Atomic vapor laser isotope separation process

DOEpatents

Wyeth, R.W.; Paisner, J.A.; Story, T.

1990-08-21

A laser spectroscopy system is utilized in an atomic vapor laser isotope separation process. The system determines spectral components of an atomic vapor utilizing a laser heterodyne technique. 23 figs.

Exploiting Diffusion Barrier and Chemical Affinity of Metal-Organic Frameworks for Efficient Hydrogen Isotope Separation.

PubMed

Kim, Jin Yeong; Balderas-Xicohténcatl, Rafael; Zhang, Linda; Kang, Sung Gu; Hirscher, Michael; Oh, Hyunchul; Moon, Hoi Ri

2017-10-25

Deuterium plays a pivotal role in industrial and scientific research, and is irreplaceable for various applications such as isotope tracing, neutron moderation, and neutron scattering. In addition, deuterium is a key energy source for fusion reactions. Thus, the isolation of deuterium from a physico-chemically almost identical isotopic mixture is a seminal challenge in modern separation technology. However, current commercial approaches suffer from extremely low separation efficiency (i.e., cryogenic distillation, selectivity of 1.5 at 24 K), requiring a cost-effective and large-scale separation technique. Herein, we report a highly effective hydrogen isotope separation system based on metal-organic frameworks (MOFs) having the highest reported separation factor as high as ∼26 at 77 K by maximizing synergistic effects of the chemical affinity quantum sieving (CAQS) and kinetic quantum sieving (KQS). For this purpose, the MOF-74 system having high hydrogen adsorption enthalpies due to strong open metal sites is chosen for CAQS functionality, and imidazole molecules (IM) are employed to the system for enhancing the KQS effect. To the best of our knowledge, this work is not only the first attempt to implement two quantum sieving effects, KQS and CAQS, in one system, but also provides experimental validation of the utility of this system for practical industrial usage by isolating high-purity D 2 through direct selective separation studies using 1:1 D 2 /H 2 mixtures.

European Bison as a Refugee Species? Evidence from Isotopic Data on Early Holocene Bison and Other Large Herbivores in Northern Europe

PubMed Central

Bocherens, Hervé; Hofman-Kamińska, Emilia; Drucker, Dorothée G.; Schmölcke, Ulrich; Kowalczyk, Rafał

2015-01-01

According to the refugee species concept, increasing replacement of open steppe by forest cover after the last glacial period and human pressure had together forced European bison (Bison bonasus)—the largest extant terrestrial mammal of Europe—into forests as a refuge habitat. The consequent decreased fitness and population density led to the gradual extinction of the species. Understanding the pre-refugee ecology of the species may help its conservation management and ensure its long time survival. In view of this, we investigated the abundance of stable isotopes (δ13C and δ15N) in radiocarbon dated skeletal remains of European bison and other large herbivores—aurochs (Bos primigenius), moose (Alces alces), and reindeer (Rangifer tarandus)—from the Early Holocene of northern Europe to reconstruct their dietary habits and pattern of habitat use in conditions of low human influence. Carbon and nitrogen isotopic compositions in collagen of the ungulate species in northern central Europe during the Early Holocene showed significant differences in the habitat use and the diet of these herbivores. The values of the δ13C and δ15N isotopes reflected the use of open habitats by bison, with their diet intermediate between that of aurochs (grazer) and of moose (browser). Our results show that, despite the partial overlap in carbon and nitrogen isotopic values of some species, Early Holocene large ungulates avoided competition by selection of different habitats or different food sources within similar environments. Although Early Holocene bison and Late Pleistocene steppe bison utilized open habitats, their diets were significantly different, as reflected by their δ15N values. Additional isotopic analyses show that modern populations of European bison utilize much more forested habitats than Early Holocene bison, which supports the refugee status of the species. PMID:25671634

Method for discriminative particle selection

DOEpatents

Post, Richard F.

1992-01-01

The invention is a method and means for separating ions or providing an ion beam. The invention generates ions of the isotopes to be separated, and then provides a traveling electric potential hill created by a sequential series of quasi static electric potential hills. By regulating the velocity and potential amplitude of the traveling electric potential hill ionized isotopes are selectively positively or negatively accelerated. Since the ionized isotopes have differing final velocities, the isotopes may be collected separately or used to produce an ion beam of a selected isotope.

Variation in fluxes estimated from nitrogen isotope discrimination corresponds with independent measures of nitrogen flux in Populus balsamifera L.

PubMed

Kalcsits, Lee A; Guy, Robert D

2016-02-01

Acquisition of mineral nitrogen by roots from the surrounding environment is often not completely efficient, in which a variable amount of leakage (efflux) relative to gross uptake (influx) occurs. The efflux/influx ratio (E/I) is, therefore, inversely related to the efficiency of nutrient uptake at the root level. Time-integrated estimates of E/I and other nitrogen-use traits may be obtainable from variation in stable isotope ratios or through compartmental analysis of tracer efflux (CATE) using radioactive or stable isotopes. To compare these two methods, Populus balsamifera L. genotypes were selected, a priori, for high or low nitrogen isotope discrimination. Vegetative cuttings were grown hydroponically, and E/I was calculated using an isotope mass balance model (IMB) and compared to E/I calculated using (15) N CATE. Both methods indicated that plants grown with ammonium had greater E/I than nitrate-grown plants. Genotypes with high or low E/I using CATE also had similarly high or low estimates of E/I using IMB, respectively. Genotype-specific means were linearly correlated (r = 0.77; P = 0.0065). Discrepancies in E/I between methods may reflect uncertainties in discrimination factors for the assimilatory enzymes, or temporal differences in uptake patterns. By utilizing genotypes with known variation in nitrogen isotope discrimination, a relationship between nitrogen isotope discrimination and bidirectional nitrogen fluxes at the root level was observed. © 2015 John Wiley & Sons Ltd.

Method for isotope separation by photodeflection

DOEpatents

Bernhardt, Anthony F.

1977-01-01

In the method of separating isotopes wherein a desired isotope species is selectively deflected out of a beam of mixed isotopes by irradiating the beam with a directed beam of light of narrowly defined frequency which is selectively absorbed by the desired species, the improvement comprising irradiating the deflected beam with light from other light sources whose frequencies are selected to cause the depopulation of any metastable excited states.

Novel diagnostics of metabolic dysfunction detected in breath and plasma by selective isotope-assisted labeling.

PubMed

Haviland, Julia A; Tonelli, Marco; Haughey, Dermot T; Porter, Warren P; Assadi-Porter, Fariba M

2012-08-01

Metabolomics is the study of a unique fingerprint of small molecules present in biological systems under healthy and disease conditions. One of the major challenges in metabolomics is validation of fingerprint molecules to identify specifically perturbed pathways in metabolic aberrations. This step is crucial to the understanding of budding metabolic pathologies and the ability to identify early indicators of common diseases such as obesity, type 2 diabetes mellitus, metabolic syndrome, polycystic ovary syndrome, and cancer. We present a novel approach to diagnosing aberrations in glucose utilization including metabolic pathway switching in a disease state. We used a well-defined prenatally exposed glucocorticoid mouse model that results in adult females with metabolic dysfunction. We applied the complementary technologies of nuclear magnetic resonance spectroscopy and cavity ring-down spectroscopy to analyze serial plasma samples and real-time breath measurements following selective (13)C-isotope-assisted labeling. These platforms allowed us to trace metabolic markers in whole animals and identify key metabolic pathway switching in prenatally glucocorticoid-treated animals. Total glucose flux is significantly proportionally increased through the major oxidative pathways of glycolysis and the pentose phosphate pathway in the prenatally glucocorticoid-treated animals relative to the control animals. This novel diagnostics approach is fast, noninvasive, and sensitive for determining specific pathway utilization, and provides a direct translational application in the health care field. Copyright © 2012 Elsevier Inc. All rights reserved.

Method for laser induced isotope enrichment

DOEpatents

Pronko, Peter P.; Vanrompay, Paul A.; Zhang, Zhiyu

2004-09-07

Methods for separating isotopes or chemical species of an element and causing enrichment of a desired isotope or chemical species of an element utilizing laser ablation plasmas to modify or fabricate a material containing such isotopes or chemical species are provided. This invention may be used for a wide variety of materials which contain elements having different isotopes or chemical species.

Fuel preparation for use in the production of medical isotopes

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

Policke, Timothy A.; Aase, Scott B.; Stagg, William R.

The present invention relates generally to the field of medical isotope production by fission of uranium-235 and the fuel utilized therein (e.g., the production of suitable Low Enriched Uranium (LEU is uranium having 20 weight percent or less uranium-235) fuel for medical isotope production) and, in particular to a method for producing LEU fuel and a LEU fuel product that is suitable for use in the production of medical isotopes. In one embodiment, the LEU fuel of the present invention is designed to be utilized in an Aqueous Homogeneous Reactor (AHR) for the production of various medical isotopes including, butmore » not limited to, molybdenum-99, cesium-137, iodine-131, strontium-89, xenon-133 and yttrium-90.« less

Approaches to Plant Hydrogen and Oxygen Isoscapes Generation

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

West, Jason B.; Kreuzer-Martin, Helen W.; Ehleringer, James

2009-12-01

Plant hydrogen and oxygen isoscapes have been utilized to address important and somewhat disparate research goals. The isotopic composition of leaf water affects the isotopic composition of atmospheric CO2 and O2 and is a logical starting point for understanding the isotopic composition of plant organic compounds since photosynthesis occurs in the leaf water environment. Leaf water isoscapes have been produced largely as part of efforts to understand atmospheric gas isotopic composition. The isotopic composition of plant organic matter has also been targeted for its potential to serve as a proxy for past environmental conditions. Spatially distributed sampling and modeling ofmore » modern plant H & O isoscapes can improve our understanding of the controls of the isotope ratios of compounds such as cellulose or n-alkanes from plants and therefore their utility for paleoreconstructions. Spatially varying plant hydrogen and oxygen isotopes have promise for yielding geographic origin information for a variety of plant products, including objects of criminal forensic interest or food products. The future has rich opportunities for the continued development of mechanistic models, methodologies for the generation of hydrogen and oxygen isoscapes, and cross-disciplinary interactions as these tools for understanding are developed, shared, and utilized to answer large-scale questions.« less

The utility of arginine-citrulline stable isotope tracer infusion technique in the assessment of nitric oxide production in MELAS syndrome

USDA-ARS?s Scientific Manuscript database

The correspondence titled “Analytical challenges in the assessment of NO synthesis from L-arginine in the MELAS syndrome” suggested challenges that can limit the utility of stable isotope infusion methodology in assessing NO production....

