent reoxidation of sulfides. Bedrock should not be overlooked as a source of S in catchment sulfate budgets.

The impact of urbanization on subsurface flow paths - A paired-catchment isotopic study

NASA Astrophysics Data System (ADS)

Bonneau, Jeremie; Burns, Matthew J.; Fletcher, Tim D.; Witt, Roman; Drysdale, Russell N.; Costelloe, Justin F.

2018-06-01

Urbanization disturbs groundwater flow through the sealing of native soils with impervious surfaces and through modifications to the subsoil by constructed drainage and other infrastructure (trenches and excavations, e.g. water supply). The impact of these disturbances on groundwater contributions to urban streams (i.e. baseflow) is poorly understood. While high flows caused by impervious runoff to streams are a common focus of urban studies, the route taken by groundwater to become streamflow in urban landscapes is not generally considered. To assess the impact of urbanization on groundwater sources to streams, both rainfall and baseflow were sampled weekly for stable isotopes of water in two nearby streams-one draining a peri-urban catchment and the other draining a forested, natural catchment. In addition, to study the rate of groundwater discharge to the stream, monthly baseflow recession behavior was investigated. We found that baseflow in the forested catchment was constant in stable isotope values (δ18O = -5.73‰ ± 0.14‰) throughout the year. Monthly baseflow recession constants were close to 1 and had little variation (ranging 0.951-0.992), indicating a well-mixed groundwater store and long residence times. In contrast, the urban baseflow isotopic composition featured distinct seasonal variations (δ18O = -3.35‰ ± 1.20‰ from October to March and δ18O = -4.54‰ ± 0.43‰ from April to September) and high week-to-week variability in summer, reflecting a contribution of recent rainfall to baseflow. Recession constants were lower (ranging 0.727-0.955) with pronounced seasonal variations, suggesting shorter residence times and the likely presence of a variety of stores and pathways. These results provide evidence that the urban catchment has diversified groundwater pathways, and its groundwater storage is drained faster than that of the forested catchment. It highlights some of the subsurface hydrological consequences of urbanization. Restoring low-flow aspects of the flow regime through nature-mimicking stormwater management requires careful consideration of how the behavior of natural groundwater pathways can be restored or replicated using innovative stormwater control measures.

Using semi-permeable membrane devices and stable nitrogen isotopes to detect anthropogenic influences on the Truckee River, USA

USGS Publications Warehouse

Saito, L.; Rosen, Michael R.; Chandra, S.; Fritsen, C.H.; Arufe, J.A.; Redd, C.

2008-01-01

Stable nitrogen isotopes (??15N) and semipermeable membrane devices (SPMDs) were used together to provide evidence of potential anthropogenic connections to aquatic organisms in the Truckee River, which flows through the Reno/Sparks metropolitan area in Nevada. Crayfish, snail, and periphyton ??15N values, and SPMD toxicity data collected during high and low flow periods at seven primary sites on the river were used with water quality and flow data for the assessment. All biota showed an increase of ??15N on both dates at sites downstream of inflows of a water-quality impaired tributary and urban drain relative to upstream. In addition, most of the lowest ??15N values on each date occurred at the most downstream site on the river. SPMDs sample lipophilic organic contaminants and can be used to assess organic contaminant toxicity to aquatic organisms because they use a membrane that mimics organic contaminant uptake by fish. In this study, results from a fluoroscan test [pyrene index (PI)] of SPMD extracts that responds to higher molecular weight polycyclic aromatic hydrocarbons (PAHs) showed patterns similar to stable isotope data, although observed peaks in PI values occurred in the urban area upstream of where peak ??15N values occurred. The CYP1A biomarker test, which responds to PAHs, certain polychlorinated biphenyls (PCBs), and organochlorines, showed peak toxic equivalents (TEQ) values farther downstream of the urban area. Thus, it is likely that PAHs were contributing to toxicity in the urban area, whereas other nonurban sources of organic carbon may have been present farther downstream. The combined use of stable isotope measurements and SPMDs provided a means of simultaneously examining whether aquatic biota are incorporating constituents from potential food sources (via stable isotopes) or exposure through water (via SPMDs). ?? Mary Ann Liebert, Inc. 2008.

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

NASA Astrophysics Data System (ADS)

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

2018-06-01

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

Reactors are indispensable for radioisotope production.

PubMed

Mushtaq, Ahmad

2010-12-01

Radioisotopes can be produced by reactors and accelerators. For certain isotopes there could be an advantage to a certain production method. However, nowadays many reports suggest, that useful isotopes needed in medicine, industry and research could be produced efficiently and dependence on reactors using enriched U-235 may be eliminated. In my view reactors and accelerators will continue to play their role side by side in the supply of suitable and economical sources of isotopes.

H-O isotopic and chemical characteristics of a precipitation-lake water-groundwater system in a desert area

NASA Astrophysics Data System (ADS)

Jin, Ke; Rao, Wenbo; Tan, Hongbing; Song, Yinxian; Yong, Bin; Zheng, Fangwen; Chen, Tangqing; Han, Liangfeng

2018-04-01

The recharge mechanism of groundwater in the Badain Jaran Desert, North China has been a focus of research and still disputable in the past two decades. In this study, the chemical and hydrogen (H) and oxygen (O) isotopic characteristics of shallow groundwater, lake water and local precipitation in the Badain Jaran Desert and neighboring areas were investigated to reveal the relationships between various water bodies and the recharge source of shallow groundwater. Isotopic and hydrogeochemical results show that (1) shallow groundwater was associated with local precipitation in the Ayouqi and Yabulai regions, (2) lake water was mainly recharged by groundwater in the desert hinterland, (3) shallow groundwater of the desert hinterland, Yabulai Mountain and Gurinai Grassland had a common recharge source. Shallow groundwater of the desert hinterland had a mean recharge elevation of 1869 m a.s.l. on the basis of the isotope-altitude relationship and thus originated chiefly from lateral infiltration of precipitation in the Yabulai Mountain. It is further concluded that shallow groundwater flowed towards the Gurinai Grassland according to the groundwater table contour map. Along the flow pathway, the H-O isotopic variations were primarily caused by the evaporation effect but chemical variations of shallow groundwater were affected by multiple factors, e.g., evaporation effect, dilution effect of occasional heavy-precipitation and dissolution of aquifer evaporites. Our findings provide new insight into the groundwater cycle and benefit the management of the limited water resources in the arid desert area.

Stormflow-hydrograph separation based on isotopes: the thrill is gone--what's next?

USGS Publications Warehouse

Burns, Douglas A.

2002-01-01

Beginning in the 1970s, the promise of a new method for separatingstormflow hydrographs using18O,2H, and3Hprovedanirresistibletemptation, and was a vast improvement over graphical separationand solute tracer methods that were prevalent at the time. Eventu-ally, hydrologists realized that this new method entailed a plethoraof assumptions about temporal and spatial homogeneity of isotopiccomposition (many of which were commonly violated). Nevertheless,hydrologists forged ahead with dozens of isotope-based hydrograph-separation studies that were published in the 1970s and 1980s.Hortonian overland flow was presumed dead. By the late 1980s,the new isotope-based hydrograph separation technique had movedinto adolescence, accompanied by typical adolescent problems suchas confusion and a search for identity. As experienced hydrologistscontinued to use the isotope technique to study stormflow hydrol-ogy in forested catchments in humid climates, their younger peersfollowed obligingly—again and again. Was Hortonian overland flowreally dead and forgotten, though? What about catchments in whichpeople live and work? And what about catchments in dry climatesand the tropics? How useful were study results when several of theassumptions about the homogeneity of source waters were commonlyviolated? What if two components could not explain the variation ofisotopic composition measured in the stream during stormflow? Andwhat about uncertainty? As with many new tools, once the initialshine wore off, the limitations of the method became a concern—oneof which was that isotope-based hydrograph separations alone couldnot reveal much about the flow paths by which water arrives at astream channel during storms.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Multiple runoff processes and multiple thresholds control agricultural runoff generation

NASA Astrophysics Data System (ADS)

Saffarpour, Shabnam; Western, Andrew W.; Adams, Russell; McDonnell, Jeffrey J.

2016-11-01

Thresholds and hydrologic connectivity associated with runoff processes are a critical concept for understanding catchment hydrologic response at the event timescale. To date, most attention has focused on single runoff response types, and the role of multiple thresholds and flow path connectivities has not been made explicit. Here we first summarise existing knowledge on the interplay between thresholds, connectivity and runoff processes at the hillslope-small catchment scale into a single figure and use it in examining how runoff response and the catchment threshold response to rainfall affect a suite of runoff generation mechanisms in a small agricultural catchment. A 1.37 ha catchment in the Lang Lang River catchment, Victoria, Australia, was instrumented and hourly data of rainfall, runoff, shallow groundwater level and isotope water samples were collected. The rainfall, runoff and antecedent soil moisture data together with water levels at several shallow piezometers are used to identify runoff processes in the study site. We use isotope and major ion results to further support the findings of the hydrometric data. We analyse 60 rainfall events that produced 38 runoff events over two runoff seasons. Our results show that the catchment hydrologic response was typically controlled by the Antecedent Soil Moisture Index and rainfall characteristics. There was a strong seasonal effect in the antecedent moisture conditions that led to marked seasonal-scale changes in runoff response. Analysis of shallow well data revealed that streamflows early in the runoff season were dominated primarily by saturation excess overland flow from the riparian area. As the runoff season progressed, the catchment soil water storage increased and the hillslopes connected to the riparian area. The hillslopes transferred a significant amount of water to the riparian zone during and following events. Then, during a particularly wet period, this connectivity to the riparian zone, and ultimately to the stream, persisted between events for a period of 1 month. These findings are supported by isotope results which showed the dominance of pre-event water, together with significant contributions of event water early (rising limb and peak) in the event hydrograph. Based on a combination of various hydrometric analyses and some isotope and major ion data, we conclude that event runoff at this site is typically a combination of subsurface event flow and saturation excess overland flow. However, during high intensity rainfall events, flashy catchment flow was observed even though the soil moisture threshold for activation of subsurface flow was not exceeded. We hypothesise that this was due to the activation of infiltration excess overland flow and/or fast lateral flow through preferential pathways on the hillslope and saturation overland flow from the riparian zone.

Groundwater residence time and paleohydrology in the Baltic Artesian basin:isotope geochemical data

NASA Astrophysics Data System (ADS)

Vaikmae, R.; Gerber, C.; Purtschert, R.; Aeschbach, W.; Raidla, V., Sr.; Lu, Z. T.; Zappala, J. C.; Mueller, P.; Mokrik, R., Sr.; Jiang, W.

2016-12-01

In this study of the Cambrian aquifer system(CAS) in the Baltic Artesian Basin(BAS) (, chemistry, stable isotopes, noble gas measurements, and dating tracers were combined for study the flow and recharge dynamics of the system over the last million years We find that the variability in chemical composition, stable isotopes and noble gas content in the basin is predominately controlled by mixing of three distinct water masses: Holocene and Pleistocene interglacial water, glacial meltwater, and brine. 81Kr is a nearly ideal dating tracer for such old systems. The radiogenic 4He and 40Ar provide additional information, but are more difficult to interpret in terms of groundwater age. In this study, we did not consider diffusive loss of 81Kr to stagnant water, which might result in an overestimation of groundwater ages ). However, the relatively high porosity and large thickness of the CAS, together with the presumed high salinity and low Kr content of the stagnant water all diminish the effect of diffusive 81Kr loss on age estimates. Our results confirm that under normal conditions, underground production of 81Kr is not affecting the dating results. 81Kr, 4He, and 40Ar all indicate a residence time of the brine of more than 1-3 Ma. Some uncertainty about the brine formation process remains, but the combination of chemical and stable isotope composition of the brine, noble gas concentrations and dating results favors evaporative enrichment of seawater. Tracer ages of interglacial water and glacial meltwater are on the order of several hundred thousand years, which means that several reversals of the flow direction in the CAS as a result of the paleoclimatology of the area have to be taken into account. Under such conditions, small vertical leakage, through fracture zones for example, might considerably impact the net flow pattern. Due to the cyclic flow direction reversals, the aquifer was probably in a transient state over most of the last 1 Ma period.

A look inside 'black box' hydrograph separation models: A study at the hydrohill catchment

USGS Publications Warehouse

Kendall, C.; McDonnell, Jeffery J.; Gu, W.

2001-01-01

Runoff sources and dominant flowpaths are still poorly understood in most catchments; consequently, most hydrograph separations are essentially 'black box' models where only external information is used. The well-instrumented 490 m2 Hydrohill artificial grassland catchment located near Nanjing (China) was used to examine internal catchment processes. Since groundwater levels never reach the soil surface at this site, two physically distinct flowpaths can unambiguously be defined: surface and subsurface runoff. This study combines hydrometric, isotopic and geochemical approaches to investigating the relations between the chloride, silica, and oxygen isotopic compositions of subsurface waters and rainfall. During a 120 mm storm over a 24 h period in 1989, 55% of event water input infiltrated and added to soil water storage; the remainder ran off as infiltration-excess overland flow. Only about 3-5% of the pre-event water was displaced out of the catchment by in-storm rainfall. About 80% of the total flow was quickflow, and 10% of the total flow was pre-event water, mostly derived from saturated flow from deeper soils. Rain water with high ??18O values from the beginning of the storm appeared to be preferentially stored in shallow soils. Groundwater at the end of the storm shows a wide range of isotopic and chemical compositions, primarily reflecting the heterogeneous distribution of the new and mixed pore waters. High chloride and silica concentrations in quickflow runoff derived from event water indicate that these species are not suitable conservative tracers of either water sources or flowpaths in this catchment. Determining the proportion of event water alone does not constrain the possible hydrologic mechanisms sufficiently to distinguish subsurface and surface flowpaths uniquely, even in this highly controlled artificial catchment. We reconcile these findings with a perceptual model of stormflow sources and flowpaths that explicitly accounts for water, isotopic, and chemical mass balance. Copyright ?? 2001 John Wiley & Sons, Ltd.

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.

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

NASA Astrophysics Data System (ADS)

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

2010-05-01

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

The stable isotope composition of halite and sulfate of hyperarid soils and its relation to aqueous transport

NASA Astrophysics Data System (ADS)

Amundson, Ronald; Barnes, Jaime D.; Ewing, Stephanie; Heimsath, Arjun; Chong, Guillermo

2012-12-01

Halite (NaCl) and gypsum or anhydrite (CaSO4) are water-soluble minerals found in soils of the driest regions of Earth, and only modest attention has been given to the hydrological processes that distribute these salts vertically in soil profiles. The two most notable chloride and sulfate-rich deserts on earth are the Dry Valleys of Antarctica and the Atacama Desert of Chile. While each is hyperarid, they possess very different hydrological regimes. We first show, using previously published S and O isotope data for sulfate minerals, that downward migration of water and sulfate is the primary mechanism responsible for depth profiles of sulfate concentration, and S and O isotopes, in both deserts. In contrast, we found quite different soluble Cl concentration and Cl isotope profiles between the two deserts. For Antarctic soils with an ice layer near the soil surface, the Cl concentrations increase with decreasing soil depth, whereas the ratio of 37Cl/35Cl increases. Based on previous field observations by others, we found that thermally driven upward movement of brine during the winter, described by an advection/diffusion model, qualitatively mimics the observed profiles. In contrast, in the Atacama Desert where rare but relatively large rains drive Cl downward through the profiles, Cl concentrations and 37Cl/35Cl ratios increased with depth. The depth trends in Cl isotopes are more closely explained by a Rayleigh-like model of downward fluid flow. The isotope profiles, and our modeling, reveal the similarities and differences between these two very arid regions on Earth, and are relevant for constraining models of fluid flow in arid zone soil and vadose zone hydrology.

Development and application of laser microprobe techniques for oxygen isotope analysis of silicates, and, fluid/rock interaction during and after granulite-facies metamorphism, highland southwestern complex, Sri Lanka

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

Elsenheimer, D.W.

1992-01-01

The extent of fluid/rock interaction within the crust is a function of crustal depth, with large hydrothermal systems common in the brittle, hydrostatically pressured upper crust, but restricted fluid flow in the lithostatically pressured lower crust. To quantify this fluid/rock interaction, a Nd-YAG/CO[sub 2] laser microprobe system was constructed to analyze oxygen isotope ratios in silicates. Developed protocols produce high precision in [sigma][sup 18]O ([+-]0.2, 1[sigma]) and accuracy comparable to conventional extraction techniques on samples of feldspar and quartz as small as 0.3mg. Analysis of sub-millimeter domains in quartz and feldspar in granite from the Isle of Skye, Scotland, revealsmore » complex intragranular zonation. Contrasting heterogeneous and homogeneous [sigma][sup 18]O zonation patterns are revealed in samples <10m apart. These differences suggest fluid flow and isotopic exchange was highly heterogeneous. It has been proposed that granulite-facies metamorphism in the Highland Southwestern Complex (HSWC), Sri Lanka, resulted from the pervasive influx of CO[sub 2], with the marbles and calc-silicates within the HSWC a proposed fluid source. The petrologic and stable isotopic characteristic of HSWC marbles are inconsistent with extensive decarbonation. Wollastonite calc-silicates occur as deformed bands and as post-metamorphis veins with isotopic compositions that suggest vein fluids that are at least in part magmatic. Post-metamorphic magmatic activity is responsible for the formation of secondary disseminated graphite growth in the HSWC. This graphite has magmatic isotopic compositions and is associated with vein graphite and amphibolite-granulite facies transitions zones. Similar features in Kerela Khondalite Belt, South India, may suggest a common metamorphic history for the two terranes.« less

Investigation of uranium geochemistry along groundwater flow path in the Continental Intercalaire aquifer (Southern Tunisia).

PubMed

Dhaoui, Z; Chkir, N; Zouari, K; Ammar, F Hadj; Agoune, A

2016-06-01

Environmental tracers ((2)H, (18)O, isotopes of Uranium) and geochemical processes occurring within groundwaters from the Continental Intercalaire (CI) in Southern Tunisia were used to understand the hydrodynamics and the recharge conditions of this aquifer. This study investigates the chemical and isotopic compositions of the CI groundwater. The water types are dominated by Na(+), SO4(2-), Cl(-) throughout most of the basin with a general increase in total dissolved solids from the Saharan Platform margins towards the Chotts region. Large scale groundwater flow paths are toward the Chotts region. The stable isotopes composition of the analyzed groundwater ranges from -8.8 to -6‰ vs V-SMOW for δ(18)O and from -67 to -40‰ vs V-SMOW for δ(2)H. The relatively enriched stable isotopes contents suggest the contribution of the Dahar sandstones outcrops in the current recharge of the CI aquifer in an arid context. However, the most depleted values in heavy isotopes indicate a paleorecharge of the aquifer under wetter conditions revealing a long residence time of groundwaters. The results from water samples using alpha spectrometry method indicate a range in (238)U concentrations and (234)U/(238)U activity ratios (AR) of 0.044-1.285 μg kg(-1) and 1.2 to 8.84 respectively. The geochemistry of uranium isotopes in groundwater is controlled by many factors, essentially, the influence of water rock interactions, the preferential dissolution of (234)U relative to (238)U due to alpha recoil and the mixing processes between different waters with distinct AR as well as (238)U concentrations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrochemical and isotopic effects associated with petroleum fuel biodegradation pathways in a chalk aquifer.

PubMed

Spence, Michael J; Bottrell, Simon H; Thornton, Steven F; Richnow, Hans H; Spence, Keith H

2005-09-01

Hydrochemical data, compound specific carbon isotope analysis and isotopic enrichment trends in dissolved hydrocarbons and residual electron acceptors have been used to deduce BTEX and MTBE degradation pathways in a fractured chalk aquifer. BTEX compounds are mineralised sequentially within specific redox environments, with changes in electron acceptor utilisation being defined by the exhaustion of specific BTEX components. A zone of oxygen and nitrate exhaustion extends approximately 100 m downstream from the plume source, with residual sulphate, toluene, ethylbenzene and xylene. Within this zone complete removal of the TEX components occurs by bacterial sulphate reduction, with sulphur and oxygen isotopic enrichment of residual sulphate (epsilon(s) = -14.4 per thousand to -16.0 per thousand). Towards the plume margins and at greater distance along the plume flow path nitrate concentrations increase with delta15N values of up to +40 per thousand indicating extensive denitrification. Benzene and MTBE persist into the denitrification zone, with carbon isotope enrichment of benzene indicating biodegradation along the flow path. A Rayleigh kinetic isotope enrichment model for 13C-enrichment of residual benzene gives an apparent epsilon value of -0.66 per thousand. MTBE shows no significant isotopic enrichment (delta13C = -29.3 per thousand to -30.7 per thousand) and is isotopically similar to a refinery sample (delta13C = -30.1 per thousand). No significant isotopic variation in dissolved MTBE implies that either the magnitude of any biodegradation-induced isotopic fractionation is small, or that relatively little degradation has taken place in the presence of BTEX hydrocarbons. It is possible, however, that MTBE degradation occurs under aerobic conditions in the absence of BTEX since no groundwater samples were taken with co-existing MTBE and oxygen. Low benzene delta13C values are correlated with high sulphate delta34S, indicating that little benzene degradation has occurred in the sulphate reduction zone. Benzene degradation may be associated with denitrification since increased benzene delta13C is associated with increased delta15N in residual nitrate. Re-supply of electron acceptors by diffusion from the matrix into fractures and dispersive mixing is an important constraint on degradation rates and natural attenuation capacity in this dual-porosity aquifer.