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

NASA Astrophysics Data System (ADS)

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

2010-12-01

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

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

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

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

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

APPLICATIONS OF ENVIRONMENTAL ISOTOPES FOR WATERSHED INVESTIGATIONS

EPA Science Inventory

Environmental isotopes include naturally-occurring nuclides that can be applied as tracers within watersheds (Sidle, 1998). Recent advances in mass spectroscopy may supplant many traditional and costly hydrometric techniques. It is now possible, for example, to utilize isotopes a...

Preparation of isotopic molybdenum foils utilizing small quantities of material

NASA Astrophysics Data System (ADS)

Lipski, A. R.; Lee, L. L.; Liang, J. F.; Mahon, J. C.

1993-09-01

A simple method utilizing a small amount of isotopic material for production of molybdenum foils is discussed. An e-gun is used in the procedure. The Mo powder undergoes reduction-sintering and melting-solidifying steps leading to the creation of a metallic droplet suitable for further cold rolling or vacuum deposition.

Breath carbon stable isotope ratios identify changes in energy balance and substrate utilization in humans

USDA-ARS?s Scientific Manuscript database

Rapid detection of shifts in substrate utilization and energy balance would provide a compelling biofeedback tool to enable individuals to lose weight. In a pilot study, we tested whether the natural abundance of exhaled carbon stable isotope ratios (breath d13C values) reflects shifts between negat...

STABLE ISOTOPIC EVIDENCE OF CARBON AND NITROGEN USE IN CULTURED ECTOMYCORRHIZAL AND SAPROTROPHIC FUNGI

EPA Science Inventory

Stable isotopes in sporocarps have proven useful for inferring ectomycorrhizal or saprotrophic status and understanding carbon (C) and nitrogen (N) utilization. However, greater understanding of processes producing isotopic concentrations is needed. We measured natural abundanc...

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, J.D.; Meikrantz, D.H.; Tuggle, D.G.

1997-09-23

A method and apparatus are disclosed for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes. 15 figs.

Method for the purification of noble gases, nitrogen and hydrogen

DOEpatents

Baker, John D.; Meikrantz, David H.; Tuggle, Dale G.

1997-01-01

A method and apparatus for the purification and collection of hydrogen isotopes in a flowing inert gaseous mixture containing impurities, wherein metal alloy getters having the capability of sorbing non-hydrogen impurities such as oxygen, carbon dioxide, carbon monoxide, methane, ammonia, nitrogen and water vapor are utilized to purify the gaseous mixture of impurities. After purification hydrogen isotopes may be more efficiently collected. A plurality of parallel process lines utilizing metal getter alloys can be used to provide for the continuous purification and collection of the hydrogen isotopes.

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotopes in phosphate

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

Jaisi, Deb P.; Kukkadapu, Ravi K.; Stout, Lisa M.

2011-07-06

A key question to address in the development of oxygen isotope ratios in phosphate (18Op) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here we present experimental results aimed at understanding the biotic and abiotic pathway of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of specific sedimentary phosphate phases by Escherichia coli, Vibrio fischeri and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction ofmore » phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 hrs) due to efficient O-isotope exchange between phosphate and water (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate promoted the exchange of intact phosphate radicals (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli and V. fischeri ‘extracted’ loosely sorbed phosphate first while M. aquaeolei preferred iron-oxide bound phosphate. Each bacterium imprinted a biotic isotopic signature on each P phase that it took up and cycled. For example, the 18Op value of the sorbed phosphate phase shifted gradually towards equilibrium isotopic composition and the value of Fe oxide-bound phosphate showed slight changes at first, but when new iron oxides were formed, co-precipitated/occluded phosphate retained 18O values of aqueous phosphate at that time. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of 18Op as a tracer of phosphorus cycling in sediments, soils and aquatic environments and as an indicator of paleo- environmental conditions.« less

Metal stable isotopes in weathering and hydrology: Chapter 10

USGS Publications Warehouse

Bullen, Thomas D.; Holland, Heinrich; Turekian, K.

2014-01-01

This chapter highlights some of the major developments in the understanding of the causes of metal stable isotope compositional variability in and isotope fractionation between natural materials and provides numerous examples of how that understanding is providing new insights into weathering and hydrology. At this stage, our knowledge of causes of stable isotope compositional variability among natural materials is greatest for the metals lithium, magnesium, calcium, and iron, the isotopes of which have already provided important information on weathering and hydrological processes. Stable isotope compositional variability for other metals such as strontium, copper, zinc, chromium, barium, molybdenum, mercury, cadmium, and nickel has been demonstrated but is only beginning to be applied to questions related to weathering and hydrology, and several research groups are currently exploring the potential. And then there are other metals such as titanium, vanadium, rhenium, and tungsten that have yet to be explored for variability of stable isotope composition in natural materials, but which may hold untold surprises in their utility. This impressive list of metals having either demonstrated or potential stable isotope signals that could be used to address important unsolved questions related to weathering and hydrology, constitutes a powerful toolbox that will be increasingly utilized in the coming decades.

Studies on the optogalvanic effect and isotope-selective excitation of ytterbium in a hollow cathode discharge lamp using a pulsed dye laser.

PubMed

Kumar, Pankaj; Kumar, Jitendra; Prakash, Om; Saini, Vinod K; Dixit, Sudhir K; Nakhe, Shankar V

2013-09-01

This paper presents studies on the pulsed optogalvanic effect and isotope-selective excitation of Yb 555.648 nm (0 cm(-1) → 17 992.007 cm(-1)) and 581.067 nm (17 992.007 cm(-1) → 35 196.98 cm(-1)) transitions, in a Yb/Ne hollow cathode lamp. The Yb atoms were excited by narrow linewidth (500-1000 MHz) Rh110 and Rh6G dye based pulsed lasers. Optogalvanic signal inversion for ground state transition at 555.648 nm was observed beyond a hollow cathode discharge current of 8.5 mA, in contrast to normal optogalvanic signal at 581.067 nm up to maximum current of 14 mA. The isotope-selective excitation studies of Yb were carried out by recording Doppler limited optogalvanic signals as a function of dye laser wavelength. For the 581.067 nm transition, three even isotopes, (172)Yb, (174)Yb, and (176)Yb, and one odd isotope, (171)Yb, were clearly resolved. These data were compared with selective isotope excitation by 10 MHz linewidth continuous-wave dye laser. For 555.648 nm transition, isotopes were not clearly resolved, although isotope peaks of low modulation were observed.

An isotope dilution ultra high performance liquid chromatography-tandem mass spectrometry method for the simultaneous determination of sugars and humectants in tobacco products.

PubMed

Wang, Liqun; Cardenas, Roberto Bravo; Watson, Clifford

2017-09-08

CDC's Division of Laboratory Sciences developed and validated a new method for the simultaneous detection and measurement of 11 sugars, alditols and humectants in tobacco products. The method uses isotope dilution ultra high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and has demonstrated high sensitivity, selectivity, throughput and accuracy, with recoveries ranging from 90% to 113%, limits of detection ranging from 0.0002 to 0.0045μg/mL and coefficients of variation (CV%) ranging from 1.4 to 14%. Calibration curves for all analytes were linear with linearity R 2 values greater than 0.995. Quantification of tobacco components is necessary to characterize tobacco product components and their potential effects on consumer appeal, smoke chemistry and toxicology, and to potentially help distinguish tobacco product categories. The researchers analyzed a variety of tobacco products (e.g., cigarettes, little cigars, cigarillos) using the new method and documented differences in the abundance of selected analytes among product categories. Specifically, differences were detected in levels of selected sugars found in little cigars and cigarettes, which could help address appeal potential and have utility when product category is unknown, unclear, or miscategorized. Copyright © 2017. Published by Elsevier B.V.

Elementary budget of stag beetle larvae associated with selective utilization of nitrogen in decaying wood.

PubMed

Tanahashi, Masahiko; Ikeda, Hiroshi; Kubota, Kôhei

2018-05-03

Wood degradation by insects plays important roles for the forest matter cycling. Since wood is deficient in nitrogen compared to the insect body, wood-feeding insects need to assimilate the nitrogen selectively and discard an excess carbon. Such a stoichiometric imbalance between food and body will cause high metabolic cost; therefore, wood-feeding insects may somehow alleviate the stoichiometric imbalance. Here, we investigated the carbon and nitrogen budgets of the larvae of stag beetle, Dorcus rectus, which feed on decaying wood. Assimilation efficiency of ingested wood was 22%, and those values based on the carbon and nitrogen were 27 and 45%, respectively, suggesting the selective digestion of nitrogen in wood. Element-based gross growth efficiency was much higher for nitrogen (45%) than for carbon (3%). As a result, the larvae released 24% of the ingested carbon as volatile, whereas almost no gaseous exchange was observed for nitrogen. Moreover, solubility-based elementary analysis revealed that the larvae mainly utilized alkaline-soluble-water-insoluble fraction of wood, which is rich in nitrogen. Actually, the midgut of the larvae was highly alkaline (pH 10.3). Stag beetle larvae are known to exhibit coprophagy, and here we also confirmed that alkaline-soluble-water-insoluble nitrogen increased again from fresh feces to old feces in the field. Stable isotope analysis suggested the utilization of aerial nitrogen by larvae; however, its actual contribution is still disputable. Those results suggest that D. rectus larvae selectively utilize alkaline-soluble nitrogenous substrates by using their highly alkaline midgut, and perhaps associate with microbes that enhance the nitrogen recycling in feces.