Subduction and melting processes inferred from U-Series, Sr Nd Pb isotope, and trace element data, Bicol and Bataan arcs, Philippines

NASA Astrophysics Data System (ADS)

DuFrane, S. Andrew; Asmerom, Yemane; Mukasa, Samuel B.; Morris, Julie D.; Dreyer, Brian M.

2006-07-01

We present U-series, Sr-Nd-Pb isotope, and trace element data from the two principal volcanic chains on Luzon Island, developed over oppositely dipping subduction zones, to explore melting and mass transfer processes beneath arcs. The Bataan (western) and Bicol (eastern) arcs are currently subducting terrigenous and pelagic sediments, respectively, which have different trace element and isotopic compositions. The range of ( 230Th/ 238U) disequilibria for both arcs is 0.85-1.15; only lavas from Mt. Mayon (Bicol arc) have 230Th activity excesses. Bataan lavas have higher 87Sr/ 86Sr and lower 143Nd/ 144Nd than Bicol lavas ( 87Sr/ 86Sr = 0.7042-0.7046, 143Nd/ 144Nd = 0.51281-0.51290 vs. 87Sr/ 86Sr = 0.70371-0.70391, 143Nd/ 144Nd = 0.51295-0.51301) and both arcs show steep linear arrays towards sediment values on 207Pb/ 204Pb vs. 206Pb/ 204Pb diagrams. Analysis of incompatible element and isotopic data allows identification of a sediment component that, at least in part, was transferred as a partial melt to the mantle wedge peridotite. Between 1% and 5% sediment melt addition can explain the isotopic and trace element variability in the rocks from both arcs despite the differences in sediment supply. We therefore propose that sediment transfer to the mantle wedge is likely mechanically or thermally limited. It follows that most sediments are either accreted, reside in the sub-arc lithosphere, or are recycled into the convecting mantle. However, whole-sale sediment recycling into the upper mantle is unlikely in light of the global mid-ocean ridge basalt data. Fluid involvement is more difficult to characterize, but overall the Bicol arc appears to have more fluid influence than the Bataan arc. Rock suites from each arc can be related by a dynamic melting process that allows for 230Th ingrowth, either by dynamic or continuous flux melting, provided the initial ( 230Th/ 232Th) of the source is ˜0.6-0.7. The implication of either model is that inclined arrays on the U-Th equiline diagram may not have chronologic significance. Modeling also suggests that U-series disequilibria are influenced by the tectonic convergence rate, which dictates mantle matrix flow. Thus with slower matrix flow there is a greater degree of 230Th ingrowth. While other factors such as prior mantle depletion and addition of a subducted component may explain some aspects of U-series data, an overall global correlation between tectonic convergence rate and the extent of U-Th disequilibria may originate from melting processes.

A continuous 250,000 yr record of oxygen and carbon isotopes in ostracode and bulk-sediment carbonate from Bear Lake, Utah-Idaho

USGS Publications Warehouse

Bright, Jordon; Kaufman, D.S.; Forester, R.M.; Dean, W.E.

2006-01-01

Oxygen and carbon isotopes from a continuous, 120-m-long, carbonate-rich core from Bear Lake, Utah-Idaho, document dramatic fluctuations in the hydrologic budget of the lake over the last 250,000 yr. Isotopic analyses of bulk sediment samples capture millennial-scale variability. Ostracode calcite was analyzed from 78 levels, mainly from the upper half of the core where valves are better preserved, to compare the isotopic value of purely endogenic carbonate with the bulk sediment, which comprises both endogenic and detrital components. The long core exhibits three relatively brief intervals with abundant endogenic aragonite (50??10%) and enriched ??18O and ??13C. These intervals are interpreted as warm/dry periods when the lake retracted into a topographically closed basin. We correlate these intervals with the interglacial periods of marine oxygen-isotope stages 1, 5e, and 7a, consistent with the presently available geochronological control. During most of the time represented by the core, the lake was fresher than the modern lake, as evidenced by depleted ??18O and ??13C in bulk-sediment carbonate. ?? 2006 Elsevier Ltd. All rights reserved.

Genesis of the post-caldera eastern Upper Basin Member rhyolites, Yellowstone, WY: from volcanic stratigraphy, geochemistry, and radiogenic isotope modeling

NASA Astrophysics Data System (ADS)

Pritchard, Chad J.; Larson, Peter B.

2012-08-01

An array of samples from the eastern Upper Basin Member of the Plateau Rhyolite (EUBM) in the Yellowstone Plateau, Wyoming, were collected and analyzed to evaluate styles of deposition, geochemical variation, and plausible sources for low δ18O rhyolites. Similar depositional styles and geochemistry suggest that the Tuff of Sulphur Creek and Tuff of Uncle Tom's Trail were both deposited from pyroclastic density currents and are most likely part of the same unit. The middle unit of the EUBM, the Canyon flow, may be composed of multiple flows based on a wide range of Pb isotopic ratios (e.g., 206Pb/204Pb ranges from 17.54 to 17.86). The youngest EUBM, the Dunraven Road flow, appears to be a ring fracture dome and contains isotopic ratios and sparse phenocrysts that are similar to extra-caldera rhyolites of the younger Roaring Mountain Member. Petrologic textures, more radiogenic 87Sr/86Sr in plagioclase phenocrysts (0.7134-0.7185) than groundmass and whole-rock ratios (0.7099-0.7161), and δ18O depletions on the order of 5‰ found in the Tuff of Sulphur Creek and Canyon flow indicate at least a two-stage petrogenesis involving an initial source rock formed by assimilation and fractional crystallization processes, which cooled and was hydrothermally altered. The source rock was then lowered to melting depth by caldera collapse and remelted and erupted. The presence of a low δ18O extra-caldera rhyolite indicates that country rock may have been hydrothermally altered at depth and then assimilated to form the Dunraven Road flow.

The use of intermittent and continuous recordings of jugular venous bulb oxygen saturation in the unconscious patient.

PubMed

Garlick, R; Bihari, D

1987-01-01

Monitoring clinical signs in unconscious patients provides only late information about cerebral deterioration. Ischaemia and hypoxia are the mechanisms of much of the damage. Cerebral blood flow (CBF) measurements provide direct evidence of ischaemia but are intermittent values for what may be an unstable situation. Continuous recordings of CBF and oxygenation are more likely to reveal harmful tendencies to ischaemia and hypoxia at an early stage than intermittent readings. We report our experience with intermittent and also continuous recording of the jugular venous bulb oxygen saturation (JVO2Sat) obtained by fibreoptic oximetry in a group of 10 head injured and 7 septic patients. Simultaneous measurements of CBF by an isotopic xenon clearance method were also made. The JVO2Sat has been suggested to be a reliable indicator of cerebral oxygenation, a low value being indicative of ischaemia. We discuss whether our findings support this statement. There are also variations in JVO2Sat with mean arterial blood pressure and intracranial pressure. These variations have important implications in the interpretation that can be made of one single value of JVO2Sat.

Oligocene ash flow volcanism, northern Sierra Madre Occidental: Role of mafic and intermediate-composition magmas in rhyolite genesis

NASA Astrophysics Data System (ADS)

Wark, David A.

1991-07-01

Field, geochemical, and isotopic data from the Tomochic volcanic center in Chihuahua, Mexico, are interpreted to indicate a genetic relationship between large-volume rhyolite ash-flow tuffs and associated more mafic lithologies. These lithologies include (1) porphyritic, two-pyroxene andesite (>35 Ma) that was extruded mostly before ash-flow volcanism, and (2) crystal-poor basaltic andesite that was erupted mostly after ash-flow activity (˜30 Ma) but which was also extruded earlier (˜34 Ma) with hybrid intracaldera lavas. Major silicic units at Tomochic include the Vista (˜34 Ma) and Rio Verde (˜32 Ma) rhyolite ash-flow tuffs; also present are ash-flow tuffs (˜38, 36, and 29 Ma) erupted from other sources. A model of rhyolite genesis by closed-system crystal fractionation of andesite is consistent with geochemical and isotopic data. The least evolved Vista rhyolite was formed by fractionation of ˜65% the original mass of andesite; an additional ˜55% fractionation of plagioclase, alkali feldspar, quartz, biotite, hornblende, FeTi oxides, and sphene generated the most evolved Vista sample. Rio Verde rhyolites were generated from andesite by ˜50% mass fractionation of an assemblage dominated by plagioclase, pyroxene, and FeTi oxides. Initial Nd and Sr isotope ratios of andesite-dacite lavas (ɛNd = -2.3 to -5.2; 87Sr/86Sr = 0.7060 to 0.7089) and of rhyolites (ɛNd = +0.5 to -2.7; 87Sr/86Sr = 0.7053 to 0.7066) partly overlap and extend from values near the mantle array toward values typical of old continental crust on an ɛNd-87Sr/86Sr diagram. These isotope ratios, which do not correlate with indices of differentiation, are interpreted to indicate that parental andesite already contained a crustal component (possibly >20%) before fractionation to rhyolite. The isotopic and geochemical signatures of andesites apparently reflect the incorporation of crust by subduction-related, mafic melts represented by (but more primitive than) exposed basaltic andesites, which have isotope ratios (ɛNd = +1.0 to -0.1; 87Sr/86Sr = 0.7044 to 0.7053) near "bulk earth". The pattern of volcanic evolution at the Tomochic center, specifically the transition from andesitic to rhyolite dominated, with late extrusion of basaltic andesite, also occurred in other parts of the volcanic field, and roughly coincided with a sharp decrease in the rate of Farallon plate subduction. This change in subduction rate apparently resulted in a decreased flux of mafic melts into the crust from below, and was associated with the onset of crustal extension and hence, shorter residence times for mafic melts formerly ponded in the deep crust These, in turn, resulted in (1) the change from andesitic to rhyolite-dominated volcanism as ascending intermediate-composition magmas stalled, coalesced, and differentiated to produce rhyolite, (2) extrusion of basaltic andesite upon brittle failure of the shallow crust, and (3) subsequent termination of calc-alkalic volcanism throughout the Sierra Madre Occidental.

Carbon isotope effect during abiogenic oxidation of methane

NASA Astrophysics Data System (ADS)

Kiyosu, Yasuhiro; Roy Krouse, H.

1989-11-01

The oxidation of methane during flow over CuO and Fe 2O 3 has been examined in the temperature range of 400-650°C. The reaction rate and carbon isotope fractionation are dependent upon the choice of oxide and temperature. The activation energy is lower for hematite (8.0 kcal mole -1) than for cupric oxide (16.6 kcal mole -1). The measured ratios of the isotopic rate constants α =k 12/k 13 were found to have temperature dependences given by: 10 3(α - 1) =2.93 × 10 6/T 2 + 8.11 (cupric oxide) 10 3(α - 1) =7.44 × 10 6/T 2 + 6.56 (hematite) Abiogenic oxidation of methane is probably a significant mechanism for fractionating carbon isotopes in nature.

The use of Stable Isotopes to Assess Climatic Controls on Groundwater Recharge in the Southern Sacramento Mountains, New Mexico

NASA Astrophysics Data System (ADS)

Newton, B. T.; Timmons, S. S.; Rawling, G. C.; Kludt, T.; Eastoe, C. J.

2008-12-01

We used the stable isotopes of hydrogen and oxygen to relate the temporal variability of groundwater recharge to climatic conditions in the southern Sacramento Mountains as a part of a larger regional hydrogeologic study. The southern Sacramento Mountains are the primary recharge source not only to local aquifers, but also to the Lower Pecos River Basin, the Roswell Artesian aquifer and aquifers in the Salt Basin. Aquifers in the study area mainly consist of fractured limestone. In years prior to 2006, groundwater levels within the study area showed a steady decline. We observed a significant increase in regional groundwater levels and spring discharge during and shortly after the unusually wet 2006 monsoon season. We developed a local meteoric water line (LMWL) in δ18O vs. δD space based on precipitation samples collected from several different elevations over a period of two years. The stable isotopic compositions of streams during base flow conditions define an evaporation line with a slope of 5.5 that intersects the LMWL in the region that represents winter precipitation. Spring and well samples collected in 2003 and spring samples collected in 2008 exhibit isotopic compositions that plot near the evaporation line, indicating that groundwater recharge is largely snow melt that has subsequently undergone evaporation in local streams. After the unusually wet 2006 monsoon season, the isotopic compositions of springs sampled in fall of 2006 and wells sampled in spring of 2007 deviated from the evaporation line, plotting closer to the LMWL. This observed isotopic trend is thought to represent a large input of 2006 monsoon precipitation to the groundwater system via relatively short fracture-dominated flow paths. Stable isotope results indicate that while snow melt is probably the main source of groundwater recharge in the southern Sacramento Mountains, as exhibited by the 2003 and 2008 samples, above average summer precipitation events, such as in 2006, can also contribute to significant groundwater recharge.

Evaluation of soil water stable isotope analysis by H2O(liquid)-H2O(vapor) equilibration method

NASA Astrophysics Data System (ADS)

Gralher, Benjamin; Stumpp, Christine

2014-05-01

Environmental tracers like stable isotopes of water (δ18O, δ2H) have proven to be valuable tools to study water flow and transport processes in soils. Recently, a new technique for soil water isotope analysis has been developed that employs a vapor phase being in isothermal equilibrium with the liquid phase of interest. This has increased the potential application of water stable isotopes in unsaturated zone studies as it supersedes laborious extraction of soil water. However, uncertainties of analysis and influencing factors need to be considered. Therefore, the objective of this study was to evaluate different methodologies of analysing stable isotopes in soil water in order to reduce measurement uncertainty. The methodologies included different preparation procedures of soil cores for equilibration of vapor and soil water as well as raw data correction. Two different inflatable sample containers (freezer bags, bags containing a metal layer) and equilibration atmospheres (N2, dry air) were tested. The results showed that uncertainties for δ18O were higher compared to δ2H that cannot be attributed to any specific detail of the processing routine. Particularly, soil samples with high contents of organic matter showed an apparent isotope enrichment which is indicative for fractionation due to evaporation. However, comparison of water samples obtained from suction cups with the local meteoric water line indicated negligible fractionation processes in the investigated soils. Therefore, a method was developed to correct the raw data reducing the uncertainties of the analysis.. We conclude that the evaluated method is advantageous over traditional methods regarding simplicity, resource requirements and sample throughput but careful consideration needs to be made regarding sample handling and data processing. Thus, stable isotopes of water are still a good tool to determine water flow and transport processes in the unsaturated zone.

A continuous high resolution water isotope dataset to constrain Alpine water balance estimates

NASA Astrophysics Data System (ADS)

Michelon, Anthony; Ceperley, Natalie; Beria, Harsh; Larsen, Josh; Schaefli, Bettina

2017-04-01

Water delivered from Alpine environments is a crucial resource for many countries around the world. Precipitation accumulated during cold seasons as snowpack or glaciers is often an important source of water during warm (dry) season but also a dominant contributor to the annual water balance. In Switzerland, water from high Alpine, glacier-fed catchments provides a large portion of both the hydroelectric power and water supply. However, large uncertainties regarding changes in glacier volume and snow accumulation can have significant impacts on hydrologic, biologic, physical and economic understanding, modeling, and predictions. Accurately quantifying these water resources is therefore an on-going challenge. Given the well-known difficulty observing solid precipitation (snowfall), it can be assumed that most of the uncertainty in water balance estimates for snow-dominated environments is due to: 1) Poor measurement of winter precipitation and 2) A poor estimation of timing and amount of snow melt. It is noteworthy that the timing of melt plays a crucial role even for annual water balance estimates since it might significantly influence melt runoff flow paths and thereby groundwater recharge. We use continuous monitoring of water stable isotopes over the entire annual cycle in an Alpine catchment to shed light on how such observations can constrain water balance estimates. The selected catchment is the experimental Vallon de Nant catchment in the Vaud Alps of Switzerland, where detailed hydrologic observations have recently started in addition to the existing vegetation and soil investigations. The Vallon de Nant (14 km2, and an altitude ranging from 1200 to 3051 m) is a narrow valley that accumulates large amounts of snow during winter. In spring and summer, the river discharge is mainly supplied by snowmelt, with additional inputs from a small glacier and rainfall. Continuous monitoring of water stable isotopes (δO18 and δD) is combined with measurements of climatic and hydrological parameters to quantify water fluxes. Measurements and sampling in such an environment is challenging and has rarely been done at such a high temporal resolution for a full annual cycle. We will discuss the advantage of our approach for 1) evaluating the dominant hydrological processes and pathways in Alpine environments and 2) for reducing the uncertainties of water resource estimation in Alpine catchments.

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

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

Strontium isotope constraints on fluid flow in the sheeted dike complex of fast spreading crust: Pervasive fluid flow at Pito Deep

NASA Astrophysics Data System (ADS)

Barker, A. K.; Coogan, L. A.; Gillis, K. M.; Weis, D.

2008-06-01

Fluid flow through the axial hydrothermal system at fast spreading ridges is investigated using the Sr-isotopic composition of upper crustal samples recovered from a tectonic window at Pito Deep (NE Easter microplate). Samples from the sheeted dike complex collected away from macroscopic evidence of channelized fluid flow, such as faults and centimeter-scale hydrothermal veins, show a range of 87Sr/86Sr from 0.7025 to 0.7030 averaging 0.70276 relative to a protolith with 87Sr/86Sr of ˜0.7024. There is no systematic variation in 87Sr/86Sr with depth in the sheeted dike complex. Comparison of these new data with the two other localities that similar data sets exist for (ODP Hole 504B and the Hess Deep tectonic window) reveals that the extent of Sr-isotope exchange is similar in all of these locations. Models that assume that fluid-rock reaction occurs during one-dimensional (recharge) flow lead to significant decreases in the predicted extent of isotopic modification of the rock with depth in the crust. These model results show systematic misfits when compared with the data that can only be avoided if the fluid flow is assumed to be focused in isolated channels with very slow fluid-rock exchange. In this scenario the fluid at the base of the crust is little modified in 87Sr/86Sr from seawater and thus unlike vent fluids. Additionally, this model predicts that some rocks should show no change from the fresh-rock 87Sr/86Sr, but this is not observed. Alternatively, models in which fluid-rock reaction occurs during upflow (discharge) as well as downflow, or in which fluids are recirculated within the hydrothermal system, can reproduce the observed lack of variation in 87Sr/86Sr with depth in the crust. Minimum time-integrated fluid fluxes, calculated from mass balance, are between 1.5 and 2.6 × 106 kg m-2 for all areas studied to date. However, new evidence from both the rocks and a compilation of vent fluid compositions demonstrates that some Sr is leached from the crust. Because this leaching lowers the fluid 87Sr/86Sr without changing the rock 87Sr/86Sr, these mass balance models must underestimate the time-integrated fluid flux. Additionally, these values do not account for fluid flow that is channelized within the crust.