Elementary budget of stag beetle larvae associated with selective utilization of nitrogen in decaying wood

NASA Astrophysics Data System (ADS)

Tanahashi, Masahiko; Ikeda, Hiroshi; Kubota, Kôhei

2018-06-01

Wood degradation by insects plays important roles for the forest matter cycling. Since wood is deficient in nitrogen compared to the insect body, wood-feeding insects need to assimilate the nitrogen selectively and discard an excess carbon. Such a stoichiometric imbalance between food and body will cause high metabolic cost; therefore, wood-feeding insects may somehow alleviate the stoichiometric imbalance. Here, we investigated the carbon and nitrogen budgets of the larvae of stag beetle, Dorcus rectus, which feed on decaying wood. Assimilation efficiency of ingested wood was 22%, and those values based on the carbon and nitrogen were 27 and 45%, respectively, suggesting the selective digestion of nitrogen in wood. Element-based gross growth efficiency was much higher for nitrogen (45%) than for carbon (3%). As a result, the larvae released 24% of the ingested carbon as volatile, whereas almost no gaseous exchange was observed for nitrogen. Moreover, solubility-based elementary analysis revealed that the larvae mainly utilized alkaline-soluble-water-insoluble fraction of wood, which is rich in nitrogen. Actually, the midgut of the larvae was highly alkaline (pH 10.3). Stag beetle larvae are known to exhibit coprophagy, and here we also confirmed that alkaline-soluble-water-insoluble nitrogen increased again from fresh feces to old feces in the field. Stable isotope analysis suggested the utilization of aerial nitrogen by larvae; however, its actual contribution is still disputable. Those results suggest that D. rectus larvae selectively utilize alkaline-soluble nitrogenous substrates by using their highly alkaline midgut, and perhaps associate with microbes that enhance the nitrogen recycling in feces.

Isotope separation by photoselective dissociative electron capture

DOEpatents

Stevens, C.G.

1978-08-29

Disclosed is a method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, [sup 235]UF[sub 6] is separated from a UF[sub 6] mixture by selective excitation followed by dissociative electron capture into [sup 235]UF[sub 5]- and F. 2 figs.

Isotope separation by photoselective dissociative electron capture

DOEpatents

Stevens, Charles G. [Pleasanton, CA

1978-08-29

A method of separating isotopes based on photoselective electron capture dissociation of molecules having an electron capture cross section dependence on the vibrational state of the molecule. A molecular isotope source material is irradiated to selectively excite those molecules containing a desired isotope to a predetermined vibrational state having associated therewith an electron capture energy region substantially non-overlapping with the electron capture energy ranges associated with the lowest vibration states of the molecules. The isotope source is also subjected to electrons having an energy corresponding to the non-overlapping electron capture region whereby the selectively excited molecules preferentially capture electrons and dissociate into negative ions and neutrals. The desired isotope may be in the negative ion product or in the neutral product depending upon the mechanism of dissociation of the particular isotope source used. The dissociation product enriched in the desired isotope is then separated from the reaction system by conventional means. Specifically, .sup.235 UF.sub.6 is separated from a UF.sub.6 mixture by selective excitation followed by dissociative electron capture into .sup.235 UF.sub.5 - and F.

HYDROGEN ISOTOPE TARGETS

DOEpatents

Ashley, R.W.

1958-08-12

The design of targets for use in the investigation of nuclear reactions of hydrogen isotopes by bombardment with accelerated particles is described. The target con struction eomprises a backing disc of a metal selected from the group consisting of molybdenunn and tungsten, a eoating of condensed titaniunn on the dise, and a hydrogen isotope selected from the group consisting of deuterium and tritium absorbed in the coatiag. The proeess for preparing these hydrogen isotope targets is described.

ISOTOPE CONVERSION DEVICE

DOEpatents

Wigner, E.P.; Young, G.J.; Ohlinger, L.A.

1957-12-01

This patent relates to nuclear reactors of tbe type utilizing a liquid fuel and designed to convert a non-thermally fissionable isotope to a thermally fissionable isotope by neutron absorption. A tank containing a reactive composition of a thermally fissionable isotope dispersed in a liquid moderator is disposed within an outer tank containing a slurry of a non-thermally fissionable isotope convertible to a thermally fissionable isotope by neutron absorption. A control rod is used to control the chain reaction in the reactive composition and means are provided for circulating and cooling the reactive composition and slurry in separate circuits.

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

PubMed Central

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

2014-01-01

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

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

PubMed

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

2014-01-01

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

A combined radio- and stable-isotopic study of a California coastal aquifer system

USGS Publications Warehouse

Swarzenski, Peter W.; Baskaran, Mark; Rosenbauer, Robert J.; Edwards, Brian D.; Land, Michael

2013-01-01

Stable and radioactive tracers were utilized in concert to characterize geochemical processes in a complex coastal groundwater system and to provide constraints on the kinetics of rock/water interactions. Groundwater samples from wells within the Dominguez Gap region of Los Angeles County, California were analyzed for a suite of major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−), silica, alkalinity, select trace elements (Ba, B, Sr), dissolved oxygen, stable isotopes of hydrogen (δD), oxygen (δ18O), dissolved inorganic carbon (δ13CDIC), and radioactive isotopes (3H, 222Rn and 223,224,226,228Ra). In the study area, groundwater may consist of a complex mixture of native groundwater, intruded seawater, non-native injected water, and oil-field brine water. In some wells, Cl− concentrations attained seawater-like values and in conjunction with isotopically heavier δ18O values, these tracers provide information on the extent of seawater intrusion and/or mixing with oil-field brines. Groundwater 3H above 1 tritium unit (TU) was observed only in a few select wells close to the Dominguez Gap area and most other well groundwater was aged pre-1952. Based on an initial 14C value for the study site of 90 percent modern carbon (pmc), groundwater age estimates likely extend beyond 20 kyr before present and confirm deep circulation of some native groundwater through multiple aquifers. Enriched values of groundwater δ13CDIC in the absence of SO42− imply enhanced anaerobic microbial methanogenesis. While secular equilibrium was observed for 234U/238U (activity ratios ~1) in host matrices, strong isotopic fractionation in these groundwater samples can be used to obtain information of adsorption/desorption kinetics. Calculated Ra residence times are short, and the associated desorption rate constant is about three orders of magnitude slower than that of the adsorption rate constant. Combined stable- and radio-isotopic results provide unique insights into aquifer characteristics, such as geochemical cycling, rock/water interactions, and subsurface transport and mixing.

COMPOUND-SPECIFIC ISOTOPE ANALYSIS OF MTBE AND TBA FOR BIOREMEDIATION STUDIES

EPA Science Inventory

The utility of stable isotope ratios to detect biodegradation for a number of chemical compounds including MTBE and TBA has been demonstrated in a number of laboratory or field studies. Chemical reactions tend to favor molecules with the lighter isotopic species (e.g., 12C, 1H), ...

Isotope separation by selective photodissociation of glyoxal

DOEpatents

Marling, John B.

1976-01-01

Dissociation products, mainly formaldehyde and carbon monoxide, enriched in a desired isotope of carbon, oxygen, or hydrogen are obtained by the selective photodissociation of glyoxal wherein glyoxal is subjected to electromagnetic radiation of a predetermined wavelength such that photon absorption excites and induces dissociation of only those molecules of glyoxal containing the desired isotope.

Calculation and mitigation of isotopic interferences in liquid chromatography-mass spectrometry/mass spectrometry assays and its application in supporting microdose absolute bioavailability studies.

PubMed

Gu, Huidong; Wang, Jian; Aubry, Anne-Françoise; Jiang, Hao; Zeng, Jianing; Easter, John; Wang, Jun-sheng; Dockens, Randy; Bifano, Marc; Burrell, Richard; Arnold, Mark E

2012-06-05

A methodology for the accurate calculation and mitigation of isotopic interferences in liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) assays and its application in supporting microdose absolute bioavailability studies are reported for the first time. For simplicity, this calculation methodology and the strategy to minimize the isotopic interference are demonstrated using a simple molecule entity, then applied to actual development drugs. The exact isotopic interferences calculated with this methodology were often much less than the traditionally used, overestimated isotopic interferences simply based on the molecular isotope abundance. One application of the methodology is the selection of a stable isotopically labeled internal standard (SIL-IS) for an LC-MS/MS bioanalytical assay. The second application is the selection of an SIL analogue for use in intravenous (i.v.) microdosing for the determination of absolute bioavailability. In the case of microdosing, the traditional approach of calculating isotopic interferences can result in selecting a labeling scheme that overlabels the i.v.-dosed drug or leads to incorrect conclusions on the feasibility of using an SIL drug and analysis by LC-MS/MS. The methodology presented here can guide the synthesis by accurately calculating the isotopic interferences when labeling at different positions, using different selective reaction monitoring (SRM) transitions or adding more labeling positions. This methodology has been successfully applied to the selection of the labeled i.v.-dosed drugs for use in two microdose absolute bioavailability studies, before initiating the chemical synthesis. With this methodology, significant time and cost saving can be achieved in supporting microdose absolute bioavailability studies with stable labeled drugs.

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

Complementary constraints from carbon (13C) and nitrogen (15N) isotopes on the glacial ocean's soft-tissue biological pump

NASA Astrophysics Data System (ADS)

Schmittner, A.; Somes, C. J.

2016-06-01

A three-dimensional, process-based model of the ocean's carbon and nitrogen cycles, including 13C and 15N isotopes, is used to explore effects of idealized changes in the soft-tissue biological pump. Results are presented from one preindustrial control run (piCtrl) and six simulations of the Last Glacial Maximum (LGM) with increasing values of the spatially constant maximum phytoplankton growth rate μmax, which accelerates biological nutrient utilization mimicking iron fertilization. The default LGM simulation, without increasing μmax and with a shallower and weaker Atlantic Meridional Overturning Circulation and increased sea ice cover, leads to 280 Pg more respired organic carbon (Corg) storage in the deep ocean with respect to piCtrl. Dissolved oxygen concentrations in the colder glacial thermocline increase, which reduces water column denitrification and, with delay, nitrogen fixation, thus increasing the ocean's fixed nitrogen inventory and decreasing δ15NNO3 almost everywhere. This simulation already fits sediment reconstructions of carbon and nitrogen isotopes relatively well, but it overestimates deep ocean δ13CDIC and underestimates δ15NNO3 at high latitudes. Increasing μmax enhances Corg and lowers deep ocean δ13CDIC, improving the agreement with sediment data. In the model's Antarctic and North Pacific Oceans modest increases in μmax result in higher δ15NNO3 due to enhanced local nutrient utilization, improving the agreement with reconstructions there. Models with moderately increased μmax fit both isotope data best, whereas large increases in nutrient utilization are inconsistent with nitrogen isotopes although they still fit the carbon isotopes reasonably well. The best fitting models reproduce major features of the glacial δ13CDIC, δ15N, and oxygen reconstructions while simulating increased Corg by 510-670 Pg compared with the preindustrial ocean. These results are consistent with the idea that the soft-tissue pump was more efficient during the LGM. Both circulation and biological nutrient utilization could contribute. However, these conclusions are preliminary given our idealized experiments, which do not consider changes in benthic denitrification and spatially inhomogenous changes in aeolian iron fluxes. The analysis illustrates interactions between the carbon and nitrogen cycles as well as the complementary constraints provided by their isotopes. Whereas carbon isotopes are sensitive to circulation changes and indicate well the three-dimensional Corg distribution, nitrogen isotopes are more sensitive to biological nutrient utilization.

Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography

PubMed Central

Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

2012-01-01

Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemical entities are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its 15N4-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC–NCI-MS using selected-ion monitoring outperformed LC–ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5 h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. PMID:22342210

Capture of the volatile carbonyl metabolite of flecainide on 2,4-dinitrophenylhydrazine cartridge for quantitation by stable-isotope dilution mass spectrometry coupled with chromatography.

PubMed

Prokai, Laszlo; Szarka, Szabolcs; Wang, Xiaoli; Prokai-Tatrai, Katalin

2012-04-06

Carbonyl compounds are common byproducts of many metabolic processes. These volatile chemicals are usually derivatized before mass spectrometric analysis to enhance the sensitivity of their detections. The classically used reagent for this purpose is 2,4-dinitrophenylhydrazine (DNPH) that forms the corresponding hydrazones. When DNPH is immobilized on specific cartridges it permits solvent-free collection and simultaneous derivatization of aldehydes and ketones from gaseous samples. The utility of this approach was tested by assembling a simple apparatus for the in vitro generation of trifluoroacetaldehyde (TFAA) and its subsequent capture on the attached DNPH cartridge. TFAA was generated via cytochrome P450-catalyzed dealkylation of flecainide, an antiarrhythmic agent, in pooled human liver microsomes. Stable-isotope dilution mass spectrometry coupled with GC and LC using negative chemical ionization (NCI) and electrospray ionization (ESI) was evaluated for quantitative analyses. To eliminate isotope effects observed with the use of deuterium-labeled DNPH, we selected its (15)N(4)-labeled analog to synthesize the appropriate TFAA adduct, as internal standard. Quantitation by GC-NCI-MS using selected-ion monitoring outperformed LC-ESI-MS methods considering limits of detection and linearity of the assays. The microsomal metabolism of 1.5 μmol of flecainide for 1.5h resulted in 2.6 ± 0.5 μg TFAA-DNPH, corresponding to 9.3 ± 1.7 nmol TFAA, captured by the cartridge. Copyright © 2012 Elsevier B.V. All rights reserved.

Photochemical isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1987-01-01

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

Laser isotope separation

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Boyer, Keith; Greiner, Norman R.

1988-01-01

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Isotope separation by laser means

DOEpatents

Robinson, C. Paul; Jensen, Reed J.; Cotter, Theodore P.; Greiner, Norman R.; Boyer, Keith

1982-06-15

A process for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium.

A protocol for pressurized liquid extraction and processing methods to isolate modern and ancient bone cholesterol for compound-specific stable isotope analysis.

PubMed

Laffey, Ann O; Krigbaum, John; Zimmerman, Andrew R

2017-02-15

Bone lipid compound-specific isotope analysis (CSIA) and bone collagen and apatite stable isotope ratio analysis are important sources of ecological and paleodietary information. Pressurized liquid extraction (PLE) is quicker and utilizes less solvent than traditional methods of lipid extraction such as soxhlet and ultrasonication. This study facilitates dietary analysis by optimizing and testing a standardized methodology for PLE of bone cholesterol. Modern and archaeological bones were extracted by PLE using varied temperatures, solvent solutions, and sample weights. The efficiency of PLE was assessed via quantification of cholesterol yields. Stable isotopic ratio integrity was evaluated by comparing isotopic signatures (δ 13 C and δ 18 O values) of cholesterol derived from whole bone, bone collagen and bone apatite. Gas chromatography/mass spectrometry (GC/MS) and gas chromatography isotope ratio mass spectrometry (GC/IRMS) were conducted on purified collagen and lipid extracts to assess isotopic responses to PLE. Lipid yield was optimized at two PLE extraction cycles of 75 °C using dichloromethane/methanol (2:1 v/v) as a solvent with 0.25-0.75 g bone sample. Following lipid extraction, saponification combined with the derivatization of the neutral fraction using trimethylsilylation yielded nearly twice the cholesterol of non-saponified or non-derivatized samples. It was also found that lipids extracted from purified bone collagen and apatite could be used for cholesterol CSIA. There was no difference in the bulk δ 13 C values of collagen extracted from bone with or without lipid. However, there was a significant depletion in 18 O of bone apatite due to lipid presence or processing. These results should assist sample selection and provide an effective, alternative extraction method for bone cholesterol that may be used for isotopic and paleodietary analysis. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

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

USDA-ARS?s Scientific Manuscript database

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

Complementary Constraints from Carbon (13C) and Nitrogen (15N) Isotopes on the Efficiency of the Glacial Ocean's Soft-Tissue Biological Pump

NASA Astrophysics Data System (ADS)

Schmittner, A.; Somes, C. J.

2016-12-01

A three-dimensional, process-based model of the ocean's carbon and nitrogen cycles, including 13C and 15N isotopes, is used to explore effects of idealized changes in the soft-tissue biological pump. Results are presented from one preindustrial control run and six simulations of the Last Glacial Maximum (LGM) with increasing values of the spatially constant maximum phytoplankton growth rate μmax, which mimicks iron fertilization. The default LGM simulation, without increasing μmax and with a shallower and weaker Atlantic Meridional Overturning Circulation and increased sea ice cover, leads to 280 Pg more respired organic carbon (Corg) than the pre-industrial control. Dissolved oxygen in the thermocline increase, which reduces water column denitrification and nitrogen fixation, thus increasing the ocean's fixed nitrogen inventory and decreasing δ15NNO3. This simulation already fits observed carbon and nitrogen isotopes relatively well, but it overestimates deep ocean δ13CDIC and underestimates δ15NNO3 at high latitudes. Increasing μmax enhances Corg and lowers deep ocean δ13CDIC, improving the fit. Modest increases in μmax result in higher subpolar δ15NNO3 due to enhanced local nutrient utilization, and better agreement with reconstructions. Large increases in nutrient utilization are inconsistent with nitrogen isotopes although they still fit the carbon isotopes reasonably well. The best fitting models with modest increases in μmax reproduce major features of the glacial δ13CDIC, δ15N, and oxygen reconstructions while simulating increased Corg by 510-670 Pg. These results are consistent with the idea that the soft-tissue pump was more efficient during the LGM. Both circulation and biological nutrient utilization contribute. However, these conclusions are preliminary given our idealized experiments, which do not consider changes in benthic denitrification and spatially inhomogenous changes in aeolian iron fluxes. The analysis illustrates interactions between the carbon and nitrogen cycles as well as the complementary constraints provided by their isotopes. Whereas carbon isotopes are sensitive to circulation changes and indicate well the three-dimensional Corg distribution, nitrogen isotopes are more sensitive to biological nutrient utilization.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, R.J.; Cecchi, J.L.

1983-07-26

This invention relates generally to the field of gas desorption from metals; and, more particularly, to a method of enhancing the selective desorption of a particular isotope of a gas from metals. Enhanced selective desorption is especially useful in the operation of fusion devices.

Diode-laser-based RIMS measurements of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1998-12-01

Double- and triple-resonance excitation schemes for the ionization of strontium are presented. Use of single-mode diode lasers for the resonance excitations provides a high degree of optical isotopic selectivity: with double-resonance, selectivity of >104 for 90Sr against the stable Sr isotopes has been demonstrated. Measurement of lineshapes and stable isotope shifts in the triple-resonance process indicate that optical selectivity should increase to ˜109. When combined with mass spectrometer selectivity this is sufficient for measurement of 90Sr at background environmental levels. Additionally, autoionizing resonances have been investigated for improving ionization efficiency with lower power lasers.

ABSORPTION ANALYZER

DOEpatents

Brooksbank, W.A. Jr.; Leddicotte, G.W.; Strain, J.E.; Hendon, H.H. Jr.

1961-11-14

A means was developed for continuously computing and indicating the isotopic assay of a process solution and for automatically controlling the process output of isotope separation equipment to provide a continuous output of the desired isotopic ratio. A counter tube is surrounded with a sample to be analyzed so that the tube is exactly in the center of the sample. A source of fast neutrons is provided and is spaced from the sample. The neutrons from the source are thermalized by causing them to pass through a neutron moderator, and the neutrons are allowed to diffuse radially through the sample to actuate the counter. A reference counter in a known sample of pure solvent is also actuated by the thermal neutrons from the neutron source. The number of neutrons which actuate the detectors is a function of a concentration of the elements in solution and their neutron absorption cross sections. The pulses produced by the detectors responsive to each neu tron passing therethrough are amplified and counted. The respective times required to accumulate a selected number of counts are measured by associated timing devices. The concentration of a particular element in solution may be determined by utilizing the following relation: T2/Ti = BCR, where B is a constant proportional to the absorption cross sections, T2 is the time of count collection for the unknown solution, Ti is the time of count collection for the pure solvent, R is the isotopic ratlo, and C is the molar concentration of the element to be determined. Knowing the slope constant B for any element and when the chemical concentration is known, the isotopic concentration may be readily determined, and conversely when the isotopic ratio is known, the chemical concentrations may be determined. (AEC)

An Isotope-Powered Thermal Storage unit for space applications

NASA Technical Reports Server (NTRS)

Lisano, Michael E.; Rose, M. F.