A method to investigate inter-aquifer leakage using hydraulics and multiple environmental tracers

NASA Astrophysics Data System (ADS)

Priestley, Stacey; Love, Andrew; Wohling, Daniel; Post, Vincent; Shand, Paul; Kipfer, Rolf; Tyroller, Lina

2016-04-01

Informed aquifer management decisions regarding sustainable yields or potential exploitation require an understanding of the groundwater system (Alley et al. 2002, Cherry and Parker 2004). Recently, the increase in coal seam gas (CSG) or shale gas production has highlighted the need for a better understanding of inter-aquifer leakage and contaminant migration. In most groundwater systems, the quantity or location of inter-aquifer leakage is unknown. Not taking into account leakage rates in the analysis of large scale flow systems can also lead to significant errors in the estimates of groundwater flow rates in aquifers (Love et al. 1993, Toth 2009). There is an urgent need for robust methods to investigate inter-aquifer leakage at a regional scale. This study builds on previous groundwater flow and inter-aquifer leakage studies to provide a methodology to investigate inter-aquifer leakage in a regional sedimentary basin using hydraulics and a multi-tracer approach. The methodology incorporates geological, hydrogeological and hydrochemical information in the basin to determine the likelihood and location of inter-aquifer leakage. Of particular benefit is the analysis of hydraulic heads and environmental tracers at nested piezometers, or where these are unavailable bore couplets comprising bores above and below the aquitard of interest within a localised geographical area. The proposed methodology has been successful in investigating inter-aquifer leakage in the Arckaringa Basin, South Australia. The suite of environmental tracers and isotopes used to analyse inter-aquifer leakage included the stable isotopes of water, radiocarbon, chloride-36, 87Sr/86Sr and helium isotopes. There is evidence for inter-aquifer leakage in the centre of the basin ~40 km along the regional flow path. This inter-aquifer leakage has been identified by a slight draw-down in the upper aquifer during pumping in the lower aquifer, overlap in Sr isotopes, δ2H, δ18O and chloride concentrations as well as hydrochemical evidence of mixing with shallower groundwater with shorter residence times. References Alley W. M. Healy R. W. Labaugh J. W. Reilly T. E. 2002. Hydrology - Flow and storage in groundwater systems. Science 296: 1985-1990. Cherry J. A. Parker, B. L. 2004. Role of Aquitards in the Protection of Aquifers from Contamination: A "State of Science" Report. Denver, USA. AWWA Research Foundation. Love A. J. Herczeg A. L. Armstrong D. Stadter F. Mazor E. 1993. Groundwater-Flow Regime within the Gambier Embayment of the Otway Basin, Australia - Evidence from Hydraulics and Hydrochemistry. Journal of Hydrology 143: 297-338. Tóth J. 2009. Gravitational Systems of Groundwater Flow: Theory, Evaluation, Utilization. Cambridge University Press.

Insights into Seasonal Variations in Phosphorus Concentrations and Cycling in Monterey Bay

NASA Astrophysics Data System (ADS)

Kong, M.; Defforey, D.; Paytan, A.; Roberts, K.

2014-12-01

Phosphorus (P) is an essential nutrient for life as it is a structural constituent in many cell components and a key player in cellular energy metabolism. Therefore, P availability can impact primary productivity. Here we quantify dissolved and particulate P compounds and trace P sources and cycling in Monterey Bay over the course of a year. This time series gives insights into monthly and seasonal variations in the surface water chemistry of this region. Preliminary characterization of seawater samples involves measuring total P and soluble reactive P (SRP) concentrations. 31P nuclear magnetic resonance spectroscopy (31P NMR) is used to determine the chemical structure of organic phosphorus compounds present in surface seawater. The isotopic signature of phosphatic oxygen (δ18Op) is used as a proxy for studying P cycling and sources. Oxygen isotope ratios in phosphate are determined by continuous-flow isotope mass ratio spectrometry (CF-IRMS) following purification of dissolved P from seawater samples and precipitation as silver phosphate. We expect to observe seasonal changes in P concentrations, as well as differences in organic P composition and P sources. The chemical structure of organic P compounds will affect their bioavailability and thus the extent to which they can fuel primary productivity in Monterey Bay. δ18Op will reflect source signatures and provide information on turnover rates of P in surface waters. Results from this work will provide valuable insights into seasonal changes in P cycling in surface waters and have important implications for understanding primary productivity in the Monterey Bay ecosystem.

METHOD OF CENTRIFUGE OPERATION

DOEpatents

Cohen, K.

1960-05-10

A method of isotope separation is described in which two streams are flowed axially of, and countercurrently through, a cylindrical centrifuge bowl. Under the influence of a centrifugal field, the light fraction is concentrated in a stream flowing through the central portion of the bowl, whereas the heavy fraction is concentrated in a stream at the periphery thereof.

Hydrologic Contributions of Springs to the Logan River, Utah

NASA Astrophysics Data System (ADS)

Gooseff, M. N.; Evans, J.; Kolesar, P.; Lachmar, T.; Payn, R.

2005-05-01

The Logan River flows through a fractured karst watershed of the Bear River mountain range in northern Utah, and provides significant water supply to the city of Logan, Utah. Springs flowing into the Logan River are important sources of water after annual snowmelt has been exhausted. In this work, we present results from a year of monitoring water chemistry and stable isotopes (D, 18O, and 13C) in two major springs and in the Logan River upstream and downstream of the combined spring inputs. The two springs, DeWitt and Spring Hollow, flow into the river within 1.5 km of each other. Annual patterns of Si and Mg suggest a flushing pattern, with reduced concentrations during snowmelt, and increasing concentrations throughout baseflow recession, at all for sampling locations. Cl concentrations are likewise greatly depressed after the snowmelt pulse but afterward remain consistently low at all four sites. Stable isotope data show that spring water is generally more enriched in D and 18O than river water, with an enriching pattern throughout annual stream flow recession.

Carbon allocation belowground in Pinus pinaster using stable carbon isotope pulse labeling technique

NASA Astrophysics Data System (ADS)

Dannoura, M.; Bosc, A.; Chipeaux, C.; Sartore, M.; Lambrot, C.; Trichet, P.; Bakker, M.; Loustau, D.; Epron, D.

2010-12-01

Carbon allocation belowground competes with aboveground growth and biomass production. In the other hand, it contributes to resource acquisition such as nutrient, water and carbon sequestration in soil. Thus, a better characterization of carbon flow from plant to soil and its residence time within each compartment is an important issue for understanding and modeling forest ecosystem carbon budget. 13C pulse labeling of whole crown was conducted at 4 seasons to study the fate of assimilated carbon by photosynthesis into the root on 12 year old Pinus pinaster planted in the INRA domain of Pierroton. Maritime pine is the most widely planted species in South-West Europe. Stem, root and soil CO2 effluxes and their isotope composition were measured continuously by tunable diode laser absorption spectroscopy with a trace gas analyzer (TGA 100A; Campbell Scientific) coupled to flow-through chambers. 13CO2 recovery and peak were observed in respiration of each compartment after labeling. It appeared sequentially from top of stem to bottom, and to coarse root. The maximum velocity of carbon transfer was calculated as the difference in time lag of recovery between two positions on the trunk or on the root. It ranged between 0.08-0.2 m h-1 in stem and between 0.04-0.12 m h-1 in coarse root. This velocity was higher in warmer season, and the difference between time lag of recovery and peak increased after first frost. Photosynthates arrived underground 1.5 to 5 days after labeling, at similar time in soil CO2 effluxes and coarse root respiration. 0.08-1.4 g of carbon was respired per tree during first 20 days following labeling. It presented 0.6 -10% of 13C used for labeling and it is strongly related to seasons. The isotope signal was detected in fine root organs and microbial biomass by periodical core sampling. The peak was observed 6 days after labeling in early summer while it was delayed more than 10 days in autumn and winter with less amount of carbon allocated belowground.

Deep circulation changes in the South Atlantic since the Last Glacial Maximum from Nd isotope and multi-proxy records

NASA Astrophysics Data System (ADS)

Wei, R.; Abouchami, W.; Zahn, R.; Masque, P.

2016-01-01

We report down-core sedimentary Nd isotope (εNd) records from two South Atlantic sediment cores, MD02-2594 and GeoB3603-2, located on the western South African continental margin. The core sites are positioned downstream of the present-day flow path of North Atlantic Deep Water (NADW) and close to the Southern Ocean, which makes them suitable for reconstructing past variability in NADW circulation over the last glacial cycle. The Fe-Mn leachates εNd records show a coherent decreasing trend from glacial radiogenic values towards less radiogenic values during the Holocene. This trend is confirmed by εNd in fish debris and mixed planktonic foraminifera, albeit with an offset during the Holocene to lower values relative to the leachates, matching the present-day composition of NADW in the Cape Basin. We interpret the εNd changes as reflecting the glacial shoaling of Southern Ocean waters to shallower depths combined with the admixing of southward flowing Northern Component Water (NCW). A compilation of Atlantic εNd records reveals increasing radiogenic isotope signatures towards the south and with increasing depth. This signal is most prominent during the Last Glacial Maximum (LGM) and of similar amplitude across the Atlantic basin, suggesting continuous deep water production in the North Atlantic and export to the South Atlantic and the Southern Ocean. The amplitude of the εNd change from the LGM to Holocene is largest in the southernmost cores, implying a greater sensitivity to the deglacial strengthening of NADW at these sites. This signal impacted most prominently the South Atlantic deep and bottom water layers that were particularly deprived of NCW during the LGM. The εNd variations correlate with changes in 231Pa/230Th ratios and benthic δ13C across the deglacial transition. Together with the contrasting 231Pa/230Th: εNd pattern of the North and South Atlantic, this indicates a progressive reorganization of the AMOC to full strength during the Holocene.

Highly Efficient Quantum Sieving in Porous Graphene-like Carbon Nitride for Light Isotopes Separation

NASA Astrophysics Data System (ADS)

Qu, Yuanyuan; Li, Feng; Zhou, Hongcai; Zhao, Mingwen

2016-01-01

Light isotopes separation, such as 3He/4He, H2/D2, H2/T2, etc., is crucial for various advanced technologies including isotope labeling, nuclear weapons, cryogenics and power generation. However, their nearly identical chemical properties made the separation challenging. The low productivity of the present isotopes separation approaches hinders the relevant applications. An efficient membrane with high performance for isotopes separation is quite appealing. Based on first-principles calculations, we theoretically demonstrated that highly efficient light isotopes separation, such as 3He/4He, can be reached in a porous graphene-like carbon nitride material via quantum sieving effect. Under moderate tensile strain, the quantum sieving of the carbon nitride membrane can be effectively tuned in a continuous way, leading to a temperature window with high 3He/4He selectivity and permeance acceptable for efficient isotopes harvest in industrial application. This mechanism also holds for separation of other light isotopes, such as H2/D2, H2/T2. Such tunable quantum sieving opens a promising avenue for light isotopes separation for industrial application.

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

Kautsky, Mark; Ranalli, Tony; Dander, David

The objective of this investigation was to identify and differentiate potential non- mill-related water inputs to a shallow terrace groundwater system through the use of aqueous chemical and isotopic tracers at a former uranium- and vanadium-ore processing facility. Terrace groundwater in the vicinity of the Shiprock, New Mexico, site is hypothesized to be largely anthropogenic because natural rates of recharge in the terrace are likely insufficient to sustain a continuous water table in the terrace alluvial system, as observed in several analogue terrace locations east of the site and in response to post-mill dewatering efforts across the site. The terracemore » is composed of alluvial sand and gravel and weathered and unweathered Mancos Shale. Terrace groundwater exists and flows in the alluvium and to a much less extent in the Mancos Shale. Historical data established that in both the terrace and floodplain below the terrace, mill-derived uranium and sulfate is found primarily in the alluvium and the upper portion of the weathered Mancos Shale. Groundwater extraction is being conducted in the vicinity of former mill operations and in washes and seeps to dewater the formation and remove contamination, thus eliminating these exposure pathways and minimizing movement to the floodplain. However, past and present contribution of non-mill anthropogenic water sources may be hindering the dewatering effort, resulting in reduced remedy effectiveness. Groundwater source signatures can be determined based on chemical and isotopic ratios and are used to help identify and delineate both mill and non-mill water contributions. Aqueous chemical and isotopic tracers, such as 234U/238U activity ratios and uranium concentrations, δ34S sulfate and sulfate concentrations, tritium concentrations, and δ2Hwater and δ18O water are being used in this Phase I study. The aqueous chemical and isotopic analysis has identified areas on the terrace where groundwater is derived from mill-related activities and areas where the groundwater is associated with non-mill activities. A separate field effort of Phase II work will follow, including investigating additional locations for these isotopes and examination of δ18Osulfate , δ34Ssulfate , and chlorofluorocarbon signatures.« less

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.

Stable carbon and oxygen isotope ratios of winter flounder otoliths assess connectivity between juvenile and adult habitats

NASA Astrophysics Data System (ADS)

Pruell, Richard; Taplin, Bryan

2017-04-01

Winter flounder populations (Pseudopleuronectes americanus) have significantly declined in recent years along the Rhode Island, USA coastline. The reasons for this decline are not completely clear; however, habitat loss may be a factor. Therefore, knowledge of connectivity between juvenile nearshore habitats and the adult offshore populations may be important for improved management of this fishery. This study was undertaken to determine if stable carbon (δ13C) and oxygen (δ18O) isotope ratios in otoliths could be used to differentiate the locations that serve as important juvenile habitats for winter flounder. It is generally believed that winter flounder spawn during late winter in nearshore areas, and juvenile fish reside in shallow-water habitats along the coastline during their first summer. Once young-of-the-year flounder undergo metamorphosis and settle, they remain in close proximity to that site until fall. Adult fish move offshore during the late winter and spring, and then return to their natal estuaries during the fall and winter to spawn. Juvenile flounder were collected yearly over a three-year period from 18 juvenile habitats with a wide range of salinities. Several years later adult flounder of the same cohorts were obtained from similar inshore locations and also from the offshore fishery. Sagital otoliths were removed from the adult flounder and the core of the otolith representing the juvenile period was obtained using a Micromill drilling system. These juvenile otolith cores from adult fish and whole sagittal otoliths from juvenile flounder were analyzed for δ13C and δ18O using continuous-flow isotope ratio mass spectrometry. Results from these analyses show significant differences in δ13C and δ18O signatures among water bodies (bay, coastal ponds and an estuarine river). Preliminary analysis indicates that the isotope ratios of the juvenile cores from adult flounder and whole otoliths from juvenile fish collected at the same locations were similar. Isotope data for juvenile cores from adult flounder obtained from the offshore fishery indicate that many of these flounder spent their first year in high salinity areas and not in estuarine systems.

Determination of the δ34S of low-concentration sulfate in water; RSIL lab code 1949

USGS Publications Warehouse

Revesz, Kinga; Qi, Haiping; Coplen, Tyler B.

2006-01-01

The purpose of the Reston Stable Isotope Laboratory (RSIL) lab code 1949 is to determine the δ(34S/32S), abbreviated as δ34S, of dissolved sulfate having a concentration less than 20 milligrams per liter. Dissolved sulfate is collected on an anion-exchange resin in the field, eluted in the laboratory with 3 M KCl, and precipitated with BaCl2 at pH 3 to 4 as BaSO4. The precipitated BaSO4 is filtered and dried before introduction into an elemental analyzer (EA) Carlo Erba NC 2500. The EA is used to convert sulfur in a BaSO4 solid sample into SO2 gas, and the EA is connected to a continuous flow isotope-ratio mass spectrometer (CF-IRMS), which determines differences in the isotope-amount ratios of stable sulfur isotopes (34S/32S) of the product SO2 gas. The combustion is quantitative; no isotopic fractionation is involved. Samples are placed in a tin capsule and loaded into the Costech Zero Blank Autosampler of the EA. Under computer control, samples are dropped into a heated reaction tube that combines the oxidation and reduction reactions. The combustion takes place in a helium atmosphere containing an excess of oxygen gas at the oxidation zone at the top of the reaction tube. Combustion products are transported by a helium carrier through the reduction zone at the bottom of the reaction tube to remove excess oxygen and through a separate drying tube to remove any water. The gas-phase products, mainly CO2, N2, and SO2, are separated by a gas chromatograph. The gas is then introduced into the isotope-ratio mass spectrometer (IRMS) through a Finnigan MAT (now Thermo Scientific) ConFlo II interface, which is also used to inject SO2 reference gas and helium for sample dilution. The IRMS is a Thermo Scientific Delta V Plus CF-IRMS. It has a universal triple collector with two wide cups and a narrow cup in the middle. It is capable of measuring mass/charge (m/z) 64 and 66 simultaneously. The ion beams from SO2 are as follows: m/z 64 = SO2 = 32S16O16O; m/z 66 = SO2 = 34S16O16O primarily.

Water drives the deuterium content of the methane emitted from plants

NASA Astrophysics Data System (ADS)

Vigano, I.; Holzinger, R.; Keppler, F.; Greule, M.; Brand, W. A.; Geilmann, H.; van Weelden, H.; Röckmann, T.

2010-07-01

The spatial distribution of the deuterium content of precipitation has a well-established latitudinal variation that is reflected in organic molecules in plants growing at different locations. Some laboratory and field studies have already shown that the deuterium content of methane emitted from methanogens can be partially related to δD variations of the water in the surrounding environment. Here we present a similar relation for the methane emitted from plant biomass under UV radiation. To show this relation, we determined the hydrogen isotopic composition of methane released from leaves of a range of plants grown with water of different deuterium content (δD = -130‰ to +115‰). The plant leaves were irradiated with UV light and the CH 4 isotopic composition was measured by continuous flow isotope ratio mass spectrometry (CF-IRMS). Furthermore, the deuterium content of bulk biomass and of the methoxyl (OCH 3) groups of the biomass was measured. The D/H ratio successively decreases from bulk biomass (δD = -106‰ to -50‰) via methoxyl groups (δD = -310‰ to -115‰) to the CH 4 emitted (δD = -581‰ to -196‰). The range of isotope ratios in bulk biomass and OCH 3 groups is smaller than in the water used to grow the plants. Methoxyl groups, which contain only non-exchangeable hydrogen, can be used to assess the fraction of external water that was incorporated before OCH 3 groups were formed. Surprisingly, the CH 4 formed under UV irradiation has a wider isotopic range than the OCH 3 groups. Although the precise production pathway cannot be fully determined, the presented experiments indicate that methoxyl groups are not the only source substrate for CH 4, but that other sources, including very depleted ones, must contribute. The main limitation to the interpretation of the data is the possible influence of exchangeable water, which could not be quantified. Future studies should include measurements of leaf water and avoid interaction between different plants via the gas phase. Despite these deficiencies, the results suggest that the deuterium content of the methane generated from plants under UV irradiation is closely linked to δD in precipitation. This dependency, which should also exist for other biogenic methane sources could be evaluated with global isotope models.

Geochemical constraints on the temperature and timing of carbonate formation and lithification in the Nankai Trough, NanTroSEIZE transect

NASA Astrophysics Data System (ADS)

Sample, James C.; Torres, Marta E.; Fisher, Andrew; Hong, Wei-Li; Destrigneville, Christine; Defliese, William F.; Tripati, Aradhna E.

2017-02-01

Information about diagenetic processes and temperatures during burial of sediments entering the subduction zone is important for understanding changes in physical properties and seismic behavior during deformation. The geochemistry of authigenic carbonates from accretionary prisms can serve as proxies for conditions during carbonate cementation and resultant lithification. We report results from the Nankai accretionary prism recovered from Integrated Ocean Drilling Program (IODP) sites C0011 and C0012 and we document continued cementation of deep sediment sections prior to subduction. Elemental and isotope data provide evidence for complex mixing of different isotopic reservoirs in pore waters contributing to carbonate chemical signatures. Carbon stable isotope values exhibit a broad range (δ13CV-PDB = +0.1‰ to -22.5‰) that corresponds to different stages of cement formation during burial. Carbonate formation temperatures from carbonate-clumped isotope geochemistry range from 16 °C to 63 °C at Site C0011 and 8.7 °C to 68 °C at Site C0012. The correspondence between the clumped-isotope temperatures and extrapolations of measured in situ temperatures indicate the carbonate is continuing to form at present. Calculated water isotopic compositions are in some cases enriched in 18O relative to measured interstitial waters suggesting a component of inherited seawater or input from clay-bound water. Low oxygen isotope values and the observed Ba/Ca ratios are also consistent with carbonate cementation at depth. Strontium isotopes of interstitial waters (87Sr/86Sr of 0.7059-0.7069) and carbonates (87Sr/86Sr of 0.70715-0.70891) support formation of carbonates from a mixture of strontium reservoirs including current interstitial waters and relic seawater contemporaneous with deposition. Collectively our data reflect mixed sources of dissolved inorganic carbon and cations that include authigenic phases driven by organic carbon and volcanic alteration reactions. Physical properties of input sediments continue to undergo modification by carbonate cementation at present. Due to ongoing recrystallization, temperatures from carbonate-clumped isotopes reflect the modern geothermal gradient and may serve as useful measures of geothermal gradients in other siliciclastic basins where carbonate cementation occurs. We conclude that clumped-isotope signatures in authigenic carbonates from accretionary prisms are important proxies for the timing and conditions of cementation in active margins. Our results highlight the importance of using multi-proxy approaches to elucidate the history of carbonate cementation, particularly to establish carbonate precipitation at depth and its potential impact on the physical and mechanical properties of the sediment prior to subduction.