1991-01-01

An Isotope-Powered Thermal Storage Unit (ITSU), that would store and utilize heat energy in a 'pulsed' fashion in space operations, is described. Properties of various radioisotopes are considered in conjunction with characteristics of thermal energy storage materials, to evaluate possible implementation of such a device. The utility of the unit is discussed in light of various space applications, including rocket propulsion, power generation, and spacecraft thermal management.

ROBOCAL: Gamma-ray isotopic hardware/software interface

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

Hurd, J.R.; Bonner, C.A.; Ostenak, C.A.

1989-01-01

ROBOCAL, presently being developed at the Los Alamos National Laboratory, is a full-scale prototypical robotic system for remotely performing calorimetric and gamma-ray isotopics measurements of nuclear materials. It features a fully automated vertical stacker-retriever for storing and retrieving packaged nuclear materials from a multi-drawer system, and a fully automated, uniquely integrated gantry robot for programmable selection and transfer of nuclear materials to calorimetric and gamma-ray isotopic measurement stations. Since ROBOCAL is to require almost no operator intervention, a mechanical control system is required in addition to a totally automated assay system. The assay system must be a completely integrated datamore » acquisition and isotopic analysis package fully capable of performing state-of-the-art homogeneous and heterogeneous analyses on many varied matrices. The TRIFID assay system being discussed at this conference by J. G. Fleissner of the Rocky Flats Plant has been adopted because of its many automated features. These include: MCA/ADC setup and acquisition; spectral storage and analysis utilizing an expert system formalism; report generation with internal measurement control printout; user friendly screens and menus. The mechanical control portion consists primarily of two detector platforms and a sample platform, each with independent movement. Some minor modifications and additions are needed with TRIFID to interface the assay and mechanical portions with the CimRoc 4000 software controlling the robot. 6 refs., 5 figs., 3 tabs.« less

Laser isotope separation

DOEpatents

Robinson, C.P.; Reed, J.J.; Cotter, T.P.; Boyer, K.; Greiner, N.R.

1975-11-26

A process and apparatus for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light is described. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photolysis, photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photolysis, photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium.

Photochemical isotope separation

DOEpatents

Robinson, C.P.; Jensen, R.J.; Cotter, T.P.; Greiner, N.R.; Boyer, K.

1987-04-28

A process is described for separating isotopes by selective excitation of isotopic species of a volatile compound by tuned laser light. A highly cooled gas of the volatile compound is produced in which the isotopic shift is sharpened and defined. Before substantial condensation occurs, the cooled gas is irradiated with laser light precisely tuned to a desired wavelength to selectively excite a particular isotopic species in the cooled gas. The laser light may impart sufficient energy to the excited species to cause it to undergo photochemical reaction or even to photoionize. Alternatively, a two-photon irradiation may be applied to the cooled gas to induce photochemical reaction or photoionization. The process is particularly applicable to the separation of isotopes of uranium and plutonium. 8 figs.

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

Treesearch

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

2012-01-01

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

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

Boyles, Kelly R.; Chajkowski, Sarah M.; Disselkamp, Robert S.

An H/D isotope effect study of the (H2 versus D2) hydrogenation of the aqueous substrates 3-buten-2-ol (3B2OL) and 1,4-pentadien-3-ol (14PD3OL) was performed using Pd-black catalyst. Either H2O or D2O solvents were employed (for alcohol H/D isotope substitution). Two experimental processing conditions of cavitating ultrasound (CUS) and stirred/silent (SS) methods were used. Products formed include 2-butanol and 2-butanone for the former, and 3-pentanol and 3-pentanone for the latter. The observed selectivity and pseudo-first order reaction rate coefficients (e.g., activity) to these products enabled a mechanistic interpretation of the various reaction conditions to be proposed. Experiments utilized a 50 mL batch reactormore » maintained at 298 K, employed 5.4 atm of H2 or D2 gas, while seven aliquots were collected during the course of the reaction. We have utilized 1-propanol as an inert dopant in all experiments to enable the rapid onset of cavitation in the CUS systems as described earlier [R.S. Disselkamp et al., J. Catal., 227, 552 (2004)]. The following conclusions were noted. First, the activity of the CUS compared to SS processing were ~100-fold larger. Second, variable catalyst loading experiments for stirred/silent D2 hydrogenation processing indicated that mass transfer of hydrogen gas to the Pd-surface played a role such that higher catalyst loading reduced surface D-atom concentrations and reduced saturated alcohol formation (e.g., via reduced H-addition to surface alkyl radicals). Third, for CUS processing the ketone selectivities for experiments employing water compared to D2O indicated that 3B2OL were twice as large, whereas for 14PD3OL they were comparable. This suggests, somewhat surprisingly, that for 3B2OL enol tautomerization to ketone is a slow, and possibly rate-controlling, process. Finally, again for CUS processing, the similarity in ketone selectivities (all ~17%) for H2 compared to D2 hydrogenation for both 3B2OL and 14PD3OL suggest that both H/D isotopes have rapid surface diffusion and hence give rise to nearly equal selectivies. Restated, the thermal or cavitating ultrasound activation is much greater than the surface H/D diffusion barrier.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

System and method for high precision isotope ratio destructive analysis

DOEpatents

Bushaw, Bruce A; Anheier, Norman C; Phillips, Jon R

2013-07-02

A system and process are disclosed that provide high accuracy and high precision destructive analysis measurements for isotope ratio determination of relative isotope abundance distributions in liquids, solids, and particulate samples. The invention utilizes a collinear probe beam to interrogate a laser ablated plume. This invention provides enhanced single-shot detection sensitivity approaching the femtogram range, and isotope ratios that can be determined at approximately 1% or better precision and accuracy (relative standard deviation).

Method and system for radioisotope generation

DOEpatents

Toth, James J.; Soderquist, Chuck Z.; Greenwood, Lawrence R.; Mattigod, Shas V.; Fryxell, Glen E.; O'Hara, Matthew J.

2014-07-15

A system and a process for producing selected isotopic daughter products from parent materials characterized by the steps of loading the parent material upon a sorbent having a functional group configured to selectively bind the parent material under designated conditions, generating the selected isotopic daughter products, and eluting said selected isotopic daughter products from the sorbent. In one embodiment, the process also includes the step of passing an eluent formed by the elution step through a second sorbent material that is configured to remove a preselected material from said eluent. In some applications a passage of the material through a third sorbent material after passage through the second sorbent material is also performed.

Isotope separation by photochromatography

DOEpatents

Suslick, Kenneth S.

1977-01-01

An isotope separation method which comprises physically adsorbing an isotopically mixed molecular species on an adsorptive surface and irradiating the adsorbed molecules with radiation of a predetermined wavelength which will selectively excite a desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thereby separate them from the unexcited undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes.

Evaluation of uranium transitions for isotopically-selective laser induced fluorescence with diode lasers (technical report for ST064)

NASA Astrophysics Data System (ADS)

Cannon, B. D.

1993-10-01

Isotopically-selective excitation of uranium atoms by diode lasers can be the basis for a portable instrument to perform uranium isotopic assays in the field. Such an instrument would improve the ability of on-site inspections to detect and deter nuclear proliferation. Published and unpublished spectroscopic data on atomic uranium were examined to identify candidate transitions for isotopically-selective laser excitation with diode lasers. Eleven candidate transitions were identified and evaluated for their potential usefulness for a portable uranium assay instrument. Eight of these transitions are suitable for laser induced fluorescence using different excitation and detection wavelengths, which will improve sensitivity and elemental selectivity. Data sheets on the 25 uranium transitions in the wavelength range 629 nm to 1,000 nm that originate in the ground or first excited states of neutral atomic uranium are included. Each data sheet provides the wavelength, upper and lower energy levels, angular momentum quantum numbers, U-235 isotope shift (relative to U-238, and high-resolution spectra of weapons-grade uranium (93% U-235 and 7% U-238).

Extreme Monsoon Rainfall Signatures Preserved in the Invasive Terrestrial Gastropod Lissachatina fulica

NASA Astrophysics Data System (ADS)

Ghosh, Prosenjit; Rangarajan, Ravi; Thirumalai, Kaustubh; Naggs, Fred

2017-11-01

Indian summer monsoon (ISM) rainfall lasts for a period of 4 months with large variations recorded in terms of rainfall intensity during its period between June and September. Proxy reconstructions of past ISM rainfall variability are required due to the paucity of long instrumental records. However, reconstructing subseasonal rainfall is extremely difficult using conventional hydroclimate proxies due to inadequate sample resolution. Here, we demonstrate the utility of the stable oxygen isotope composition of gastropod shells in reconstructing past rainfall on subseasonal timescales. We present a comparative isotopic study on present day rainwater and stable isotope ratios of precipitate found in the incremental growth bands of giant African land snail Lissachatina fulica (Bowdich) from modern day (2009) and in the historical past (1918). Isotopic signatures present in the growth bands allowed for the identification of ISM rainfall variability in terms of its active and dry spells in the modern as well as past gastropod record. Our results demonstrate the utility of gastropod growth band stable isotope ratios in semiquantitative reconstructions of seasonal rainfall patterns. High resolution climate records extracted from gastropod growth band stable isotopes (museum and archived specimens) can expand the scope for understanding past subseasonal-to-seasonal climate variability.

Iron-Isotopic Fractionation Studies Using Multiple Collector Inductively Coupled Plasma Mass Spectrometry

NASA Technical Reports Server (NTRS)

Anbar, A. D.; Zhang, C.; Barling, J.; Roe, J. E.; Nealson, K. H.