Groundwater Flow Processes and Human Impact along the Arid US-Mexican Border, Evidenced by Environmental Tracers: The Case of Tecate, Baja California.

PubMed

Mahlknecht, Jürgen; Daessle, Luis Walter; Esteller, Maria Vicenta; Torres-Martinez, Juan Antonio; Mora, Abrahan

2018-04-30

With the increasing population, urbanization and industry in the arid area of Tecate, there is a concomitant increase in contaminants being introduced into the Tecate River and its aquifer. This contamination is damaging the usable groundwater supply and making local residents and commercial enterprises increasingly dependent on imported water from the Colorado River basin. In this study we apply a suite of chemical and isotopic tracers in order to evaluate groundwater flow and assess contamination trends. Groundwater recharge occurs through mountain-block and mountain-front recharge at higher elevations of the ranges. Groundwater from the unconfined, alluvial aquifer indicates recent recharge and little evolution. The increase in salinity along the flow path is due to interaction with weathering rock-forming silicate minerals and anthropogenic sources such as urban wastewater, residual solids and agricultural runoff from fertilizers, livestock manure and/or septic tanks and latrines. A spatial analysis shows local differences and the impact of the infiltration of imported waters from the Colorado River basin. The general trend of impaired water quality has scarcely been documented in the last decades, but it is expected to continue. Since the groundwater system is highly vulnerable, it is necessary to protect groundwater sources.

Groundwater Flow Processes and Human Impact along the Arid US-Mexican Border, Evidenced by Environmental Tracers: The Case of Tecate, Baja California

PubMed Central

Daessle, Luis Walter; Esteller, Maria Vicenta; Torres-Martinez, Juan Antonio; Mora, Abrahan

2018-01-01

With the increasing population, urbanization and industry in the arid area of Tecate, there is a concomitant increase in contaminants being introduced into the Tecate River and its aquifer. This contamination is damaging the usable groundwater supply and making local residents and commercial enterprises increasingly dependent on imported water from the Colorado River basin. In this study we apply a suite of chemical and isotopic tracers in order to evaluate groundwater flow and assess contamination trends. Groundwater recharge occurs through mountain-block and mountain-front recharge at higher elevations of the ranges. Groundwater from the unconfined, alluvial aquifer indicates recent recharge and little evolution. The increase in salinity along the flow path is due to interaction with weathering rock-forming silicate minerals and anthropogenic sources such as urban wastewater, residual solids and agricultural runoff from fertilizers, livestock manure and/or septic tanks and latrines. A spatial analysis shows local differences and the impact of the infiltration of imported waters from the Colorado River basin. The general trend of impaired water quality has scarcely been documented in the last decades, but it is expected to continue. Since the groundwater system is highly vulnerable, it is necessary to protect groundwater sources. PMID:29710847

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.

Using Natural Geochemical Tracers to Discern the Dominant Sources of Freshwater into Biscayne Bay, Southeast Florida

NASA Astrophysics Data System (ADS)

Stalker, J. C.; Price, R. M.; Swart, P. K.

2005-05-01

Biscayne Bay is a sub-tropical estuary located on the carbonate platform of south Florida. The water occupying Biscayne Bay is a balance of saltwater influx from the open ocean and freshwater inputs from precipitation, surface water runoff, and submarine groundwater discharge. The bays watershed includes a total of 3 million inhabitants, the major urban centers of Miami and Ft. Lauderdale, as well as the Everglades system. With the development of south Florida, the natural diffuse groundwater and stream flow into the bay has been replaced by a large system of canals and levees in an effort to control flooding and drain swampland. The Comprehensive Everglades Restoration Plan includes changes in the freshwater deliveries to Biscayne Bay from point-source discharges via canals to non-point source discharges via wetlands and groundwater flow. The balance of salinity in Biscayne Bay effects sensitive seagrass and tidal ecosystems including numerous species of corals and other biota. A comprehensive understanding of the flow of freshwater into the bay is crucial to future planned developments and restorations. The goal of this study is to use naturally occurring geochemical constituents as tracers to identify and quantify the sources of freshwater, i.e. rainfall, canal flow, and groundwater, discharge to Biscayne Bay. In this study, discrete samples of precipitation, canal water, terrestrial groundwater, marine groundwater, and bay surface water are collected monthly and analyzed for the stable isotopes of hydrogen and oxygen as well as for major cations and anions. Initial results indicate that fresh groundwater has an isotopic signature (del 18O = -2.66 per mil, del D, -7.60 per mil) similar to rainfall (del 18O = -2.86 per mil, del D =-4.78 per mil). In contrast canal water has a heavy isotopic signature (del 18O = -0.46 per mil, del D = -2.48 per mil) due to evaporation. Thus it is possible to use stable isotopes of oxygen and hydrogen to separate canal water from precipitation and groundwater as a source of freshwater into the bay. Other geochemical constituents, such as calcium and magnesium are being investigated to further discern between the sources of canal water, rainfall and fresh groundwater. Both the stable isotopes and ion values will be placed in a mixing model to quantify and discern the dominant sources of freshwater into the Bay in both time and space.

Geochemical and isotopic determination of deep groundwater contributions and salinity to the shallow groundwater and surface water systems, Mesilla Basin, New Mexico, Texas, and Mexico

NASA Astrophysics Data System (ADS)

Robertson, A.; Carroll, K. C.; Kubicki, C.; Purtshert, R.

2017-12-01

The Mesilla Basin/Conejos-Médanos aquifer system, extending from southern New Mexico to Chihuahua, Mexico, is a priority transboundary aquifer under the 2006 United States­-Mexico Transboundary Aquifer Assessment Act. Declining water levels, deteriorating water quality, and increasing groundwater use by municipal, industrial, and agricultural users on both sides of the international border raise concerns about long-term aquifer sustainability. Relative contributions of present-day and "paleo" recharge to sustainable fresh groundwater yields has not been determined and evidence suggests that a large source of salinity at the distal end of the Mesilla Basin is saline discharge from deep groundwater flow. The magnitude and distribution of those deep saline flow paths are not determined. The contribution of deep groundwater to discharge and salinity in the shallow groundwater and surface water of the Mesilla Basin will be determined by collecting discrete groundwater samples and analyzing for aqueous geochemical and isotopic tracers, as well as the radioisotopes of argon and krypton. Analytes include major ions, trace elements, the stable isotopes of water, strontium and boron isotopes, uranium isotopes, the carbon isotopes of dissolved inorganic carbon, noble gas concentrations and helium isotope ratios. Dissolved gases are extracted and captured from groundwater wells using membrane contactors in a process known as ultra-trace sampling. Gas samples are analyzed for radioisotope ratios of krypton by the ATTA method and argon by low-level counting. Effectiveness of the ultra-trace sampling device and method was evaluated by comparing results of tritium concentrations to the krypton-85 content. Good agreement between the analyses, especially in samples with undetectable tritium, indicates that the ultra-trace procedure is effective and confirms that introduction of atmospheric air has not occurred. The geochemistry data indicate a complex system of geochemical endmembers, and mixing between these endmembers. Ongoing work seeks to better constrain groundwater ages and mixing models through the coupled use of conventional aqueous geochemical and isotopic analysis and the ultra-trace constituents.

Groundwater mixing and mineralization processes in a mountain-oasis-desert basin, northwest China: hydrogeochemistry and environmental tracer indicators

NASA Astrophysics Data System (ADS)

Ma, Bin; Jin, Menggui; Liang, Xing; Li, Jing

2018-02-01

Hydrogeochemistry and environmental tracers (2H, 18O, 87Sr/86Sr) in precipitation, river and reservoir water, and groundwater have been used to determine groundwater recharge sources, and to identify mixing characteristics and mineralization processes in the Manas River Basin (MRB), which is a typical mountain-oasis-desert ecosystem in arid northwest China. The oasis component is artificial (irrigation). Groundwater with enriched stable isotope content originates from local precipitation and surface-water leakage in the piedmont alluvial-oasis plain. Groundwater with more depleted isotopes in the north oasis plain and desert is recharged by lateral flow from the adjacent mountains, for which recharge is associated with high altitude and/or paleo-water infiltrating during a period of much colder climate. Little evaporation and isotope exchange between groundwater and rock and soil minerals occurred in the mountain, piedmont and oasis plain. Groundwater δ2H and δ18O values show more homogeneous values along the groundwater flow direction and with well depths, indicating inter-aquifer mixing processes. A regional contrast of groundwater allows the 87Sr/86Sr ratios and δ18O values to be useful in a combination with Cl, Na, Mg, Ca and Sr concentrations to distinguish the groundwater mixing characteristics. Two main processes are identified: groundwater lateral-flow mixing and river leakage in the piedmont alluvial-oasis plain, and vertical mixing in the north oasis plain and the desert. The 87Sr/86Sr ratios and selected ion ratios reveal that carbonate dissolution and mixing with silicate from the southern mountain area are primarily controlling the strontium isotope hydrogeochemistry.

A geochemical study of Nea-Kameni hyalodacites (Santorini Volcano, Aegean island arc). Inferences concerning the origin and effects of solfataras and magmatic evolution

NASA Astrophysics Data System (ADS)

Briqueu, Louis; Lancelot, Joël R.

1984-03-01

Since the Santorini Volcano (Aegean arc, eastern Mediterranean Sea) collapsed, volcanic activity has been located at the center of the flooded caldera. Over the past 800 years, five lava flows have formed one of the central islets (Nea-Kameni). Since 1951, when the last eruption occurred, a permanent fumarolic activity has remained. We present chemical analyses (major elements, trace-elements and Sr isotopic ratios) of ten samples from the five hyalodacitic lava flows, showing different stages of alteration, from a completely fresh lava up to one bearing native sulfur and other sublimates. Only the macroscopic aspect of these hyalodacites is affected by fumarolic activity. The elements that are mobile as a result of hydrothermal processes, such as the alkaline (K, Rb) or the chalcophile elements (Zn, Pb), show great homogeneity; the same can be said for the Sr isotopic compositions which range from 0.7046 to 0.7049. None of the analyzed samples has an Sr isotopic composition as high as those reported by Puchelt and Hoefs (1971) for rock samples collected in the same lava flows. If we take into account the marine surroundings of Nea-Kameni islet, these observations put severe restraints on the different hypotheses regarding the origin of the halogens (seawater or meteoric water). The contamination processes of these dacitic lavas are clearly less important than assumed by other authors according to previous Sr isotopic data. Finally, the homogeneity of the elements with low partition coefficients is sufficient to show that the magma has not undergone any perceptible evolution during the last 300 years.

Inter-relationship between shallow and deep aquifers under the influence of deep groundwater exploitation in the North China Plain

NASA Astrophysics Data System (ADS)

Han, Dongmei; Cao, Guoliang; Love, Andrew J.

2017-04-01

In the North China Plain (NCP), the interaction between shallow and deep groundwater flow systems enhanced by groundwater extraction has been investigated using multi-isotopic and chemical tracers for understanding the mechanism of salt water transport, which has long been one of the major regional environmental hydrogeological problems in NCP. Information about the problem will be determined using multiple lines of evidence, including field surveys of drilling and water sampling, as well as laboratory experiments and physical and numerical simulations. A conceptual model of groundwater flow system along WE cross-section from piedmont area to coastal region (Shijiazhuang-Hengshui-Cangzhou) has been developed and verified by geochemical modeling. A combined hydrogeochemical and isotopic investigation using ion relationships such as Cl/Br ratios, and environment isotopes (δ 18O, δ 2H, δ 34SSO4-δ 18OSO4, δ 15NNO_3-δ 18ONO_3, δ 13C and 87Sr/86Sr) was reviewed and carried for determining the sources of aquifer recharge, the origin of solutes and the mixing processes in groundwater flow system under the anthropogenic pumping and pollution. Results indicate that hydrochemistry of groundwater is characterized by mixing between end-members coming directly from Piedmont recharge areas, saline groundwater formed during geohistorical transgression in the shallow aquifers of central plain, and to groundwater circulating in a deeply buried Quaternary sediments. We also reviewed the groundwater age (tritium contents, 14C ages, 3H-3He ages, basin-scale flow modeling ages of groundwater) to recognize the local distributed recharge in this strongly exploited aquifer system. Finally, combined with the 1-D Cl transport modeling for the pore water of clay-rich aquitard, we reveal that salt transport in the aquitard is primarily controlled by vertical diffusion on million years' time scale, and the observed the salinized groundwater in deep aquifer may be caused by passing through ``windows'' or preferential flow path, rather than vertical flow through the aquitard.

Organic matter dynamics and stable isotope signature as tracers of the sources of suspended sediment

NASA Astrophysics Data System (ADS)

Schindler Wildhaber, Y.; Liechti, R.; Alewell, C.

2012-06-01

Suspended sediment (SS) and organic matter in rivers can harm brown trout Salmo trutta by affecting the health and fitness of free swimming fish and by causing siltation of the riverbed. The temporal and spatial dynamics of sediment, carbon (C), and nitrogen (N) during the brown trout spawning season in a small river of the Swiss Plateau were assessed and C isotopes as well as the C/N atomic ratio were used to distinguish autochthonous and allochthonous sources of organic matter in SS loads. The visual basic program IsoSource with 13Ctot and 15N as input isotopes was used to quantify the temporal and spatial sources of SS. Organic matter concentrations in the infiltrated and suspended sediment were highest during low flow periods with small sediment loads and lowest during high flow periods with high sediment loads. Peak values in nitrate and dissolved organic C were measured during high flow and high rainfall, probably due to leaching from pasture and arable land. The organic matter was of allochthonous sources as indicated by the C/N atomic ratio and δ13Corg. Organic matter in SS increased from up- to downstream due to an increase of pasture and arable land downstream of the river. The mean fraction of SS originating from upper watershed riverbed sediment decreased from up to downstream and increased during high flow at all measuring sites along the course of the river. During base flow conditions, the major sources of SS are pasture, forest and arable land. The latter increased during rainy and warmer winter periods, most likely because both triggered snow melt and thus erosion. The measured increase in DOC and nitrate concentrations during high flow support these modeling results. Enhanced soil erosion processes on pasture and arable land are expected with increasing heavy rain events and less snow during winter seasons due to climate change. Consequently, SS and organic matter in the river will increase, which will possibly affect brown trout negatively.

Isotope ratio mass spectrometry coupled to liquid and gas chromatography for wine ethanol characterization.

PubMed

Cabañero, Ana I; Recio, Jose L; Rupérez, Mercedes

2008-10-01

Two new procedures for wine ethanol 13C/12C isotope ratio determination, using high-performance liquid chromatography and gas chromatography isotope ratio mass spectrometry (HPLC/IRMS and GC/IRMS), have been developed to improve isotopic methods dedicated to the study of wine authenticity. Parameters influencing separation of ethanol from wine matrix such as column, temperature, mobile phase, flow rates and injection mode were investigated. Twenty-three wine samples from various origins were analyzed for validation of the procedures. The analytical precision was better than 0.15 per thousand, and no significant isotopic fractionation was observed employing both separative techniques coupled to IRMS. No significant differences and a very strong correlation (r = 0.99) were observed between the 13C/12C ratios obtained by the official method (elemental analyzer/isotope ratio mass spectrometry) and the proposed new methodology. The potential advantages of the developed methods over the traditional one are speed (reducing time required from hours to minutes) and simplicity. In addition, these are the first isotopic methods that allow 13C/12C determination directly from a liquid sample with no previous ethanol isolation, overcoming technical difficulties associated with sample treatment.

Isotopic and noble gas geochemistry in geothermal research

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

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

1997-12-31

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

Sedimentary organic molecules: Origins and information content

NASA Technical Reports Server (NTRS)

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

1991-01-01

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

Tracing nitrates and sulphates in river basins using isotope techniques.

PubMed

Rock, L; Mayer, B

2006-01-01

The objective of this paper is to outline how stable isotope techniques can contribute to the elucidation of the sources and the fate of riverine nitrate and sulphate in watershed studies. The example used is the Oldman River Basin (OMRB), located in southern Alberta (Canada). Increasing sulphate concentrations and decreasing delta(34)S values along the flowpath of the Oldman River indicate that oxidation of pyrite in tills is a major source of riverine sulphate in the agriculturally used portion of the OMRB. Chemical and isotopic data showed that manure-derived nitrogen contributes significantly to the increase in nitrate concentrations in the Oldman River and its tributaries draining agricultural land. It is suggested that hydrological conditions control agricultural return flows to the surface water bodies in southern Alberta and impart significant seasonal variations on concentrations and isotopic compositions of riverine nitrate. Combining isotopic, chemical, and hydrometric data permitted us to estimate the relative contribution of major sources to the total solute fluxes. Hence, we submit that isotopic measurements can make an important contribution to the identification of nutrient and pollutant sources and to river basin management.

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.

Catchment Storage and Transport on Timescales from Minutes to Millennia

NASA Astrophysics Data System (ADS)

Kirchner, J. W.

2017-12-01

Landscapes are characterized by preferential flow and pervasive heterogeneity on all scales. They therefore store and transmit water and solutes over a wide spectrum of time scales, with important implications for contaminant transport, weathering rates, and runoff chemistry. Theoretical analyses predict, and syntheses of age tracer data confirm, that waters in aquifers are older - often by orders of magnitude - than in the rivers that flow from them, and that this disconnect between water ages arises from aquifer heterogeneity. Recent theoretical studies also suggest that catchment transit time distributions are nonstationary, reflecting temporal variability in precipitation forcing, structural heterogeneity in catchments themselves, and the nonlinearity of the mechanisms controlling storage and transport in the subsurface. The challenge of empirically estimating these nonstationary transit time distributions in real-world catchments, however, has only begun to be explored. In recent years, long-term isotope time series have been collected in many research catchments, and new technologies have emerged that allow quasi-continuous measurements of isotopes in precipitation and streamflow. These new data streams create new opportunities to study how rainfall becomes streamflow following the onset of precipitation. Here I present novel methods for quantifying the fraction of current rainfall in streamflow across ensembles of precipitation events. Benchmark tests with nonstationary catchment models demonstrate that this approach quantitatively measures the short tail of the transit time distribution for a wide range of catchment response characteristics. In combination with reactive tracer time series, this approach can potentially be extended to measure short-term chemical reaction rates at the catchment scale. Applications using high-frequency tracer time series from several experimental catchments demonstrate the utility of the new approach outlined here.

Accounting for the effects of lipids in stable isotope (δ13C and δ15N values) analysis of skin and blubber of balaenopterid whales.

PubMed

Ryan, Conor; McHugh, Brendan; Trueman, Clive N; Harrod, Chris; Berrow, Simon D; O'Connor, Ian

2012-12-15

Stable isotope values (δ(13)C and δ(15)N) of darted skin and blubber biopsies can shed light on habitat use and diet of cetaceans, which are otherwise difficult to study. Non-dietary factors affect isotopic variability, chiefly the depletion of (13)C due to the presence of (12)C-rich lipids. The efficacy of post hoc lipid-correction models (normalization) must be tested. For tissues with high natural lipid content (e.g., whale skin and blubber), chemical lipid extraction or normalization is necessary. C:N ratios, δ(13)C values and δ(15)N values were determined for duplicate control and lipid-extracted skin and blubber of fin (Balaenoptera physalus), humpback (Megaptera novaeangliae) and minke whales (B. acutorostrata) by continuous-flow elemental analysis isotope ratio mass spectrometry (CF-EA-IRMS). Six different normalization models were tested to correct δ(13)C values for the presence of lipids. Following lipid extraction, significant increases in δ(13)C values were observed for both tissues in the three species. Significant increases were also found for δ(15)N values in minke whale skin and fin whale blubber. In fin whale skin, the δ(15)N values decreased, with no change observed in humpback whale skin. Non-linear models generally out-performed linear models and the suitability of models varied by species and tissue, indicating the need for high model specificity, even among these closely related taxa. Given the poor predictive power of the models to estimate lipid-free δ(13)C values, and the unpredictable changes in δ(15)N values due to lipid-extraction, we recommend against arithmetical normalization in accounting for lipid effects on δ(13)C values for balaenopterid skin or blubber samples. Rather, we recommend that duplicate analysis of lipid-extracted (δ(13)C values) and non-treated tissues (δ(15)N values) be used. Copyright © 2012 John Wiley & Sons, Ltd.

New insights into the rate dependence of sulfur isotope fractionation during dissimilatory sulfate reduction

NASA Astrophysics Data System (ADS)

Giannetta, M.; Druhan, J. L.; Sanford, R. A.

2016-12-01

The vast majority of experiments concerning the isotope partitioning of sulfate reducing bacteria (SRB) are conducted under artificially optimized growth conditions. In contrast, many natural environments supporting SRB reflect limited nutrient availability. In this study, we couple the cell-specific reduction rate of a common SRB to the characteristic partitioning of stable sulfur isotopes. However, our method is novel in that we regulate the addition of electron donor such that cell growth is minimized and cell-specific reduction rates are constant, thus simulating the low reactivity characteristic of natural conditions. Anoxic bioreactors containing equal amounts of Desulfovibrio vulgariswere continuously injected with formate to control the rate of dissimilatory sulfate reduction (DSR). Cell growth was minimized through two means, (1) a high initial culture density ensured the ratio of nutrients per cell was low; (2) the oxidation state of carbon in formate is unfavorable to cell biomass accumulation. Negligible cell growth was verified by flow cytometry. Four controlled DSR rates ranging from 0.32 to 1.8 µmole/hour exhibited fractionation factor (ɛ) values ranging from 9‰ to 4‰ over 1200 to 300 hours, respectively. These results demonstrate a unique value of ɛ for each rate of DSR, where larger S isotope partitioning is characteristic of a slower cell-specific rate of sulfate reduction. The results of this study provide a unique dataset that can be used to constrain variations in ɛ as a function of DSR rate. Specifically, the dataset offers a foundation to test recently proposed analytical models and predict variations in observed ɛ as a result of a multi-step reactive pathway. Based on these results, we suggest a novel rate expression for incorporation into reactive transport models. Such a rate law supports extrapolation of experimental behavior into natural conditions over modern to geologic timescales.

Pyrolysis-gas chromatography-isotope ratio mass spectrometry for monitoring natural additives in polylactic acid active food packages.

PubMed

Llana-Ruíz-Cabello, M; Pichardo, S; Jiménez-Morillo, N T; González-Vila, F J; Guillamón, E; Bermúdez, J M; Aucejo, S; Camean, A M; González-Pérez, J A

2017-11-24

Compound-specific isotope analysis (CSIA) usually requires preparative steps (pretreatments, extraction, derivatization) to get amenable chromatographic analytes from bulk geological, biological or synthetic materials. Analytical pyrolysis (Py-GC/MS) can help to overcome such sample manipulation. This communication describe the results obtained by hyphenating analytical pyrolysis (Py-GC) with carbon isotope-ratio mass spectrometry (IRMS) for the analysis of a polylactic acid (PLA) a based bio-plastic extruded with variable quantities of a natural plant extract or oregano essential oil. The chemical structural information of pyrolysates was first determined by conventional analytical pyrolysis and the measure of δ 13 C in specific compounds was done by coupling a pyrolysis unit to a gas chromatograph connected to a continuous flow IRMS unit (Py-GC-C-IRMS). Using this Py-CSIA device it was possible to trace natural additives with depleted δ 13 C values produced by C3 photosystem vegetation (cymene: -26.7‰±2.52; terpinene: -27.1‰±0.13 and carvacrol: -27.5‰±1.80 from oregano and two unknown structures: -23.3‰±3.32 and -24.4‰±1.70 and butyl valerate: -24.1‰±3.55 from Allium spp.), within the naturally isotopically enriched bio-plastic backbone derived from corn (C4 vegetation) starch (cyclopentanones: -14.2‰±2.11; lactide enantiomers: -9.2‰±1.56 and larger polymeric units: -17.2‰±1.71). This is the first application of Py-CSIA to characterize a bio-plastic and is shown as a promising tool to study such materials, providing not only a fingerprinting, but also valuable information about the origin of the materials, allowing the traceability of additives and minimizing sample preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface-Cycling of Rhenium and its Isotopes

DTIC Science & Technology

2009-06-01

Fisher Scientific) in the WHOI plasma facility. Samples were introduced using a PFA MicroFlow nebulizer (Elemental Scientific Incorporated), a quartz...Samples were introduced using a PFA MicroFlow nebulizer (Elemental Scientific Incorporated), a quartz spray chamber, and regular cones. Analyses are done in...189Os. Samples dissolved in 1 mL of 0.5 molL−1 HNO3 are introduced using a PFA MicroFlow nebulizer (Elemental Scientific Incorporated), a quartz spray

A new multiprogrammable isotopic powered cardiac pacemaker

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

Smyth, N.P.; Purdy, D.L.; Sager, D.

1982-09-01

A new multiprogrammable, isotopic-powered cardiac pacemaker was implanted in six patients as a custom device. Five were initial implants and one was a replacement. The patients were studied for up to two years. In five of the six cases it was found advantageous to change one of the programmable parameters. Multiprogrammability is obviously as important in an isotopic pulse generator as in a lithium unit, if not more so, because of the unit's greater longevity. Further studies are continuing in an FDA approved clinical trial.

Comprehensive authentication of (E)-alpha(beta)-ionone from raspberries, using constant flow MDGC-C/P-IRMS and enantio-MDGC-MS.

PubMed

Sewenig, Sabine; Bullinger, Dino; Hener, Uwe; Mosandl, Armin

2005-02-23

A new coupling system of GC-GC, connected via a Multi Column Switching Device MCS2 for measuring isotope ratios, is introduced. By means of several standard substances the precise and accurate measurement of isotopic values is proved. First applications concerning the authentication of raspberry aroma compounds are established. Consequently, the combination of constant flow multidimensional gas chromatography-combustion/pyrolysis-isotope ratio mass spectrometry (MDGC-C/P-IRMS) is applied to the authenticity assessment of (E)-alpha(beta)-ionone from six different raspberry cultivars. Furthermore, 12 commercially available raspberry products and samples of (E)-alpha(beta)-ionone, some declared to be natural, are investigated. delta(2)Eta(V)(-)(SMOW) and delta(13)C(V)(-)(PDB) values of (E)-alpha(beta)-ionone are determined, and characteristic authenticity ranges were concluded from raspberries by correlation of both delta(2)Eta(V)(-)(SMOW) and delta(13)C( V)(-)(PDB) values. The results are correlated with the determination of enantiomeric purities of (E)-alpha-ionone, using stir bar sorptive extraction enantio-multidimensional gas chromatography mass spectrometry (SBSE-enantio-MDGC-MS).

Determination of Plutonium Isotope Ratios at Very Low Levels by ICP-MS using On-Line Electrochemically Modulated Separations

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

Liezers, Martin; Lehn, Scott A; Olsen, Khris B

2009-10-01

Electrochemically modulated separations (EMS) are shown to be a rapid and selective means of extracting and concentrating Pu from complex solutions prior to isotopic analysis by inductively coupled plasma mass spectrometry (ICP-MS). This separation is performed in a flow injection mode, on-line with the ICP-MS. A three-electrode, flow-by electrochemical cell is used to accumulate Pu at an anodized glassy carbon electrode by redox conversion of Pu(III) to Pu (IV&VI). The entire process takes place in 2% v/v (0.46M) HNO 3. No redox chemicals or acid concentration changes are required. Plutonium accumulation and release is redox dependent and controlled by themore » applied cell potential. Thus large transient volumetric concentration enhancements can be achieved. Based on more negative U(IV) potentials relative to Pu(IV), separation of Pu from uranium is efficient, thereby eliminating uranium hydride interferences. EMS-ICP-MS isotope ratio measurement performance will be presented for femtogram to attogram level plutonium concentrations.« less

Modeling the Removal of Xenon from Lithium Hydrate with Aspen HYSYS

NASA Astrophysics Data System (ADS)

Efthimion, Phillip; Gentile, Charles

2011-10-01

The Laser Inertial Fusion Engine (LIFE) project mission is to provide a long-term, carbon-free source of sustainable energy, in the form of electricity. A conceptual xenon removal system has been modeled with the aid of Aspen HYSYS, a chemical process simulator. Aspen HYSYS provides excellent capability to model chemical flow processes, which generates outputs which includes specific variables such as temperature, pressure, and molar flow. The system is designed to strip out hydrogen isotopes deuterium and tritium. The base design bubbles plasma exhaust laden with x filled with liquid helium. The system separates the xenon from the hydrogen, deuterium, and tritium with a lithium hydrate and a lithium bubbler. After the removal of the hydrogen and its isotopes, the xenon is then purified by way of the process of cryogenic distillation. The pure hydrogen, deuterium, and tritium are then sent to the isotope separation system (ISS). The removal of xenon is an integral part of the laser inertial fusion engine and Aspen HYSYS is an excellent tool to calculate how to create pure xenon.

Movements of water, solutes, and stable isotopes in the unsaturated zones of two sand plains in the upper Midwest

USGS Publications Warehouse

Komor, Stephen C.; Emerson, Douglas G.

1994-01-01

Four month-long field experiments investigated movements of water and solutes through unsaturated sand plains near Princeton, Minnesota, and Oakes, North Dakota. Atrazine and bromide were applied to bare soils and soils planted with corn. The field plots were irrigated according to local farming practices. At the end of each experiment, unsaturated soils were analyzed for atrazine and bromide concentrations and oxygen and hydrogen isotope compositions of soil water. Most soil water was affected by evaporation but groundwater beneath the plots had no evaporative isotopic signature. Therefore most recharge consisted of water that was unaffected by evaporation. Sources of such water may have included snowmelt, prolonged or high-intensity rainfalls that were not interrupted by periods of drying, and water that moved through preferential flow paths. Preferential flow also was suggested by the detection of atrazine, deethylatrazine, and bromide in groundwater shortly after each application of irrigation water at Princeton and by isolated concentrations of atrazine and bromide in soil well below the main masses of chemicals at Oakes.

Pesticide leaching via subsurface drains in different hydrologic situations

NASA Astrophysics Data System (ADS)

Zajíček, Antonín; Fučík, Petr; Liška, Marek; Dobiáš, Jakub

2017-04-01

esticides and their degradates in tile drainage waters were studied in two small, predominantly agricultural, tile-drained subcatchments in the Bohemian-Moravian Highlands, Czech Republic. The goal was to evaluate their occurence and the dymamics of their concentrations in drainage waters in different hydrologic situations using discharge and concentration monitoring together with 18O and 2H isotope analysis for Mean Residence Time (MRT) estimation and hydrograph separations during rainfall - runoff (R-R) events. The drainage and stream discharges were measured continuously at the closing outlets of three drainage groups and one small stream. During periods of prevailing base and interflow, samples were collected manually in two-week intervals for isotope analysis and during the spraying period (March to October) also for pesticide analysis. During R-R events, samples were taken by automatic samplers in intervals varying from 20 min (summer) to 1 hour (winter). To enable isotopic analysis, precipitation was sampled both manually at two-week intervals and also using an automatic rainfall sampler which collected samples of precipitation during the R-R events at 20-min. intervals. The isotopic analysis showed, that MRT of drainage base flow and interflow varies from 2,2 to 3,3 years, while MRT of base flow and interflow in surface stream is several months. During R-R events, the proportion of event water varied from 0 to 60 % in both drainage and surface runoff. The occurrence of pesticides and their degradates in drainage waters is strongly dependent on the hydrologic situation. While degradates were permanently present in drainage waters in high but varying concentrations according to instantaneous runoff composition, parent matters were detected almost exclusively during R-R events. In periods with prevailing base flow and interflow (grab samples), especially ESA forms of chloracetanilide degradates occured in high concentrations in all samples. Average sum of degradates varried between 1 730 - 5 760 ng/l. During R-R events, pesticide concentration varried according to runoff composition and time between sprayng and event. Event with no protortiom of event water in drainage runoff were typical by incereas in degradates concentrations (up to 20 000ng/l) and none or low occurence of parent matters. Events with significant event water proportion in drainage runoff were characterised by decrease in degradates concentrations and (when event happened soon affter spraying) by presence of paternal pesticides in drinage runoff. Instanteous concentrations of paren matters can be extremely high in that causes, up to 23 000 ng/l in drainage waters and up to 40 000 ng/l in small stream. Above results suggest that drainage systems could act as significant source of pesticide leaching. When parent compounds leaches via tile drainage systems, there are some border conditions that must exist together such as the occurence of R-R event soon after the pests application and the presence of event water (or water with short residence time in the catchment) in the drainage runoff.

A porewater - based stable isotope approach for the investigation of subsurface hydrological processes

NASA Astrophysics Data System (ADS)

Garvelmann, J.; Külls, C.; Weiler, M.

2011-10-01

Predicting and understanding subsurface flowpaths is still a crucial issue in hydrological research. We present an experimental approach to reveal present and past subsurface flowpaths of water in the unsaturated and saturated zone. Two hillslopes in a humid moutainous catchment have been investigated. The H2O(liquid) - H2O(vapor) equilibration laser spectroscopy method was used to obtain high resolution δ2H vertical depth profiles of porewater at various points along a fall line of a pasture hillslope in the southern Black Forest, Germany. The Porewater Stable Isotope Profile (PSIP) approach was developed to use the integrated information of several vertical depth profiles of deuterium along two transects at the hillslopes. Different shapes of depth profiles were observed in relation to hillslope position. The statistical variability (inter-quartile range and standard deviation) of each profile was used to characterize different types of depth profiles. The profiles upslope or with a weak affinity for saturation as indicated by a low topographic wetness index preserve the isotopic input signal by precipitation with a distinct seasonal variability. These observations indicate mainly vertical movement of soil water in the upper part of the hillslope before sampling. The profiles downslope or at locations with a strong affinity for saturation do not show a similar seasonal isotopic signal. The input signal is erased in the foothills and a large proportion of pore water samples are close to the isotopic values of δ2H in stream water during base flow. Near the stream indications for efficient mixing of water from lateral subsurface flow paths with vertical percolation are found.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands: Pahranagat Valley, Nevada, USA

USGS Publications Warehouse

Paces, James B.; Wurster, Frederic C.

2014-01-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge’s irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Calcium isotope fractionation in a silicate dominated Cenozoic aquifer system

NASA Astrophysics Data System (ADS)

Li, Junxia; DePaolo, Donald J.; Wang, Yanxin; Xie, Xianjun

2018-04-01

To understand the characteristics of Ca isotope composition and fractionation in silicate-dominated Quaternary aquifer system, hydrochemical and isotope studies (87Sr/86Sr, 13CDIC and 44/40Ca) were conducted on groundwater, sediment and rock samples from the Datong basin, China. Along the groundwater flow path from the basin margin to the center, groundwater hydrochemical type evolves from Ca-HCO3 to Na-HCO3/Na-Cl type, which results from aluminosilicate hydrolysis, vertical mixing, cation exchange between CaX2 and NaX, and calcite/dolomite precipitation. These processes cause the decrease in groundwater Ca concentration and the associated modest fractionation of groundwater Ca isotopes along the flowpath. The groundwater δ44/40Ca value varies from -0.11 to 0.49‰. The elevated δ44/40Ca ratios in shallow groundwater are attributed to vertical mixing involving addition of irrigation water, which had the average δ44/40Ca ratio of 0.595‰. Chemical weathering of silicate minerals and carbonate generates depleted δ44/40Ca signatures in groundwater from Heng Mountain (east area) and Huanghua Uplift (west area), respectively. Along the groundwater flow path from Heng Mountain to central area of east area, cation exchange between CaX2 and NaX on clay mineral results in the enrichment of heavier Ca isotope in groundwater. All groundwater samples are oversaturated with respect to calcite and dolomite. The groundwater environment rich in organic matter promotes the precipitation of carbonate minerals via the biodegradation of organic carbon, thereby further promoting the elevation of groundwater δ44/40Ca ratios.

Natural uranium and strontium isotope tracers of water sources and surface water-groundwater interactions in arid wetlands - Pahranagat Valley, Nevada, USA

NASA Astrophysics Data System (ADS)

Paces, James B.; Wurster, Frederic C.

2014-09-01

Near-surface physical and chemical process can strongly affect dissolved-ion concentrations and stable-isotope compositions of water in wetland settings, especially under arid climate conditions. In contrast, heavy radiogenic isotopes of strontium (87Sr/86Sr) and uranium (234U/238U) remain largely unaffected and can be used to help identify unique signatures from different sources and quantify end-member mixing that would otherwise be difficult to determine. The utility of combined Sr and U isotopes are demonstrated in this study of wetland habitats on the Pahranagat National Wildlife Refuge, which depend on supply from large-volume springs north of the Refuge, and from small-volume springs and seeps within the Refuge. Water budgets from these sources have not been quantified previously. Evaporation, transpiration, seasonally variable surface flow, and water management practices complicate the use of conventional methods for determining source contributions and mixing relations. In contrast, 87Sr/86Sr and 234U/238U remain unfractionated under these conditions, and compositions at a given site remain constant. Differences in Sr- and U-isotopic signatures between individual sites can be related by simple two- or three-component mixing models. Results indicate that surface flow constituting the Refuge's irrigation source consists of a 65:25:10 mixture of water from two distinct regionally sourced carbonate-aquifer springs, and groundwater from locally sourced volcanic aquifers. Within the Refuge, contributions from the irrigation source and local groundwater are readily determined and depend on proximity to those sources as well as water management practices.

Geochemical markers of sedimentary organic matter in Todos os Santos Bay, Bahia - Brazil. Indicators of sources and preservation.

PubMed

de Souza, José Roberto Bispo; do Rosário Zucchi, Maria; Costa, Alexandre Barreto; de Azevedo, Antonio Expedito Gomes; Spano, Saulo

2017-06-30

Natural stable isotopes, such as carbon (C) and nitrogen (N), are modern tools to assess geochemical processes. C and N in organic matter can carry fingerprints of their hydrologic flows and sedimentary processes, including any anthropogenic modification on the natural system. This study focuses on the determination of aliphatic and polycyclic aromatic hydrocarbons and isotopic ratio in the sediment of Todos os Santos Bay (TSB). The isotopic results of the total organic matter indicate varied contribution marine and terrigenous. Typical rates of PAHs mainly indicate a pyrogenic source and mixture between pyrogenic and petrogenic sources. Typical ratios for the n-alkanes indicate the presence of petroleum hydrocarbons. The isotopic composition of n-alkanes suggests a mixture of sources, with the possible contribution of petrogenic. Copyright © 2017. Published by Elsevier Ltd.

Performance and limits of liquid chromatography isotope ratio mass spectrometry system for halogenated compounds

NASA Astrophysics Data System (ADS)

Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans

2014-05-01

Compound Specific Isotope Analysis (CSIA) has been an important step for the assessment of the origin and fate of compounds in environmental science.[1] Biologically or pharmaceutically important compounds often are not amenable for gas chromatographic separation because of high polarity and lacking volatility, thermostability. In 2004 liquid chromatography isotope ratio mass spectrometry (LC-IRMS) became commercially available. LC-IRMS system intent a quantitative conversion of analytes separation into CO2 via wet oxidation with sodium persulfate in the presence of phosphoric acid while analytes are still dissolved in the aqueous liquid phase.[2] The aim of this study is to analyze the oxidation capacity of the interface of the LC-IRMS system and determine which parameters could improve oxidation of compounds which are resistant to persulfate oxidation. Oxidation capacity of the liquid chromatography isotope ratio mass spectrometry system was tested with halogenated acetic acid and a set of aromatic compounds with different substitutes. Acetic acid (AA) was taken as a model compound for complete oxidation and compared to the oxidation of other analytes on a molar basis. Correct values were obtained for di- and mono chlorinated and fluorinated and also for tribrominated acetic acid and for all studied aromatic compounds. Incomplete oxidation for trichloroacetic (TCAA) and trifluoroacetic (TFAA) acid was revealed with lower recovery compared to acetic acid and isotope fractionation leading to depleted carbon isotope composition compared to values obtained with an elementary analyzer connected to an isotope mass spectrometer Several optimization steps were tried in order to improve the oxidation of TCAA and TFAA: (i) increasing the concentration of the oxidizing agent, (ii) variation of flow rate of the oxidizing and acid solution, (iii) variation of flow rate of liquid chromatography pump (iv) addition of a catalyzer. These modifications lead to longer reaction time in the coil and increase in the concentration of radical but complete combustion of highly chlorinated or fluorinated compounds was not achieved. Due to these findings the limit for a LC-IRMS system for similar structure compounds can be predicted. 1. Elsner, M., et al., Current challenges in compound-specific stable isotope analysis of environmental organic contaminants. Analytical and Bioanalytical Chemistry, 2012. 403(9): p. 2471-2491. 2. Krummen, M., et al., A new concept for isotope ratio monitoring liquid chromatography/mass spectrometry. Rapid Communications in Mass Spectrometry, 2004. 18(19): p. 2260-2266.