1999-01-01

The importance of Fe biogeochemistry has stimulated interest in Fe isotope fractionation. Recent studies using thermal ionization mass spectrometry (TIMS) and a "double spike" demonstrate the existence of biogenic Fe isotope effects. Here, we assess the utility of multiple-collector inductively-coupled plasma mass spectrometry(MC-ICP-MS) with a desolvating sample introduction system for Fe isotope studies, and present data on Fe biominerals produced by a thermophilic bacterium. Additional information is contained in the original extended abstract.

Utilization of non-weapons-grade plutonium and highly enriched uranium with breeding of the 233U isotope in the VVER reactors using thorium and heavy water

NASA Astrophysics Data System (ADS)

Marshalkin, V. E.; Povyshev, V. M.

2015-12-01

A method for joint utilization of non-weapons-grade plutonium and highly enriched uranium in the thorium-uranium—plutonium oxide fuel of a water-moderated reactor with a varying water composition (D2O, H2O) is proposed. The method is characterized by efficient breeding of the 233U isotope and safe reactor operation and is comparatively simple to implement.

Isotope separation by photochromatography

DOEpatents

Suslick, K.S.

1975-10-03

A photochromatographic method for isotope separation is described. An isotopically mixed molecular species is adsorbed on an adsorptive surface, and the adsorbed molecules are irradiated with radiation of a predetermined wavelength which will selectively excite desired isotopic species. Sufficient energy is transferred to the excited molecules to desorb them from the surface and thus separate them from the undesired isotopic species. The method is particularly applicable to the separation of hydrogen isotopes. (BLM)

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means.

Retrospective analysis of bottlenose dolphin foraging: a legacy of anthropogenic ecosystem disturbance

USGS Publications Warehouse

Rossman, Sam; Barros, Nélio B.; Ostrom, Peggy H.; Stricker, Craig A.; Hohn, Aleta A.; Gandhi, Hasand; Wells, Randall S.

2013-01-01

We used stable isotope analysis to investigate the foraging ecology of coastal bottlenose dolphins (Tursiops truncatus) in relation to a series of anthropogenic disturbances. We first demonstrated that stable isotopes are a faithful indicator of habitat use by comparing muscle isotope values to behavioral foraging data from the same individuals. δ13C values increased, while δ34S and δ15N values decreased with the percentage of feeding observations in seagrass habitat. We then utilized stable isotope values of muscle to assess temporal variation in foraging habitat from 1991 to 2010 and collagen from tooth crown tips to assess the time period 1944 to 2007. From 1991 to 2010, δ13C values of muscle decreased while δ34S values increased indicating reduced utilization of seagrass habitat. From 1944 to 1989 δ13C values of the crown tip declined significantly, likely due to a reduction in the coverage of seagrass habitat and δ15N values significantly increased, a trend we attribute to nutrient loading from a rapidly increasing human population. Our results demonstrate the utility of using marine mammal foraging habits to retrospectively assess the extent to which anthropogenic disturbance impacts coastal food webs.

Consistent relationship between global climate and surface nitrate utilization in the western subarctic Pacific throughout the last 500 ka

NASA Astrophysics Data System (ADS)

Galbraith, Eric D.; Kienast, Markus; Jaccard, Samuel L.; Pedersen, Thomas F.; Brunelle, Brigitte G.; Sigman, Daniel M.; Kiefer, Thorsten

2008-06-01

The open subarctic Pacific is, at present, a high nitrate low chlorophyll (HNLC) region, where nitrate is perennially abundant at the surface. Theoretically, the HNLC status of this region is subject to modification by ocean circulation and/or micronutrient supply, with implications for the effectiveness of the biological pump and hence carbon sequestration in the ocean interior. Records of biogenic detritus in sediments from throughout the subarctic Pacific indicate that export production was generally lower during glacial maxima, while nitrogen isotope measurements from the Bering Sea have shown that nitrate consumption there was more complete during the last glacial period than it is today. Here, nitrogen isotopic analyses of bulk sediments (δ15Nbulk) from three deep water sites in the open subarctic Pacific are evaluated in terms of regional nitrate isotopic composition and local relative nitrate utilization. The eastern subarctic Pacific δ15Nbulk record bears great similarity to δ15Nbulk records from the western margin of North America over the last glacial cycle, suggesting that variability in the isotopic composition of subeuphotic zone nitrate, the growth substrate, is reasonably coherent throughout the northeast Pacific and dominates at these sites. However, the two western subarctic Pacific records, which lie at the heart of the HNLC region, display a different pattern, implying that significant changes in local relative nitrate utilization overlie the regional background variability. After a novel correction intended to remove the background signal associated with denitrification in the eastern tropical North Pacific, these nitrate utilization records are correlated with a benthic oxygen isotope stack reflecting global deep ocean temperature and ice volume (r2 = 0.65). The correlation implies a strong link between global climate and subarctic Pacific nitrate utilization, with nearly complete nitrate consumption during glacial periods when export production was low.

Quinone-based stable isotope probing for assessment of 13C substrate-utilizing bacteria

NASA Astrophysics Data System (ADS)

Kunihiro, Tadao; Katayama, Arata; Demachi, Toyoko; Veuger, Bart; Boschker, Henricus T. S.; van Oevelen, Dick

2015-04-01

In this study, we attempted to establish quinone-stable-isotope probing (SIP) technique to link substrate-utilizing bacterial group to chemotaxonomic group in bacterial community. To identify metabolically active bacterial group in various environments, SIP techniques combined with biomarkers have been widely utilized as an attractive method for environmental study. Quantitative approaches of the SIP technique have unique advantage to assess substrate-incorporation into bacteria. As a most major quantitative approach, SIP technique based on phospholipid-derived fatty acids (PLFA) have been applied to simultaneously assess substrate-incorporation rate into bacteria and microbial community structure. This approach is powerful to estimate the incorporation rate because of the high sensitivity due to the detection by a gas chromatograph-combustion interface-isotope ratio mass spectrometer (GC-c-IRMS). However, its phylogenetic resolution is limited by specificity of a compound-specific marker. We focused on respiratory quinone as a biomarker. Our previous study found a good correlation between concentrations of bacteria-specific PLFAs and quinones over several orders of magnitude in various marine sediments, and the quinone method has a higher resolution (bacterial phylum level) for resolving differences in bacterial community composition more than that of bacterial PLFA. Therefore, respiratory quinones are potentially good biomarkers for quantitative approaches of the SIP technique. The LC-APCI-MS method as molecular-mass based detection method for quinone was developed and provides useful structural information for identifying quinone molecular species in environmental samples. LC-MS/MS on hybrid triple quadrupole/linear ion trap, which enables to simultaneously identify and quantify compounds in a single analysis, can detect high molecular compounds with their isotope ions. Use of LC-MS/MS allows us to develop quinone-SIP based on molecular mass differences due to 13C abundance in the quinone. In this study, we verified carbon stable isotope of quinone compared with bulk carbon stable isotope of bacterial culture. Results indicated a good correlation between carbon stable isotope of quinone compared with bulk carbon stable isotope. However, our measurement conditions for detection of quinone isotope-ions incurred underestimation of 13C abundance in the quinone. The quinone-SIP technique needs further optimization for measurement conditions of LC-MS/MS.

Mechanisms linking metabolism of Helicobacter pylori to 18O and 13C-isotopes of human breath CO2

PubMed Central

Som, Suman; De, Anulekha; Banik, Gourab Dutta; Maity, Abhijit; Ghosh, Chiranjit; Pal, Mithun; Daschakraborty, Sunil B.; Chaudhuri, Sujit; Jana, Subhra; Pradhan, Manik

2015-01-01

The gastric pathogen Helicobacter pylori utilize glucose during metabolism, but the underlying mechanisms linking to oxygen-18 (18O) and carbon-13 (13C)-isotopic fractionations of breath CO2 during glucose metabolism are poorly understood. Using the excretion dynamics of 18O/16O and 13C/12C-isotope ratios of breath CO2, we found that individuals with Helicobacter pylori infections exhibited significantly higher isotopic enrichments of 18O in breath CO2 during the 2h-glucose metabolism regardless of the isotopic nature of the substrate, while no significant enrichments of 18O in breath CO2 were manifested in individuals without the infections. In contrast, the 13C-isotopic enrichments of breath CO2 were significantly higher in individuals with Helicobacter pylori compared to individuals without infections in response to 13C-enriched glucose uptake, whereas a distinguishable change of breath 13C/12C-isotope ratios was also evident when Helicobacter pylori utilize natural glucose. Moreover, monitoring the 18O and 13C-isotopic exchange in breath CO2 successfully diagnosed the eradications of Helicobacter pylori infections following a standard therapy. Our findings suggest that breath 12C18O16O and 13C16O16O can be used as potential molecular biomarkers to distinctively track the pathogenesis of Helicobacter pylori and also for eradication purposes and thus may open new perspectives into the pathogen’s physiology along with isotope-specific non-invasive diagnosis of the infection. PMID:26039789

Novel hybrid isotope separation scheme and apparatus

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which the specific isotope is to be isolated, radiating the gas with frequencies characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photoionization reaction of the desired isotope, and collecting the specific isotope ion by suitable ion collection means. 3 figures.

APPLICATION OF STABLE ISOTOPE TECHNIQUES TO AIR POLLUTION RESEARCH

EPA Science Inventory

Stable isotope techniques provide a robust, yet under-utilized tool for examining pollutant effects on plant growth and ecosystem function. Here, we survey a range of mixing model, physiological and system level applications for documenting pollutant effects. Mixing model examp...

Utilization of non-weapons-grade plutonium and highly enriched uranium with breeding of the {sup 233}U isotope in the VVER reactors using thorium and heavy water

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

Marshalkin, V. E., E-mail: marshalkin@vniief.ru; Povyshev, V. M.

A method for joint utilization of non-weapons-grade plutonium and highly enriched uranium in the thorium–uranium—plutonium oxide fuel of a water-moderated reactor with a varying water composition (D{sub 2}O, H{sub 2}O) is proposed. The method is characterized by efficient breeding of the {sup 233}U isotope and safe reactor operation and is comparatively simple to implement.