A new method for stable carbon isotope analysis of chlorofluorocarbons in contaminated groundwater

NASA Astrophysics Data System (ADS)

Horst, Axel; Lacrampe-Couloume, Georges; Sherwood Lollar, Barbara

2015-04-01

Chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) have been widely used as refrigerants, propellants, solvents, foaming agents and are important intermediates in the production of anesthetics and other fluorinated compounds. Due to their ozone depletion potential, production was banned for most uses under the Montreal Protocol (1987) and its amendments and atmospheric mixing ratios have started to decrease. In addition to the atmosphere, CFCs and HCFCs have been detected in groundwater, and emissions from various sources such as landfill sites are still ongoing. Previous studies have shown that both abiotic and biotic transformation of CFCs may occur under certain conditions. To investigate degradation that may take place in soils and groundwaters, a purge and trap method (P&T) has been developed to measure the stable carbon isotopic composition of CFCs and HCFCs extracted from waters. A set of pure phase working standards (HCFC-22, CFC-11, CFC-113) has been prepared offline and characterized by sealed tube combustion dual inlet mass spectrometry. Comparison between isotopic standards and CFCs extracted by our method demonstrates the sample P&T extraction steps do not induce significant δ13C fractionation (lt;0.5 per mill). Standards characterized by continuous flow CSIA (compound specific isotope analysis) after extraction agree with offline characterized values. Evaporation experiments were carried out to investigate any isotope effects due to volatile loss that might occur either due to sampling methods or sample handling in the lab. Monitoring δ13C values during progressive evaporation showed small isotopic fractionation associated with evaporation. Enrichment factors, obtained from Rayleigh plots, showed inverse isotope fractionation i.e depletion in 13C in the remaining compound. Notably, this effect is in the opposite direction to the fractionation (13C enrichment) that is likely to be associated with abiotic or biotic transformation effects. This bodes well for the use of CSIA to identify and monitor transformation in the field as any isotopic effects due to volatile loss would only result in a conservative estimate of transformation but not confuse the degradation signal. As a result, enrichment factors in field samples might be underestimated and lead to a more conservative estimate of degradation at contaminated sites. CFCs from several suppliers were characterized to investigate δ13C variation between sources and between different CFC compounds. Significant differences were observed between all measured compounds. However for each compound, δ13C values determined in this study were similar to ranges reported previously for other pure phase CFCs - suggesting a consistent range of source signatures may exist for each compound. As a last step of method evaluation, water samples from a contaminated industrial site were measured. This first preliminary field data will be discussed in comparison to pure phase compounds and with respect to potential degradation.

Removing the effects of metamorphism from the Neoproterozoic carbon isotope record: a case study on Islay, western Scotland

NASA Astrophysics Data System (ADS)

Skelton, Alasdair

2016-04-01

The Port Askaig Formation on Islay, western Scotland is the first discovered tillite (glacial sediment) of Neoproterozoic age. This formation is sandwiched between carbonate rocks which preserve an extreme negative carbon isotope excursion. This so called "Islay anomaly" has been correlated with other such anomalies worldwide and together with the tillites has been cited as evidence of major (worldwide) glaciation events. During subsequent mountain building, this carbonate-tillite- carbonate sequence has been folded, producing a major en-echelon anticlinal fold system. Folding was accompanied by metamorphism at greenschist facies conditions which was, in turn, accompanied by metamorphic fluid flow. Mapping of the δ18O and δ13C values of these carbonate rocks reveals that metamorphic fluids were channelled through the axial region of the anticlinal fold. The metamorphic fluid was found to have a highly negative δ13C value, which was found to be in equilibrium with metamorphosed graphitic mudstones beneath the carbonate-tillite-carbonate sequence. Devolatilisation of these mudstones is therefore a likely source of this metamorphic fluid. Removal of the effects of metamorphic fluid flow on δ13C values recorded by metamorphosed carbonate rocks on Islay allows us to re-evaluate the isotopic evidence used to reconstruct Neoproterozoic climate. We are able to show that extreme negative δ13C values can partly be attributed to metamorphic fluid flow.

Identifying sources of stream water sulfate after a summer drought in the Sleepers River watershed (Vermont, USA) using hydrological, chemical, and isotopic techniques

USGS Publications Warehouse

Mayer, B.; Shanley, J.B.; Bailey, S.W.; Mitchell, M.J.

2010-01-01

In many forested headwater catchments, peak SO42 - concentrations in stream water occur in the late summer or fall following drought potentially resulting in episodic stream acidification. The sources of highly elevated stream water SO42 - concentrations were investigated in a first order stream at the Sleepers River watershed (Vermont, USA) after the particularly dry summer of 2001 using a combination of hydrological, chemical and isotopic approaches. Throughout the summer of 2001 SO42 - concentrations in stream water doubled from ???130 to 270 ??eq/L while flows decreased. Simultaneously increasing Na+ and Ca2+ concentrations and ??34S values increasing from +7??? towards those of bedrock S (???+10.5???) indicated that chemical weathering involving hydrolysis of silicates and oxidation of sulfide minerals in schists and phyllites was the cause for the initial increase in SO42 - concentrations. During re-wetting of the watershed in late September and early October of 2001, increasing stream flows were accompanied by decreasing Na+ and Ca2+ concentrations, but SO42 - concentrations continued to increase up to 568 ??eq/L, indicating that a major source of SO42 - in addition to bedrock weathering contributed to peak SO42 - concentrations. The further increase in SO42 - concentrations coincided with an abrupt decrease of ??34S values in stream water SO42 - from maximum values near +10??? to minimum values near -3???. Soil investigations revealed that some C-horizons in the Spodsols of the watershed contained secondary sulfide minerals with ??34S values near -22???. The shift to negative ??34S values of stream water SO42 - indicates that secondary sulfides in C-horizons were oxidized to SO42 - during the particularly dry summer of 2001. The newly formed SO42 - was transported to the streams during re-wetting of the watershed contributing ???60% of the SO42 - during peak concentrations in the stream water. Thereafter, the contribution of SO42 - from oxidation of secondary sulfides in C-horizons decreased rapidly and pedogenic SO42 - reemerged as a dominant SO42 - source in concert with decreasing SO42 - concentrations in spring of 2002. The study provides evidence that a quantitative assessment of the sources of stream water SO42 - in forested watersheds is possible by combining hydrological, chemical and isotopic techniques, provided that the isotopic compositions of all potential SO42 - sources are distinctly different. ?? 2010 Elsevier Ltd.

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.

Radium isotope ((223)Ra, (224)Ra, (226)Ra and (228)Ra) distribution near Brazil's largest port, Paranaguá Bay, Brazil.

PubMed

Dias, Thais H; de Oliveira, Joselene; Sanders, Christian J; Carvalho, Franciane; Sanders, Luciana M; Machado, Eunice C; Sá, Fabian

2016-10-15

This work investigates the (223)Ra, (224)Ra, (226)Ra and (228)Ra isotope distribution in river, estuarine waters and sediments of the Paranaguá Estuarine Complex (PEC). The stratification of the Ra isotopes along water columns indicate differing natural sources. In sediments, the radium isotope activities was inversely proportional to the particle size. The highest concentrations of (223)Ra, (224)Ra, (226)Ra and (228)Ra in the water column were found in the bottom more saline waters and towards the inner of the estuary. These relatively high concentrations towards the bottom of the estuary may be attributed to the influence of tidally driven groundwater source and desorption from particles at the maximum turbidity zone. The apparent river water ages from the radium isotope ratios, (223)Ra/(224)Ra and (223)Ra/(228)Ra, indicate that the principal rivers that flow into the estuary have residence times from between 6 and 11days. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chimpanzee fauna isotopes provide new interpretations of fossil ape and hominin ecologies

PubMed Central

Nelson, Sherry V.

2013-01-01

Carbon and oxygen stable isotopes within modern and fossil tooth enamel record the aspects of an animal's diet and habitat use. This investigation reports the first isotopic analyses of enamel from a large chimpanzee community and associated fauna, thus providing a means of comparing fossil ape and early hominin palaeoecologies with those of a modern ape. Within Kibale National Park forest, oxygen isotopes differentiate primate niches, allowing for the first isotopic reconstructions of degree of frugivory versus folivory as well as use of arboreal versus terrestrial resources. In a comparison of modern and fossil community isotopic profiles, results indicate that Sivapithecus, a Miocene ape from Pakistan, fed in the forest canopy, as do chimpanzees, but inhabited a forest with less continuous canopy or fed more on leaves. Ardipithecus, an early hominin from Ethiopia, fed both arboreally and terrestrially in a more open habitat than inhabited by chimpanzees. PMID:24197413

Separation of sulfur isotopes

DOEpatents

DeWitt, Robert; Jepson, Bernhart E.; Schwind, Roger A.

1976-06-22

Sulfur isotopes are continuously separated and enriched using a closed loop reflux system wherein sulfur dioxide (SO.sub.2) is reacted with sodium hydroxide (NaOH) or the like to form sodium hydrogen sulfite (NaHSO.sub.3). Heavier sulfur isotopes are preferentially attracted to the NaHSO.sub.3, and subsequently reacted with sulfuric acid (H.sub.2 SO.sub.4) forming sodium hydrogen sulfate (NaHSO.sub.4) and SO.sub.2 gas which contains increased concentrations of the heavier sulfur isotopes. This heavy isotope enriched SO.sub.2 gas is subsequently separated and the NaHSO.sub.4 is reacted with NaOH to form sodium sulfate (Na.sub.2 SO.sub.4) which is subsequently decomposed in an electrodialysis unit to form the NaOH and H.sub.2 SO.sub.4 components which are used in the aforesaid reactions thereby effecting sulfur isotope separation and enrichment without objectionable loss of feed materials.

Feeding strategies for groundwater enhanced biodenitrification in an alluvial aquifer: chemical, microbial and isotope assessment of a 1D flow-through experiment.

PubMed

Vidal-Gavilan, G; Carrey, R; Solanas, A; Soler, A

2014-10-01

Nitrate-removal through enhanced in situ biodenitrification (EISB) is an existing alternative for the recovery of groundwater quality, and is often suggested for use in exploitation wells pumping at small flow-rates. Innovative approaches focus on wider-scale applications, coupling EISB with water-management practices and new monitoring tools. However, before this approach can be used, some water-quality issues such as the accumulation of denitrification intermediates and/or of reduced compounds from other anaerobic processes must be addressed. With such a goal, a flow-through experiment using 100mg-nitrate/L groundwater was built to simulate an EISB for an alluvial aquifer. Heterotrophic denitrification was induced through the periodic addition of a C source (ethanol), with four different C addition strategies being evaluated to improve the quality of the denitrified water. Chemical, microbial and isotope analyses of the water were performed. Biodenitrification was successfully stimulated by the daily addition of ethanol, easily achieving drinking water standards for both nitrate and nitrite, and showing an expected linear trend for nitrogen and oxygen isotope fractionation, with a εN/εO value of 1.1. Nitrate reduction to ammonium was never detected. Water quality in terms of remaining C, microbial counts, and denitrification intermediates was found to vary with the experimental time, and some secondary microbial respiration processes, mainly manganese reduction, were suspected to occur. Carbon isotope composition from the remaining ethanol also changed, from an initial enrichment in (13)C-ethanol compared to the value of the injected ethanol (-30.6‰), to a later depletion, achieving δ(13)C values well below the initial isotope composition (to a minimum of -46.7‰). This depletion in the heavy C isotope follows the trend of an inverse fractionation. Overall, our results indicated that most undesired effects on water quality may be controlled through the optimization of the C/N ratio determined from the amounts of injected ethanol vs. the amount of nitrate in groundwater, with a smaller C/N ratio causing a lower level of undesired impurities. Furthermore, the authors suggest that the biofilm life-time has a direct effect on microbial population and hence affects biodenitrification performance, influencing the accumulation of nitrite over time. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of a customized calibration unit for continuous measurements of the isotopic composition of water vapor

NASA Astrophysics Data System (ADS)

Moro, Giovanni; Zannoni, Daniele; Dreossi, Giuliano; Stenni, Barbara

2017-04-01

The objective of this work is the development, standardization and creation of a method to carry out continuous measurement of oxygen and hydrogen isotopic composition of the atmospheric water vapor using a wavelength-scanned cavity ring down spectroscopy (WS-CRDS) instrument produced by Picarro, L1102-i model. Some technical improvements of the standard instrument configuration have been made to create three different inlet gas lines: a "standard" line, a calibration line and a line connected with the external sampler. The calibration line is composed of a syringe-pump that continuously injects standard water into a steel tee heated at the temperature of 170°C and flushed with dry nitrogen gas. In this way, instantaneous and complete vaporization of the standard water takes place. The resulting steam is characterized by a well-defined composition in δD e δ18O values. To allow comparison with other international data, we have characterized the individual instrumental response to variation of the isotopic composition of the water vapor. Several humidity-isotope response functions (6000-26000 ppmv) have been estimated with three different internal standards (0.35‰ -8.75‰ -29.11‰ and -40.28‰ for δ18O; 2.31‰ -58.91‰ -222.19‰ and -317.78‰ for δD). Moreover, we have measured the instrumental drift at regular time intervals to apply the opportune corrections to instrument data. The setup has been tested using a 3.5 day continuous measurements carried out with the Picarro sampling the water vapor outside our campus in Venice and parallel sampling using the classical cryogenic trapping procedure, obtaining excellent results. Furthermore, our analysis technique has given good results for the standards with values which are similar to those obtained with the isotope ratio mass spectrometry (IRMS) technique.

Continuous profiles of microstructure, stable water isotopes and impurity content of the 2m snow pack from three polar drill sites

NASA Astrophysics Data System (ADS)

Freitag, Johannes; Schaller, Christoph; Kipfstuhl, Sepp; Hörhold, Maria; Schaidt, Maximilian; Sander, Merle; Moser, Dorothea

2017-04-01

Interpreting polar ice as climate archive requires profound knowledge about the formation of climate-proxies within the upper snow column. In order to investigate different impact factors on signal formation we performed a multiproxy- approach for 2m deep snow profiles by continuously measuring the 3D-microstructure using core-scale X-CT and the isotopic composition and impurity load in discrete samples of 1.1cm spatial resolution. The study includes profiles from a low-accumulation site on the East Antarctic plateau (Kohnen Station, DML), a typical medium-accumulation site on the North-East-Greenland ice sheet (EGRIP drilling camp) and a high-accumulation site on the Renland ice cap (East-coast of Greenland, RECAP drilling camp). Major observations are the tooth-shaped imprint of structural anisotropy and sulfate concentrations at the low accumulation site, the clear isotopic inter-annual variations that are in line with distinct impurity peaks at the high-accumulation site and the unexpected missing footprint of ice crusts and refrozen melt layers within the impurity- and isotope records for all sites.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1.3, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

Performance of alumina-supported Pt catalysts in an electron-beam-sustained CO2 laser amplifier

NASA Technical Reports Server (NTRS)

Cunningham, D. L.; Jones, P. L.; Miyake, C. I.; Moody, S. E.

1990-01-01

The performance of an alumina-supported Pt catalyst system used to maintain the gas purity in an electron-beam-sustained (636) isotope CO2 laser amplifier has been tested. The system characteristics using the two-zone, parallel flow reactor were determined for both continuous- and end-of-day reactor operation using on-line mass spectrometric sampling. The laser amplifier was run with an energy loading of typically 110 J-l/atm and an electron-beam current of 4 mA/sq cm. With these conditions and a pulse repetition frequency of 10 Hz for up to 10,000 shots, increases on the order of 100 ppm O2 were observed with the purifier on and 150 ppm with it off. The 1/e time recovery time was found to be approximately 75 minutes.

Processes controlling silicon isotopic fractionation in a forested tropical watershed: Mule Hole Critical Zone Observatory (Southern India)

NASA Astrophysics Data System (ADS)

Riotte, Jean; Meunier, Jean-Dominique; Zambardi, Thomas; Audry, Stéphane; Barboni, Doris; Anupama, Krishnamurthy; Prasad, Srinivasan; Chmeleff, Jérôme; Poitrasson, Franck; Sekhar, Muddu; Braun, Jean-Jacques

2018-05-01

Assessing the dynamics of the silica cycle in the critical zone remains challenging, particularly within the soil, where multiple processes are involved. To improve our understanding of this cycle in the Tropics, and more specifically the role played by vegetation, we combined elemental Si mass balance with the δ30Si signatures of the compartments involved in the water-plant-rock interactions of a tropical forested watershed, Mule Hole (Southern India). To accomplish this, we analysed (1) the δ30Si values of present-day litter phytoliths from tree leaves and grass, as well as soil amorphous silica (ASi); (2) the Si isotope fractionation induced by phytolith dissolution; (3) the silicon mass balance inferred from isotopes at the soil-plant scale; and (4) the consistency between water sources and the δ30Si signatures in the ephemeral stream. The δ30Si values of present-day litter phytoliths and soil ASi vary within a narrow range of 1.10-1.40‰ for all samples, but two deep vertisol samples which likely trapped phytoliths from different vegetation growing under more humid conditions, as indicated by pollen analysis. A homogeneous signature of litter is a minimum condition for using δ30Si as a proxy for the litter/phytolith source of Si. However, litter-ash dissolution experiments demonstrate that the incipient dissolution of phytoliths fractionates Si isotopes, with the preferential dissolution of 28Si over 30Si yielding δ30Si values as low as -1.41‰. Values close to the whole-sample signatures, i.e., above 1‰, were recovered in the solution after a few hours of water-ash interaction. At the soil-plant scale, the average δ30Si value of soil-infiltrating solutions is slightly lighter than the average phytolith signature, which suggests phytoliths as the source of soil dissolved Si. The isotopic budget of dissolved Si within the soil layer, which was obtained based on previous elemental fluxes, is imbalanced. Equilibrating the isotopic budget would imply that up to 4100 mol ha-1 yr-1 of silica is taken up by vegetation, which is almost twice as large as that initially estimated from the elemental budget. The additional Si flux taken up, and likely stored in woody stems, was estimated assuming that Si isotopes followed a steady-state model for the whole Si plant uptake and then followed a Rayleigh model once in the plants. The δ30Si value of the additional Si flux taken up should be close to 0‰, i.e., enriched in light Si isotopes compared to the litter. If steady-state conditions apply, the source could correspond to soil ASi dissolution or deep (saprolite) root uptake. At the outlet of the watershed, the stream exhibits low δ30Si values (0.28-0.71‰) during peak flows and high δ30Si values (1.29-1.61‰) during the recessions at the end of the rainy season. Heavy δ30Si signatures are consistent with the expected domination of seepage at the end of floods. The light δ30Si values during peak flow are slightly lower than the overland flow signature and reflect either a sampling bias of overland flow or a minor but significant contribution of another Si source within the stream, possibly the partial dissolution of phytoliths from the suspended load, with slight isotopic fractionation. This study confirms that vegetation controls the silicon cycle in this dry tropical forest. It also shows that silicon isotopes yield a better grasp of the mass balance and sources and potential mechanisms involved than the consideration of only silicon concentrations. However, this proxy still relies on working hypotheses, notably steady-state and/or Rayleigh fractionation models, which need to be confirmed in further studies.

Towards a novel continuous sublimation extraction/laser spectroscopy method for greenhouse gas measurements in the oldest ice

NASA Astrophysics Data System (ADS)

Bereiter, Bernhard; Maechler, Lars; Schmitt, Jochen; Walther, Remo; Tuzson, Béla; Scheidegger, Philipp; Emmenegger, Lukas; Fischer, Hubertus

2017-04-01

Ice cores are unique archives of ancient air providing the only direct record of past greenhouse gases - key in reconstructing the roles of greenhouse gases in past climate changes. The European Partnership in Ice Core Sciences (EuroPICS) plans to drill an ice core extending over 1.5 Ma, nearly doubling the time span of the existing greenhouse record and covering the time period of the Mid Pleistocene Transition. The ice covering the time interval from 1-1.5 Ma is expected to be close to the bedrock and, due to glacial flow, extremely thinned. A 10,000 yr glacial/interglacial transition can be compressed in 1 m of ice. The targeted 100 yr resolution therefore constrains the sample size to 15-30 g containing only 1-2ml STP air. Within the deepSlice project we aim to unlock such atmospheric archives in extremely thinned ice by developing a novel coupled semi-continuous sublimation extraction/laser spectroscopy system. Vacuum sublimation, with an infrared source, has been chosen as extraction method as it allows 100% gas extraction of all gas species from ice without changing the isotopic composition of CO2. In order to reduce ice waste and accelerate sample throughput, we are building a sublimation extraction system that is able to continuously sublimate an ice-core section and subsequently collect discrete full air samples. For the gas analytics, we develop a custom-made mid-infrared laser spectrometer allowing simultaneous measurement of the CO2, CH4 and N2O concentrations as well as the isotopic composition of CO2 on air samples of only 1-2 ml STP. The two systems will be coupled via cryo-trapping of the sample air in dip tubes, followed by expansion of the sample air into the laser spectrometer. Due to the nondestructive laser technique, the air sample can be recollected and reused for further analytics.

Inorganic Carbon Isotopes and Chemical Characterization of Watershed Drainages, Barrow, Alaska, 2013

DOE Data Explorer

Heikoop, Jeffrey H.; Throckmorton, Heather M.; Wilson, Cathy J.; Newman, Brent D.

2016-02-22

Data include results from geochemical and isotopic analyses for samples collected in Barrow, Alaska during July and September 2013. Samples were soil pore waters from 17 drainages that could be interlake (basins with polygonal terrain), different-aged drain thaw lake basins (young, medium, old, or ancient), or a combination of different aged basins. Samples taken in different drainage flow types at three different depths at each location in and around the Barrow Environmental Observatory.

Hydrological and geochemical processes constraining groundwater salinity in wetland areas related to evaporitic (karst) systems. A case study from Southern Spain

NASA Astrophysics Data System (ADS)

Gil-Márquez, J. M.; Barberá, J. A.; Andreo, B.; Mudarra, M.

2017-01-01

Chemical and isotopic evolution of groundwater in an evaporite karst plateau (including wetland areas and saline to hyper-saline springs) located at S Spain was studied. Physicochemical parameters, major ions and stable isotopes were analyzed in rain, brine spring, wetland and leakage water samples, from which the most common mineral saturation indexes were computed and geochemical and isotopic modelling were performed. Results show an apparent relationship between the elevation of brine springs and their water mineralization, indicating that drainage at higher altitude may be associated to gravity-driven flows, since brackish groundwater is isotopically fractionated due to evaporation. On the other hand, the lower altitude springs could drain deeper flows with longer residence time, resulting in highly mineralized and warmer (briny) groundwater. The dissolution of halite and gypsum has proved to be the main geochemical processes, which are favored by the great ionic strength of groundwater. Calcite precipitation occurs in brackish waters draining wetlands, being boosted by common ion effect (when CaSO4 waters are present) and solute concentration caused by evaporation. Modelling results strongly support the hypothesis that most of the selected springs geochemically evolve in a common (S-N) flowpath. The methods used in this research contribute to a better understanding of the hydrogeological processes occurring in the studied evaporitic system, but also in equivalent hydrological environments worldwide.

Strontium isotopic signatures of the streams and lakes of Taylor Valley, Southern Victoria Land, Antarctica: Chemical weathering in a polar climate

USGS Publications Warehouse

Lyons, W.B.; Nezat, C.A.; Benson, L.V.; Bullen, T.D.; Graham, E.Y.; Kidd, J.; Welch, K.A.

2002-01-01

We have collected and analyzed a series of water samples from three closed-basin lakes (Lakes Bonney, Fryxell, and Hoare) in Taylor Valley, Antarctica, and the streams that flow into them. In all three lakes, the hypolimnetic waters have different 87Sr/86Sr ratios than the surface waters, with the deep water of Lakes Fryxell and Hoare being less radiogenic than the surface waters. The opposite occurs in Lake Bonney. The Lake Fryxell isotopic ratios are lower than modern-day ocean water and most of the whole-rock ratios of the surrounding geologic materials. A conceivable source of Sr to the system could be either the Cenozoic volcanic rocks that make up a small portion of the till deposited in the valley during the Last Glacial Maximum or from marble derived from the local basement rocks. The more radiogenic ratios from Lake Bonney originate from ancient salt deposits that flow into the lake from Taylor Glacier and the weathering of minerals with more radiogenic Sr isotopic ratios within the tills. The Sr isotopic data from the streams and lakes of Taylor Valley strongly support the notion documented by previous investigators that chemical weathering has been, and is currently, a major process in determining the overall aquatic chemistry of these lakes in this polar desert environment.

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

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

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

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

Characterizing The Microbial Lability And Isotopic (14C, 13C) Signatures Of Marine Organic Matter With A Novel Culture Vessel System

NASA Astrophysics Data System (ADS)

Beaupre, S. R.; Mahmoudi, N.; Pearson, A.

2016-02-01

The rate at which non-living organic matter is respired in the ocean is an unconstrained and important property of the marine carbon cycle. Studies of inherent mineralization rates are complicated by the fact that marine organic matter is a mixture of compounds that vary in reactivity and concentration. While natural radiocarbon ages (14C, half-life = 5730 yr) have served as proxies for lability, they have not been used extensively to characterize that fraction of marine organic matter that is biologically accessible. To address this problem, we developed a novel batch culture system to monitor the time-dependent production rates and isotopic signatures of CO2 released during microbial degradation of natural organic matter. The system simulated a nepheloid layer by maintaining a slurry of decarbonated sediment and minimal media (M9) in a custom 2-liter culture vessel. The natural microbial community was allowed to develop within the sediment, and respired CO2 was continuously sparged from the medium with helium and oxygen, quantified in real time with an infrared gas analyzer, and isolated as a series of contiguous fractions for subsequent isotopic (∆14C, d13C) characterization. Control experiments indicated the accumulation of just 4.5 mg of background carbon per hour of continuous gas flow, which constituted ≤ 10 % of the respired carbon mass in each fraction. Since ∆14C values are conserved during molecular transformations, this low-blank system enables the detection of subtle shifts in the "age" of organic matter respired during the course of a culture experiment. Analyses of sediments from Falmouth, MA revealed both a variable CO2 production rate and an increase in post-bomb ∆14C values during a 10-day incubation. This suggests that the microbial lability of organic matter at this site decreased non-linearly with apparent 14C age, and that the least labile fraction observed was not more than 50 years old. These results underscore the complex relationship between microbial communities, organic matter composition, and its 14C age distribution.

24-Hour protein, arginine and citrulline metabolism in fed critically ill children – a stable isotope tracer study

PubMed Central

de Betue, Carlijn T.I.; Garcia Casal, Xiomara C.; van Waardenburg, Dick A.; Schexnayder, Stephen M.; Joosten, Koen F.M.; Deutz, Nicolaas E.P.; Engelen, Marielle P.K.J.

2017-01-01

Background & aims The reference method to study protein and arginine metabolism in critically ill children is measuring plasma amino acid appearances with stable isotopes during a short (4–8h) time period and extrapolate results to 24-hour. However, 24-hour measurements may be variable due to critical illness related factors and a circadian rhythm could be present. Since only short duration stable isotope studies in critically ill children have been conducted before, the aim of this study was to investigate 24-hour appearance of specific amino acids representing protein and arginine metabolism, with stable isotope techniques in continuously fed critically ill children. Methods In eight critically ill children, admitted to the pediatric (n=4) or cardiovascular (n=4) intensive care unit, aged 0–10 years, receiving continuous (par)enteral nutrition with protein intake 1.0–3.7 g/kg/day, a 24-hour stable isotope tracer protocol was carried out. L-[ring-2H5]-phenylalanine, L-[3,3-2H2]-tyrosine, L-[5,5,5-2H3]-leucine, L-[guanido-15N2]-arginine and L-[5-13C-3,3,4,4-2H4]-citrulline were infused intravenously and L-[15N]-phenylalanine and L-[1-13C]leucine enterally. Arterial blood was sampled every hour. Results Coefficients of variation, representing intra-individual variability, of the amino acid appearances of phenylalanine, tyrosine, leucine, arginine and citrulline were high, on average 14–19% for intravenous tracers and 23–26% for enteral tracers. No evident circadian rhythm was present. The pattern and overall 24-hour level of whole body protein balance differed per individual. Conclusions In continuously fed stable critically ill children, the amino acid appearances of phenylalanine, tyrosine, leucine, arginine and citrulline show high variability. This should be kept in mind when performing stable isotope studies in this population. There was no apparent circadian rhythm. PMID:28089618

Flow pattern and residence time of groundwater within the south-eastern Taoudeni sedimentary basin (Burkina Faso, Mali)

NASA Astrophysics Data System (ADS)

Huneau, F.; Dakoure, D.; Celle-Jeanton, H.; Vitvar, T.; Ito, M.; Traore, S.; Compaore, N. F.; Jirakova, H.; Le Coustumer, P.

2011-10-01

SummaryThe knowledge about groundwater flow conditions within the Southeastern Taoudeni Basin Aquifer shared by Burkina Faso and Mali is relatively limited with very little information on potentiometric heads, recharge processes, residence time and water quality. A better evaluation of groundwater resources in this area is a strategic point for water resources management in the entire Soudano-Sahelian region which endures since the beginning of the twentieth century a continuous decrease in precipitation amount. This paper provides a transboundary synthesis using water ( 18O, 2H and 3H) and carbon isotopes ( 13C and 14C) in conjunction with hydrogeological and hydrochemical data. The objectives are to improve the conceptual model of groundwater recharge and flow within this sandstone reservoir, and to assess the changes in the aquifer due to water abstraction and recent climate changes including an insight into Sahelian aquifers palaeorecharge processes. The local meteoric water line for the Bobo-Dioulasso station is proposed: δ 2H = 8.0 (±0.5)δ 18O + 10.2 (±2.1). Two main tendencies can be derived from groundwater chemistry. First, a slight evolution from the Ca-Mg-HCO 3 type towards a Na-K-HCO 3 type that indicates developed interactions between groundwater and clay minerals related to the residence time of groundwater. A second tendency towards Cl-NO 3-SO 4-HCO 3 water types indicates the anthropogenic influence on groundwater related to the poor sanitary conditions observed around wells. The carbon-14 activity measured on the TDIC varies between 0.3 and 122 pmC, so our record contains samples covering a wide period from Actual to Pleistocene suggesting a continuous recharge of the system through time even if the Sahel region has endured many different climate phases which have influenced the infiltration and recharge processes. All groundwater samples have stable isotope compositions in the range of the present day regional and global meteoric water line which suggests that the sampled groundwater was not significantly affected by evaporation during recharge. Evolved waters are depleted relative to unevolved samples by 1.5-2‰ in δ 18O and 10-15‰ in δ 2H. The whole dataset support the hypothesis of a largely unified homogeneous aquifer system with a multilayered structure but it also points out the very low renewability of the resource and a strong anthropogenic contamination of the shallowest horizons.

Groundwater, springs, and stream flow generation in an alpine meadow of a tropical glacierized catchment

NASA Astrophysics Data System (ADS)

Gordon, R.; Lautz, L. K.; McKenzie, J. M.; Mark, B. G.; Chavez, D.

2013-12-01

Melting tropical glaciers supply approximately half of dry season stream discharge in glacierized valleys of the Cordillera Blanca, Peru. The remainder of streamflow originates as groundwater stored in alpine meadows, moraines and talus slopes. A better understanding of the dynamics of alpine groundwater, including sources and contributions to streamflow, is important for making accurate estimates of glacial inputs to the hydrologic budget, and for our ability to make predictions about future water resources as glaciers retreat. Our field study, conducted during the dry season in the Llanganuco valley, focused on a 0.5-km2 alpine meadow complex at 4400 m elevation, which includes talus slopes, terminal moraines, and a debris fan. Two glacial lakes and springs throughout the complex feed a network of stream channels that flow across the meadow (~2 km total length). We combined tracer measurements of stream and spring discharge and groundwater-surface water exchange with synoptic sampling of water isotopic and geochemical composition, in order to characterize and quantify contributions to streamflow from different geomorphic features. Surface water inputs to the stream channels totaled 58 l/s, while the stream gained an additional 57 l/s from groundwater inputs. Water chemistry is primarily controlled by flowpath type (surface/subsurface) and length, as well as bedrock lithology, while stable water isotopic composition appears to be controlled by water source (glacial lake, meadow or deep groundwater). Stream water chemistry is most similar to meadow groundwater springs, but isotopic composition suggests that the majority of stream water, which issues from springs at the meadow/fan interface, is from the same glacial source as the up-gradient lake. Groundwater sampled from piezometers in confined meadow aquifers is unique in both chemistry and isotopic composition, but does not contribute a large percentage of stream water exiting this small meadow, as quantified by discharge measurements and isotopic mixing. However, we expect that as streams flow down through extensive meadows and wetlands in many Cordillera Blanca valleys, meadow groundwater is a more significant contributor to streamflow. Results from this small, high meadow in Llanganuco will be compared to a larger and lower-elevation meadow system in the Quilcayhuanca valley.

New Applications of Cosmogenic Radioactive Isotopes to Study Water Travel Times

NASA Astrophysics Data System (ADS)

Visser, A.; Thaw, M.; Deinhart, A.; Bibby, R. K.; Esser, B.

2017-12-01

The travel time of water moving through a landscape influences nutrient dynamics and biogeochemical cycles. Constraining water travel times helps to understand the functioning of the critical zone. Water travel times cannot be observed directly but can be constrained by measurements of cosmogenic radioactive isotopes. We studied a small (4.6 km2) subalpine (1660-2117 m) catchment in a Mediterranean climate (8 °C, 1200 mm/yr) in the California Sierra Nevada to assess subsurface water storage dynamics and investigate flow paths and flow velocities. We analyzed a combination of three cosmogenic radioactive isotopes with half-lives varying from 87 days (sulfur-35), 2.6 years (sodium-22) to 12.3 years (tritium) in precipitation and stream samples. Water stable isotopes and solute chemistry aided the interpretation of the cosmogenic isotopes. Tritium samples (1L) are analyzed by noble gas mass spectrometry after helium-3 accumulation. Samples for sulfur-35 and sodium-22 are collected by processing 20-1000 L of water through an anion and cation exchange column in-situ. Sulfur-35 is analyzed by liquid scintillation counting after chemical purification and precipitation. Sodium-22 is analyzed by gamma counting after eluting the cations into a 4L Marinelli beaker. Monthly collected precipitation samples show variability of deposition rate for tritium and sulfur-35. Sodium-22 levels in cumulative yearly precipitation samples are consistent with recent studies in the US and Japan. The observed variability of deposition rates complicates direct use as decaying age tracers. The level and variability of tritium in monthly stream samples indicate a mean residence time on the order of 10 years and only small contributions of younger water during high flow conditions. Sulfur-35 and sodium-22 concentrations were critically interpreted considering possible uptake by vegetation and cation exchange. Detections of sodium-22 confirm a small fraction of younger (< 5 years) water. Low concentrations of sulfur-35 suggest very small contributions of same-year snowmelt or precipitation. Results from two contrasting years (severe drought in 2015 and near-normal conditions in 2016) illustrate travel time responses to hydrological conditions and further characterize the catchment properties.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

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

PubMed

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

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

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

USGS Publications Warehouse

Borrok, D.M.; Wanty, R.B.; Ian, Ridley W.; Lamothe, P.J.; Kimball, B.A.; Verplanck, P.L.; Runkel, R.L.

2009-01-01

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, ??56Fe and ??66Zn isotopic signatures of filtered stream water samples varied by ???3.5??? and 0.4???, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in ??56Fe were linked to redox and precipitation reactions occurring in the stream, while changes in ??66Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<-2.0???) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4???). Acidic drainage from mine wastes contributed heavier dissolved Fe (???+0.5???) and lighter Zn (???+0.2???) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (??56Fe ??? 0???) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds. ?? 2009 Elsevier Ltd.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Effects of hydrological forcing on the structure of a tropical estuarine food web

Treesearch

Trisha B. Atwood; Tracy N. Wiegner; Richard A. MacKenzie

2012-01-01

River flow can impact which sources of particulate organic matter (POM) fuel estuarine food webs. Here, we used stable carbon (C) and nitrogen (N) isotope analyses to compare how contributions of diff erent POM sources (terrestrial, estuarine, and marine) to the diets of zooplankton and juvenile fishes differed between low and high river flow conditions, as well as...

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

NASA Technical Reports Server (NTRS)

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

1993-01-01

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

STABLE ISOTOPE GEOCHEMISTRY OF THERMAL FLUIDS FROM LASSEN VOLCANIC NATIONAL PARK, CALIFORNIA.

USGS Publications Warehouse

Janik, Cathy J.; Nehring, Nancy L.; Truesdell, Alfred H.

1983-01-01

In the Lassen vapor-dominated geothermal system, surface manifestations of thermal fluids at high elevations (1800-2500 m) include superheated and drowned fumaroles, steam-heated acid-sulfate hot springs, and low-chloride bicarbonate springs. Neutral high-chloride hot water discharges at lower elevations. Deuterium and oxygen-18 data establish genetic connections between these fluids and with local meteoric waters. Steam from the highest temperature fumarole at Bumpass Hell and water from the highest chloride hot spring have isotopic compositions corresponding to vapor-liquid equilibrium at 235 degree C. Carbon and sulfur isotope data suggest that the CO//2 and H//2S in the system did not entirely originate from magmatic sources, but probably include contributions from thermal metamorphism of marine sedimentary rocks. Observations suggest that carbon and sulfur isotope variations are useful indicators of gas reactions and flow paths in geothermal systems. Refs.