Isotope enrichment by frequency-tripled temperature tuned neodymium laser photolysis of formaldehyde

DOEpatents

Marling, John B.

1977-01-01

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation provided by a frequency-tripled, temperature tuned neodymium laser.

Measurement of strontium isotope ratio in nitric acid extract of peanut testa by ICP-Q-MS after removal of Rb by extraction with pure water.

PubMed

Zhu, Yanbei; Hioki, Akiharu; Chiba, Koichi

2014-02-01

The difference in the distributions of Sr and Rb in peanut seeds was utilized to develop a precise method for Sr isotope ratio measurement by inductively coupled plasma quadruple mass spectrometry (ICP-Q-MS). The testa instead of the whole peanut seed was selected as the sample because apparent enrichment of Sr in comparison to Rb was found in the testa. Furthermore, Rb in the testa was removed by pure water extraction with the aid of sonication to remove the isobaric interference in Sr isotope ratio measurement. The testa taken from one peanut seed was treated as one sample for the analysis. After optimization of the operating conditions, pure water (10 mL for each sample) extraction in 30 min with sonication was able to remove over 95% of Rb in the testa, while after the Rb removal Sr could be completely extracted using 10 mL of 0.3 mol L(-1) HNO3 for each sample. The integration time in ICP-Q-MS measurement was optimized to achieve a lower measurement uncertainty in a shorter time; the results showed that 1s was required and enough for the precise measurement of Sr isotope ratios giving a relative standard uncertainty (n=10) of ca. 0.1%. The present method was applied to peanut seeds grown in Japan, China, USA, India, and South Africa. © 2013 Published by Elsevier B.V.

Compilation of minimum and maximum isotope ratios of selected elements in naturally occurring terrestrial materials and reagents

USGS Publications Warehouse

Coplen, T.B.; Hopple, J.A.; Böhlke, J.K.; Peiser, H.S.; Rieder, S.E.; Krouse, H.R.; Rosman, K.J.R.; Ding, T.; Vocke, R.D.; Revesz, K.M.; Lamberty, A.; Taylor, P.; De Bievre, P.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope abundance variations potentially are large enough to result in future expansion of their atomic weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope-abundance variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio. There are no internationally distributed isotopic reference materials for the elements zinc, selenium, molybdenum, palladium, and tellurium. Preparation of such materials will help to make isotope ratio measurements among laboratories comparable. The minimum and maximum concentrations of a selected isotope in naturally occurring terrestrial materials for selected chemical elements reviewed in this report are given below: Isotope Minimum mole fraction Maximum mole fraction -------------------------------------------------------------------------------- 2H 0 .000 0255 0 .000 1838 7Li 0 .9227 0 .9278 11B 0 .7961 0 .8107 13C 0 .009 629 0 .011 466 15N 0 .003 462 0 .004 210 18O 0 .001 875 0 .002 218 26Mg 0 .1099 0 .1103 30Si 0 .030 816 0 .031 023 34S 0 .0398 0 .0473 37Cl 0 .240 77 0 .243 56 44Ca 0 .020 82 0 .020 92 53Cr 0 .095 01 0 .095 53 56Fe 0 .917 42 0 .917 60 65Cu 0 .3066 0 .3102 205Tl 0 .704 72 0 .705 06 The numerical values above have uncertainties that depend upon the uncertainties of the determinations of the absolute isotope-abundance variations of reference materials of the elements. Because reference materials used for absolute isotope-abundance measurements have not been included in relative isotope abundance investigations of zinc, selenium, molybdenum, palladium, and tellurium, ranges in isotopic composition are not listed for these elements, although such ranges may be measurable with state-of-the-art mass spectrometry. This report is available at the url: http://pubs.water.usgs.gov/wri014222.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, Christopher A.; Worden, Earl F.

1995-01-01

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of .sup.167 Er. The hyperfine structure of .sup.167 Er was used to find two three-step photoionization pathways having a common upper energy level.

Method and apparatus for noble gas atom detection with isotopic selectivity

DOEpatents

Hurst, G. Samuel; Payne, Marvin G.; Chen, Chung-Hsuan; Parks, James E.

1984-01-01

Apparatus and methods of operation are described for determining, with isotopic selectivity, the number of noble gas atoms in a sample. The analysis is conducted within an evacuated chamber which can be isolated by a valve from a vacuum pumping system capable of producing a pressure of 10.sup.-8 Torr. Provision is made to pass pulses of laser beams through the chamber, these pulses having wavelengths appropriate for the resonance ionization of atoms of the noble gas under analysis. A mass filter within the chamber selects ions of a specific isotope of the noble gas, and means are provided to accelerate these selected ions sufficiently for implantation into a target. Specific types of targets are discussed. An electron measuring device produces a signal relatable to the number of ions implanted into the target and thus to the number of atoms of the selected isotope of the noble gas removed from the gas sample. The measurement can be continued until a substantial fraction, or all, of the atoms in the sample have been counted. Furthermore, additional embodiments of the apparatus are described for bunching the atoms of a noble gas for more rapid analysis, and for changing the target for repetitive cycling of the gas in the chamber. The number of repetitions of the cyclic steps depend upon the concentration of the isotope of interest, the separative efficiency of the mass filter, etc. The cycles are continued until a desired selectivity is achieved. Also described are components and a method of operation for a pre-enrichment operation for use when an introduction of a total sample would elevate the pressure within the chamber to levels in excess of those for operation of the mass filter, specifically a quadrupole mass filter. Specific examples of three noble gas isotope analyses are described.

Ion laser isotope enrichment by photo-predissociation of formaldehyde

DOEpatents

Marling, John B.

1977-06-17

Enrichment of carbon, hydrogen and/or oxygen isotopes by means of isotopically selective photo-predissociation of formaldehyde is achieved by irradiation with a fixed frequency ion laser, specifically, a neon, cadmium, or xenon ion laser.

Expanding the utility of 4-cyano-L-phenylalanine as a vibrational reporter of protein environments.

PubMed

Bazewicz, Christopher G; Lipkin, Jacob S; Smith, Emily E; Liskov, Melanie T; Brewer, Scott H

2012-09-06

The ability to genetically incorporate amino acids modified with spectroscopic reporters site-specifically into proteins with high efficiency and fidelity has greatly enhanced the ability to probe local protein structure and dynamics. Here, we have synthesized the unnatural amino acid (UAA), 4-cyano-L-phenylalanine (pCNPhe), containing the nitrile vibrational reporter and three isotopomers ((15)N, (13)C, (13)C(15)N) of this UAA to enhance the ability of pCNPhe to study local protein environments. Each pCNPhe isotopic variant was genetically incorporated in an efficient, site-specific manner into superfolder green fluorescent protein (sfGFP) in response to an amber codon with high fidelity utilizing an engineered, orthogonal aminoacyl-tRNA synthetase. The isotopomers of 4-cyano-L-phenylalanine permitted the nitrile symmetric stretch vibration of these UAAs to be unambiguously assigned utilizing the magnitude and direction of the isotopic shift of this vibration. The sensitivity of the nitrile symmetric stretching frequency of each isotopic variant to the local environment was measured by individually incorporating the probes into two distinct local environments of sfGFP. The UAAs were also utilized in concert to probe multiple local environments in sfGFP simultaneously to increase the utility of 4-cyano-L-phenylalanine.

The Influence of Coastal Access on Isotope Variation in Icelandic Arctic Foxes

PubMed Central

Dalerum, Fredrik; Perbro, Anna; Magnusdottir, Rannveig; Hersteinsson, Pall; Angerbjörn, Anders

2012-01-01

To quantify the ecological effects of predator populations, it is important to evaluate how population-level specializations are dictated by intra- versus inter-individual dietary variation. Coastal habitats contain prey from the terrestrial biome, the marine biome and prey confined to the coastal region. Such habitats have therefore been suggested to better support predator populations compared to habitats without coastal access. We used stable isotope data on a small generalist predator, the arctic fox, to infer dietary strategies between adult and juvenile individuals with and without coastal access on Iceland. Our results suggest that foxes in coastal habitats exhibited a broader isotope niche breadth compared to foxes in inland habitats. This broader niche was related to a greater diversity of individual strategies rather than to a uniform increase in individual niche breadth or by individuals retaining their specialization but increasing their niche differentiation. Juveniles in coastal habitats exhibited a narrower isotope niche breadth compared to both adults and juveniles in inland habitats, and juveniles in inland habitats inhabited a lower proportion of their total isotope niche compared to adults and juveniles from coastal habitats. Juveniles in both habitats exhibited lower intra-individual variation compared to adults. Based on these results, we suggest that foxes in both habitats were highly selective with respect to the resources they used to feed offspring, but that foxes in coastal habitats preferentially utilized marine resources for this purpose. We stress that coastal habitats should be regarded as high priority areas for conservation of generalist predators as they appear to offer a wide variety of dietary options that allow for greater flexibility in dietary strategies. PMID:22396749

The influence of coastal access on isotope variation in Icelandic arctic foxes.

PubMed

Dalerum, Fredrik; Perbro, Anna; Magnusdottir, Rannveig; Hersteinsson, Pall; Angerbjörn, Anders

2012-01-01

To quantify the ecological effects of predator populations, it is important to evaluate how population-level specializations are dictated by intra- versus inter-individual dietary variation. Coastal habitats contain prey from the terrestrial biome, the marine biome and prey confined to the coastal region. Such habitats have therefore been suggested to better support predator populations compared to habitats without coastal access. We used stable isotope data on a small generalist predator, the arctic fox, to infer dietary strategies between adult and juvenile individuals with and without coastal access on Iceland. Our results suggest that foxes in coastal habitats exhibited a broader isotope niche breadth compared to foxes in inland habitats. This broader niche was related to a greater diversity of individual strategies rather than to a uniform increase in individual niche breadth or by individuals retaining their specialization but increasing their niche differentiation. Juveniles in coastal habitats exhibited a narrower isotope niche breadth compared to both adults and juveniles in inland habitats, and juveniles in inland habitats inhabited a lower proportion of their total isotope niche compared to adults and juveniles from coastal habitats. Juveniles in both habitats exhibited lower intra-individual variation compared to adults. Based on these results, we suggest that foxes in both habitats were highly selective with respect to the resources they used to feed offspring, but that foxes in coastal habitats preferentially utilized marine resources for this purpose. We stress that coastal habitats should be regarded as high priority areas for conservation of generalist predators as they appear to offer a wide variety of dietary options that allow for greater flexibility in dietary strategies.