Nuclear astrophysics with radioactive ions at FAIR

NASA Astrophysics Data System (ADS)

Reifarth, R.; Altstadt, S.; Göbel, K.; Heftrich, T.; Heil, M.; Koloczek, A.; Langer, C.; Plag, R.; Pohl, M.; Sonnabend, K.; Weigand, M.; Adachi, T.; Aksouh, F.; Al-Khalili, J.; AlGarawi, M.; AlGhamdi, S.; Alkhazov, G.; Alkhomashi, N.; Alvarez-Pol, H.; Alvarez-Rodriguez, R.; Andreev, V.; Andrei, B.; Atar, L.; Aumann, T.; Avdeichikov, V.; Bacri, C.; Bagchi, S.; Barbieri, C.; Beceiro, S.; Beck, C.; Beinrucker, C.; Belier, G.; Bemmerer, D.; Bendel, M.; Benlliure, J.; Benzoni, G.; Berjillos, R.; Bertini, D.; Bertulani, C.; Bishop, S.; Blasi, N.; Bloch, T.; Blumenfeld, Y.; Bonaccorso, A.; Boretzky, K.; Botvina, A.; Boudard, A.; Boutachkov, P.; Boztosun, I.; Bracco, A.; Brambilla, S.; Briz Monago, J.; Caamano, M.; Caesar, C.; Camera, F.; Casarejos, E.; Catford, W.; Cederkall, J.; Cederwall, B.; Chartier, M.; Chatillon, A.; Cherciu, M.; Chulkov, L.; Coleman-Smith, P.; Cortina-Gil, D.; Crespi, F.; Crespo, R.; Cresswell, J.; Csatlós, M.; Déchery, F.; Davids, B.; Davinson, T.; Derya, V.; Detistov, P.; Diaz Fernandez, P.; DiJulio, D.; Dmitry, S.; Doré, D.; Dueñas, J.; Dupont, E.; Egelhof, P.; Egorova, I.; Elekes, Z.; Enders, J.; Endres, J.; Ershov, S.; Ershova, O.; Fernandez-Dominguez, B.; Fetisov, A.; Fiori, E.; Fomichev, A.; Fonseca, M.; Fraile, L.; Freer, M.; Friese, J.; Borge, M. G.; Galaviz Redondo, D.; Gannon, S.; Garg, U.; Gasparic, I.; Gasques, L.; Gastineau, B.; Geissel, H.; Gernhäuser, R.; Ghosh, T.; Gilbert, M.; Glorius, J.; Golubev, P.; Gorshkov, A.; Gourishetty, A.; Grigorenko, L.; Gulyas, J.; Haiduc, M.; Hammache, F.; Harakeh, M.; Hass, M.; Heine, M.; Hennig, A.; Henriques, A.; Herzberg, R.; Holl, M.; Ignatov, A.; Ignatyuk, A.; Ilieva, S.; Ivanov, M.; Iwasa, N.; Jakobsson, B.; Johansson, H.; Jonson, B.; Joshi, P.; Junghans, A.; Jurado, B.; Körner, G.; Kalantar, N.; Kanungo, R.; Kelic-Heil, A.; Kezzar, K.; Khan, E.; Khanzadeev, A.; Kiselev, O.; Kogimtzis, M.; Körper, D.; Kräckmann, S.; Kröll, T.; Krücken, R.; Krasznahorkay, A.; Kratz, J.; Kresan, D.; Krings, T.; Krumbholz, A.; Krupko, S.; Kulessa, R.; Kumar, S.; Kurz, N.; Kuzmin, E.; Labiche, M.; Langanke, K.; Lazarus, I.; Le Bleis, T.; Lederer, C.; Lemasson, A.; Lemmon, R.; Liberati, V.; Litvinov, Y.; Löher, B.; Lopez Herraiz, J.; Münzenberg, G.; Machado, J.; Maev, E.; Mahata, K.; Mancusi, D.; Marganiec, J.; Martinez Perez, M.; Marusov, V.; Mengoni, D.; Million, B.; Morcelle, V.; Moreno, O.; Movsesyan, A.; Nacher, E.; Najafi, M.; Nakamura, T.; Naqvi, F.; Nikolski, E.; Nilsson, T.; Nociforo, C.; Nolan, P.; Novatsky, B.; Nyman, G.; Ornelas, A.; Palit, R.; Pandit, S.; Panin, V.; Paradela, C.; Parkar, V.; Paschalis, S.; Pawłowski, P.; Perea, A.; Pereira, J.; Petrache, C.; Petri, M.; Pickstone, S.; Pietralla, N.; Pietri, S.; Pivovarov, Y.; Potlog, P.; Prokofiev, A.; Rastrepina, G.; Rauscher, T.; Ribeiro, G.; Ricciardi, M.; Richter, A.; Rigollet, C.; Riisager, K.; Rios, A.; Ritter, C.; Rodriguez Frutos, T.; Rodriguez Vignote, J.; Röder, M.; Romig, C.; Rossi, D.; Roussel-Chomaz, P.; Rout, P.; Roy, S.; Söderström, P.; Saha Sarkar, M.; Sakuta, S.; Salsac, M.; Sampson, J.; Sanchez, J.; Rio Saez, del; Sanchez Rosado, J.; Sanjari, S.; Sarriguren, P.; Sauerwein, A.; Savran, D.; Scheidenberger, C.; Scheit, H.; Schmidt, S.; Schmitt, C.; Schnorrenberger, L.; Schrock, P.; Schwengner, R.; Seddon, D.; Sherrill, B.; Shrivastava, A.; Sidorchuk, S.; Silva, J.; Simon, H.; Simpson, E.; Singh, P.; Slobodan, D.; Sohler, D.; Spieker, M.; Stach, D.; Stan, E.; Stanoiu, M.; Stepantsov, S.; Stevenson, P.; Strieder, F.; Stuhl, L.; Suda, T.; Sümmerer, K.; Streicher, B.; Taieb, J.; Takechi, M.; Tanihata, I.; Taylor, J.; Tengblad, O.; Ter-Akopian, G.; Terashima, S.; Teubig, P.; Thies, R.; Thoennessen, M.; Thomas, T.; Thornhill, J.; Thungstrom, G.; Timar, J.; Togano, Y.; Tomohiro, U.; Tornyi, T.; Tostevin, J.; Townsley, C.; Trautmann, W.; Trivedi, T.; Typel, S.; Uberseder, E.; Udias, J.; Uesaka, T.; Uvarov, L.; Vajta, Z.; Velho, P.; Vikhrov, V.; Volknandt, M.; Volkov, V.; von Neumann-Cosel, P.; von Schmid, M.; Wagner, A.; Wamers, F.; Weick, H.; Wells, D.; Westerberg, L.; Wieland, O.; Wiescher, M.; Wimmer, C.; Wimmer, K.; Winfield, J. S.; Winkel, M.; Woods, P.; Wyss, R.; Yakorev, D.; Yavor, M.; Zamora Cardona, J.; Zartova, I.; Zerguerras, T.; Zgura, M.; Zhdanov, A.; Zhukov, M.; Zieblinski, M.; Zilges, A.; Zuber, K.

2016-01-01

The nucleosynthesis of elements beyond iron is dominated by neutron captures in the s and r processes. However, 32 stable, proton-rich isotopes cannot be formed during those processes, because they are shielded from the s-process flow and r-process, β-decay chains. These nuclei are attributed to the p and rp process. For all those processes, current research in nuclear astrophysics addresses the need for more precise reaction data involving radioactive isotopes. Depending on the particular reaction, direct or inverse kinematics, forward or time-reversed direction are investigated to determine or at least to constrain the desired reaction cross sections. The Facility for Antiproton and Ion Research (FAIR) will offer unique, unprecedented opportunities to investigate many of the important reactions. The high yield of radioactive isotopes, even far away from the valley of stability, allows the investigation of isotopes involved in processes as exotic as the r or rp processes.

Partitioning water and carbon fluxes in a Mediterranean oak woodland using stable oxygen isotopes

NASA Astrophysics Data System (ADS)

Dubbert, Maren; Piayda, Arndt; Cuntz, Matthias; Correia, Alexandra; Silva, Filipe Costa e.; Pereira, Joao; Werner, Christiane

2014-05-01

Water is a key factor driving ecosystem productivity, especially in water-limited ecosystems. A separation of the component fluxes is needed to gain a functional understanding on the development of net ecosystem water fluxes and their coupling with biogeochemical cycles. Oxygen isotope signatures are valuable tracers for water movements within the ecosystem because of the distinct isotopic compositions of water in soil and vegetation. In the past, determination of isotopic signatures of evaporative or transpirational fluxes has been challenging since measurements of water vapor isotopes were difficult to obtain using cold-trap methods, delivering data with low time resolution. Recent developments in laser spectroscopy now enable direct high frequency measurements of the isotopic composition of atmospheric water vapor (δv), evapotranspiration (δET), and its components and allow validations of common modeling approaches for estimating δE and δT based on Craig and Gordon (1965). Here, a novel approach was used, combining a custom build flow-through gas-exchange branch chamber with a Cavity Ring-Down Spectrometer in a Mediteranean cork-oak woodland where two vegetation layers respond differently to drought: oak-trees (Quercus suber L.) avoid drought due to their access to ground water while herbaceous plants survive the summer as seeds. We aimed at 1) testing the Craig and Gordon equation for soil evaporation against directly measured δE and 2) quantifying the role of non-steady-state transpiration under natural conditions. Thirdly, we used this approach to quantify the impact of the understory herbaceous vegetation on ecosystem carbon and water fluxes throughout the year and disentangle how ET components of the ecosystem relate to carbon dioxide exchange. We present one year data comparing modeled and measured stable oxygen isotope signatures (δ18O) of soil evaporation, confirming that the Craig and Gordon equation leads to good agreement with measured δ18O of evaporation (Dubbert et al. 2013). Moreover, we found continuously strong deviations from isotopic steady-state in plant transpiration combined with large isoforcing on the atmosphere. This implies that assuming plant transpiration to be in the steady-state can have a huge impact at least for studies that distinguish relatively short time intervals (hours, e.g. partitioning studies). Finally. partitioning ecosystem ET and NEE into its three sources revealed a strong contribution of soil evaporation (E) and herbaceous transpiration (T) to ecosystem ET during spring and fall. In contrast, soil respiration (R) and herbaceous net carbon gain contributed to a lesser amount to ecosystem NEE during spring and fall, leading to consistently smaller water use efficiencies (WUE) of the herbaceous understory compared to the cork-oaks. Craig H, Gordon, LI. 1965. Deuterium and oxygen-18 variations in the ocean and the marine atmosphere. Paper presented at the Stable Isotopes in Oceanographic Studies and Paleotemperatures, Spoleto, Italy. Dubbert M, Cuntz M, Piayda A, Maguas C, Werner C, 2013: Partitioning evapotranspiration - Testing the Craig and Gordon model with field measurements of oxygen isotope ratios of evaporative fluxes. J Hydrol.

Dansgaard-Oeschger cycles observed in the Greenland ReCAP ice core project

NASA Astrophysics Data System (ADS)

Kjær, Helle Astrid; Vallelonga, Paul; Vinther, Bo; Simonsen, Marius; Maffezzoli, Niccoló; Gkinis, Vasileios; Svensson, Anders; Jensen, Camilla Marie; Dallmayr, Remi; Spolaor, Andrea; Edwards, Ross

2017-04-01

The new REnland ice CAP (RECAP) ice core was drilled in summer 2015 in Greenland and measured by means of Continuous flow analysis (CFA) during the last 3 months of 2015. The Renland ice core was obtained as part of the ReCAP project, extending 584.11 meters to the bottom of the Renland ice cap located in east Greenland. The unique position on a mountain saddle above 2000 meters altitude, but close to the coast, ensures that the Renland ice core offers high accumulation, but also reaches far back in time. Results show that despite the short length the RECAP ice core holds ice all the way back to the past warm interglacial period, the Eemian. The glacial section is strongly thinned and covers on 20 meters of the ReCAP core, but nonetheless due to the high resolution of the measurements all 25 expected DO events could be identified. The record was analyzed for multiple elements including the water isotopes, forest fire tracers NH4+ and black carbon, insoluble dust particles by means of Abakus laser particle counter and the dust ion Ca2+, sea salt Na+, and sea ice proxies as well as acidity useful for finding volcanic layers to date the core. Below the glacial section another 20 meters of warm Eemian ice have been analysed. Here we present the chemistry results as obtained by continuous flow analysis (CFA) and compare the glacial section with the chemistry profile from other Greenland ice cores.

Improved radiocarbon analyses of modern human hair to determine the year-of-death by cross-flow nanofiltered amino acids: common contaminants, implications for isotopic analysis, and recommendations.

PubMed

Santos, Guaciara M; De La Torre, Hector A Martinez; Boudin, Mathieu; Bonafini, Marco; Saverwyns, Steven

2015-10-15

In forensic investigation, radiocarbon ((14)C) measurements of human tissues (i.e., nails and hair) can help determine the year-of-death. However, the frequent use of cosmetics can bias hair (14)C results as well as stable isotope values. Evidence shows that hair exogenous impurities percolate beyond the cuticle layer, and therefore conventional pretreatments are ineffective in removing them. We conducted isotopic analysis ((14)C, δ(13)C, δ(15)N and C/N) of conventionally treated and cross-flow nanofiltered amino acid (CFNAA)-treated samples (scalp- and body-hair) from a single female subject using fingernails as a reference. The subject studied frequently applies a permanent dark-brown dye kit to her scalp-hair and uses other care products for daily cleansing. We also performed pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) analyses of CFNAA-treated scalp-hair to identify contaminant remnants that could possibly interfere with isotopic analyses. The conventionally treated scalp- and body-hair showed (14)C offsets of ~21‰ and ~9‰, respectively. These offsets confirm the contamination by petrochemicals in modern human hair. A single CFNAA extraction reduced those offsets by ~34%. No significant improvement was observed when sequential extractions were performed, as it appears that the procedure introduced some foreign contaminants. A chromatogram of the CFNAA scalp-hair pyrolysis products showed the presence of petroleum and plant/animal compound residues, which can bias isotopic analyses. We have demonstrated that CFNAA extractions can partially remove cosmetic contaminants embedded in human hair. We conclude that fingernails are still the best source of keratin protein for year-of-death determinations and isotopic analysis, with body-hair and/or scalp-hair coupled with CFNAA extraction a close second. Copyright © 2015 John Wiley & Sons, Ltd.

Development of an on-line flow injection Sr/matrix separation method for accurate, high-throughput determination of Sr isotope ratios by multiple collector-inductively coupled plasma-mass spectrometry.

PubMed

Galler, Patrick; Limbeck, Andreas; Boulyga, Sergei F; Stingeder, Gerhard; Hirata, Takafumi; Prohaska, Thomas

2007-07-01

This work introduces a newly developed on-line flow injection (FI) Sr/Rb separation method as an alternative to the common, manual Sr/matrix batch separation procedure, since total analysis time is often limited by sample preparation despite the fast rate of data acquisition possible by inductively coupled plasma-mass spectrometers (ICPMS). Separation columns containing approximately 100 muL of Sr-specific resin were used for on-line FI Sr/matrix separation with subsequent determination of (87)Sr/(86)Sr isotope ratios by multiple collector ICPMS. The occurrence of memory effects exhibited by the Sr-specific resin, a major restriction to the repetitive use of this costly material, could successfully be overcome. The method was fully validated by means of certified reference materials. A set of two biological and six geological Sr- and Rb-bearing samples was successfully characterized for its (87)Sr/(86)Sr isotope ratios with precisions of 0.01-0.04% 2 RSD (n = 5-10). Based on our measurements we suggest (87)Sr/(86)Sr isotope ratios of 0.713 15 +/- 0.000 16 (2 SD) and 0.709 31 +/- 0.000 06 (2 SD) for the NIST SRM 1400 bone ash and the NIST SRM 1486 bone meal, respectively. Measured (87)Sr/(86)Sr isotope ratios for five basalt samples are in excellent agreement with published data with deviations from the published value ranging from 0 to 0.03%. A mica sample with a Rb/Sr ratio of approximately 1 was successfully characterized for its (87)Sr/(86)Sr isotope signature to be 0.718 24 +/- 0.000 29 (2 SD) by the proposed method. Synthetic samples with Rb/Sr ratios of up to 10/1 could successfully be measured without significant interferences on mass 87, which would otherwise bias the accuracy and uncertainty of the obtained data.

Linear model describing three components of flow in karst aquifers using 18O data

USGS Publications Warehouse

Long, Andrew J.; Putnam, L.D.

2004-01-01

The stable isotope of oxygen, 18O, is used as a naturally occurring ground-water tracer. Time-series data for ??18O are analyzed to model the distinct responses and relative proportions of the conduit, intermediate, and diffuse flow components in karst aquifers. This analysis also describes mathematically the dynamics of the transient fluid interchange between conduits and diffusive networks. Conduit and intermediate flow are described by linear-systems methods, whereas diffuse flow is described by mass-balance methods. An automated optimization process estimates parameters of lognormal, Pearson type III, and gamma distributions, which are used as transfer functions in linear-systems analysis. Diffuse flow and mixing parameters also are estimated by these optimization methods. Results indicate the relative proximity of a well to a main conduit flowpath and can help to predict the movement and residence times of potential contaminants. The three-component linear model is applied to five wells, which respond to changes in the isotopic composition of point recharge water from a sinking stream in the Madison aquifer in the Black Hills of South Dakota. Flow velocities as much as 540 m/d and system memories of as much as 71 years are estimated by this method. Also, the mean, median, and standard deviation of traveltimes; time to peak response; and the relative fraction of flow for each of the three components are determined for these wells. This analysis infers that flow may branch apart and rejoin as a result of an anastomotic (or channeled) karst network.

Soil CO2 emissions as a proxy for heat and mass flow assessment, Taupō Volcanic Zone, New Zealand

USGS Publications Warehouse

Bloomberg, S.; Werner, Cynthia A.; Rissmann, C.F.; Mazot, A.; Horton, Travis B.; Gravley, D; Kennedy, B.; Oze, C

2014-01-01

The quantification of heat and mass flow between deep reservoirs and the surface is important for understanding magmatic and hydrothermal systems. Here, we use high-resolution measurement of carbon dioxide flux (φCO2) and heat flow at the surface to characterize the mass (CO2 and steam) and heat released to the atmosphere from two magma-hydrothermal systems. Our soil gas and heat flow surveys at Rotokawa and White Island in the Taupō Volcanic Zone, New Zealand, include over 3000 direct measurements of φCO2 and soil temperature and 60 carbon isotopic values on soil gases. Carbon dioxide flux was separated into background and magmatic/hydrothermal populations based on the measured values and isotopic characterization. Total CO2 emission rates (ΣCO2) of 441 ± 84 t d−1 and 124 ± 18 t d−1were calculated for Rotokawa (2.9 km2) and for the crater floor at White Island (0.3 km2), respectively. The total CO2 emissions differ from previously published values by +386 t d−1 at Rotokawa and +25 t d−1 at White Island, demonstrating that earlier research underestimated emissions by 700% (Rotokawa) and 25% (White Island). These differences suggest that soil CO2 emissions facilitate more robust estimates of the thermal energy and mass flux in geothermal systems than traditional approaches. Combining the magmatic/hydrothermal-sourced CO2 emission (constrained using stable isotopes) with reservoir H2O:CO2mass ratios and the enthalpy of evaporation, the surface expression of thermal energy release for the Rotokawa hydrothermal system (226 MWt) is 10 times greater than the White Island crater floor (22.5 MWt).

A geochemical approach to determine sources and movement of saline groundwater in a coastal aquifer

USGS Publications Warehouse

Anders, Robert; Mendez, Gregory O.; Futa, Kiyoto; Danskin, Wesley R.

2014-01-01

Geochemical evaluation of the sources and movement of saline groundwater in coastal aquifers can aid in the initial mapping of the subsurface when geological information is unavailable. Chloride concentrations of groundwater in a coastal aquifer near San Diego, California, range from about 57 to 39,400 mg/L. On the basis of relative proportions of major-ions, the chemical composition is classified as Na-Ca-Cl-SO4, Na-Cl, or Na-Ca-Cl type water. δ2H and δ18O values range from −47.7‰ to −12.8‰ and from −7.0‰ to −1.2‰, respectively. The isotopically depleted groundwater occurs in the deeper part of the coastal aquifer, and the isotopically enriched groundwater occurs in zones of sea water intrusion. 87Sr/86Sr ratios range from about 0.7050 to 0.7090, and differ between shallower and deeper flow paths in the coastal aquifer. 3H and 14C analyses indicate that most of the groundwater was recharged many thousands of years ago. The analysis of multiple chemical and isotopic tracers indicates that the sources and movement of saline groundwater in the San Diego coastal aquifer are dominated by: (1) recharge of local precipitation in relatively shallow parts of the flow system; (2) regional flow of recharge of higher-elevation precipitation along deep flow paths that freshen a previously saline aquifer; and (3) intrusion of sea water that entered the aquifer primarily during premodern times. Two northwest-to-southeast trending sections show the spatial distribution of the different geochemical groups and suggest the subsurface in the coastal aquifer can be separated into two predominant hydrostratigraphic layers.

Submarine radial vents on Mauna Loa Volcano, Hawaìi

NASA Astrophysics Data System (ADS)

Wanless, V. Dorsey; Garcia, M. O.; Trusdell, F. A.; Rhodes, J. M.; Norman, M. D.; Weis, Dominique; Fornari, D. J.; Kurz, M. D.; Guillou, Hervé

2006-05-01

A 2002 multibeam sonar survey of Mauna Loa's western flank revealed ten submarine radial vents and three submarine lava flows. Only one submarine radial vent was known previously. The ages of these vents are constrained by eyewitness accounts, geologic relationships, Mn-Fe coatings, and geochemical stratigraphy; they range from 128 years B.P. to possibly 47 ka. Eight of the radial vents produced degassed lavas despite eruption in water depths sufficient to inhibit sulfur degassing. These vents formed truncated cones and short lava flows. Two vents produced undegassed lavas that created "irregular" cones and longer lava flows. Compositionally and isotopically, the submarine radial vent lavas are typical of Mauna Loa lavas, except two cones that erupted alkalic lavas. He-Sr isotopes for the radial vent lavas follow Mauna Loa's evolutionary trend. The compositional and isotopic heterogeneity of these lavas indicates most had distinct parental magmas. Bathymetry and acoustic backscatter results, along with photography and sampling during four JASON2 dives, are used to produce a detailed geologic map to evaluate Mauna Loa's submarine geologic history. The new map shows that the 1877 submarine eruption was much larger than previously thought, resulting in a 10% increase for recent volcanism. Furthermore, although alkalic lavas were found at two radial vents, there is no systematic increase in alkalinity among these or other Mauna Loa lavas as expected for a dying volcano. These results refute an interpretation that Mauna Loa's volcanism is waning. The submarine radial vents and flows cover 29 km2 of seafloor and comprise a total volume of ˜2 × 109 m3 of lava, reinforcing the idea that submarine lava eruptions are important in the growth of oceanic island volcanoes even after they emerged above sea level.