Nitrogen cycle dynamics in the Late Cretaceous Greenhouse

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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.

Isotope-abundance variations of selected elements (IUPAC technical report)

USGS Publications Warehouse

Coplen, T.B.; Böhlke, J.K.; De Bievre, P.; Ding, T.; Holden, N.E.; Hopple, J.A.; Krouse, H.R.; Lamberty, A.; Peiser, H.S.; Revesz, K.; Rieder, S.E.; Rosman, K.J.R.; Roth, E.; Taylor, P.D.P.; Vocke, R.D.; Xiao, Y.K.

2002-01-01

Documented variations in the isotopic compositions of some chemical elements are responsible for expanded uncertainties in the standard atomic weights published by the Commission on Atomic Weights and Isotopic Abundances of the International Union of Pure and Applied Chemistry. This report summarizes reported variations in the isotopic compositions of 20 elements that are due to physical and chemical fractionation processes (not due to radioactive decay) and their effects on the standard atomic-weight uncertainties. For 11 of those elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, silicon, sulfur, chlorine, copper, and selenium), standard atomic-weight uncertainties have been assigned values that are substantially larger than analytical uncertainties because of common isotope-abundance variations in materials of natural terrestrial origin. For 2 elements (chromium and thallium), recently reported isotope-abundance variations potentially are large enough to result in future expansion of their atomic-weight uncertainties. For 7 elements (magnesium, calcium, iron, zinc, molybdenum, palladium, and tellurium), documented isotope variations in materials of natural terrestrial origin are too small to have a significant effect on their standard atomic-weight uncertainties. This compilation indicates the extent to which the atomic weight of an element in a given material may differ from the standard atomic weight of the element. For most elements given above, data are graphically illustrated by a diagram in which the materials are specified in the ordinate and the compositional ranges are plotted along the abscissa in scales of (1) atomic weight, (2) mole fraction of a selected isotope, and (3) delta value of a selected isotope ratio.

A comparison of lead-isotope measurements on exploration-type samples using inductively coupled plasma and thermal ionization mass spectrometry

USGS Publications Warehouse

Gulson, B.L.; Meier, A.L.; Church, S.E.; Mizon, K.J.

1989-01-01

Thermal ionization mass spectrometry (TI-MS) has long been the method of choice for Pb-isotope determinations. More recently, however, inductively coupled plasma mass spectrometry (ICP-MS) has been used to determine Pb-isotope ratios for mineral exploration. The ICP-MS technique, although not as precise as TI-MS, may promote a wider application of Ph-isotope ratio methods because it allows individual isotopes to be determined more rapidly, generally without need for chemical separation (e.g., Smith et al., 1984; Hinners et al., 1987). To demonstrate the utility of the ICP-MS method, we have conducted a series of Pb-isotope measurements on several suites of samples using both TI-MS and ICP-MS. ?? 1989.

Device and method for separating oxygen isotopes

DOEpatents

Rockwood, Stephen D.; Sander, Robert K.

1984-01-01

A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

Laser isotope separation of erbium and other isotopes

DOEpatents

Haynam, C.A.; Worden, E.F.

1995-08-22

Laser isotope separation is accomplished using at least two photoionization pathways of an isotope simultaneously, where each pathway comprises two or more transition steps. This separation method has been applied to the selective photoionization of erbium isotopes, particularly for the enrichment of {sup 167}Er. The hyperfine structure of {sup 167}Er was used to find two three-step photoionization pathways having a common upper energy level. 3 figs.

Stable hydrogen and oxygen isotopes of tap water reveal structure of the San Francisco Bay Area's water system and adjustments during a major drought.

PubMed

Tipple, Brett J; Jameel, Yusuf; Chau, Thuan H; Mancuso, Christy J; Bowen, Gabriel J; Dufour, Alexis; Chesson, Lesley A; Ehleringer, James R

2017-08-01

Water availability and sustainability in the Western United States is a major flashpoint among expanding communities, growing industries, and productive agricultural lands. This issue came to a head in 2015 in the State of California, when the State mandated a 25% reduction in urban water use following a multi-year drought that significantly depleted water resources. Water demands and challenges in supplying water are only expected to intensify as climate perturbations, such as the 2012-2015 California Drought, become more common. As a consequence, there is an increased need to understand linkages between urban centers, water transport and usage, and the impacts of climate change on water resources. To assess if stable hydrogen and oxygen isotope ratios could increase the understanding of these relationships within a megalopolis in the Western United States, we collected and analyzed 723 tap waters across the San Francisco Bay Area during seven collection campaigns spanning 21 months during 2013-2015. The San Francisco Bay Area was selected as it has well-characterized water management strategies and the 2012-2105 California Drought dramatically affected its water resources. Consistent with known water management strategies and previously collected isotope data, we found large spatiotemporal variations in the δ 2 H and δ 18 O values of tap waters within the Bay Area. This is indicative of complex water transport systems and varying municipality-scale management decisions. We observed δ 2 H and δ 18 O values of tap water consistent with waters originating from snowmelt from the Sierra Nevada Mountains, local precipitation, ground water, and partially evaporated reservoir sources. A cluster analysis of the isotope data collected in this study grouped waters from 43 static sampling sites that were associated with specific water utility providers within the San Francisco Bay Area and known management practices. Various management responses to the drought, such as source switching, bringing in new sources, and water conservation, were observed in the isotope data. Finally, we estimated evaporative loss from one utility's reservoir system during the 2015 water year using a modified Craig-Gordon model to estimate the consequences of the drought on this resource. We estimated that upwards of 6.6% of the water in this reservoir system was lost to evaporation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method for separating boron isotopes

DOEpatents

Rockwood, Stephen D.

1978-01-01

A method of separating boron isotopes .sup.10 B and .sup.11 B by laser-induced selective excitation and photodissociation of BCl.sub.3 molecules containing a particular boron isotope. The photodissociation products react with an appropriate chemical scavenger and the reaction products may readily be separated from undissociated BCl.sub.3, thus effecting the desired separation of the boron isotopes.

Molecular Medicine: Synthesis and In Vivo Detection of Agents for use in Boron Neutron Capture Therapy. Final Report

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

Kabalka, G. W.

2005-06-28

The primary objective of the project was the development of in vivo methods for the detection and evaluation of tumors in humans. The project was focused on utilizing positron emission tomography (PET) to monitor the distribution and pharamacokinetics of a current boron neutron capture therapy (BNCT) agent, p-boronophenylalanine (BPA) by labeling it with a fluorine-18, a positron emitting isotope. The PET data was then used to develop enhanced treatment planning protocols. The study also involved the synthesis of new tumor selective BNCTagents that could be labeled with radioactive nuclides for the in vivo detection of boron.

Basis for calculating cross sections for nuclear magnetic resonance spin-modulated polarized neutron scattering.

PubMed

Kotlarchyk, Michael; Thurston, George M

2016-12-28

In this work we study the potential for utilizing the scattering of polarized neutrons from nuclei whose spin has been modulated using nuclear magnetic resonance (NMR). From first principles, we present an in-depth development of the differential scattering cross sections that would arise in such measurements from a hypothetical target system containing nuclei with non-zero spins. In particular, we investigate the modulation of the polarized scattering cross sections following the application of radio frequency pulses that impart initial transverse rotations to selected sets of spin-1/2 nuclei. The long-term aim is to provide a foundational treatment of the scattering cross section associated with enhancing scattering signals from selected nuclei using NMR techniques, thus employing minimal chemical or isotopic alterations, so as to advance the knowledge of macromolecular or liquid structure.

SAS2H Generated Isotopic Concentrations For B&W 15X15 PWR Assembly (SCPB:N/A)

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

J.W. Davis

This analysis is prepared by the Mined Geologic Disposal System (MGDS) Waste Package Development Department (WPDD) to provide pressurized water reactor (PWR) isotopic composition data as a function of time for use in criticality analyses. The objectives of this evaluation are to generate burnup and decay dependant isotopic inventories and to provide these inventories in a form which can easily be utilized in subsequent criticality calculations.

Alkyl group substitution by oxime-bound palladium(II) (the Shaw reaction): Alkly group selectivity and deuterium isotope effects

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

Wells, A.P.; Kitching, W.

1992-08-01

This report provides information regarding the selectivity of alkyl groups and the nature of the transition state for C-H palladation by oxime-bound palladium(II) (the Shaw reaction). The kinetic deuterium isotope effects are also presented. 21 refs.

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

EPA Science Inventory

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

18O-labeled proteome reference as global internal standards for targeted quantification by selected reaction monitoring-mass spectrometry.

PubMed

Kim, Jong-Seo; Fillmore, Thomas L; Liu, Tao; Robinson, Errol; Hossain, Mahmud; Champion, Boyd L; Moore, Ronald J; Camp, David G; Smith, Richard D; Qian, Wei-Jun

2011-12-01

Selected reaction monitoring (SRM)-MS is an emerging technology for high throughput targeted protein quantification and verification in biomarker discovery studies; however, the cost associated with the application of stable isotope-labeled synthetic peptides as internal standards can be prohibitive for screening a large number of candidate proteins as often required in the preverification phase of discovery studies. Herein we present a proof of concept study using an (18)O-labeled proteome reference as global internal standards (GIS) for SRM-based relative quantification. The (18)O-labeled proteome reference (or GIS) can be readily prepared and contains a heavy isotope ((18)O)-labeled internal standard for every possible tryptic peptide. Our results showed that the percentage of heavy isotope ((18)O) incorporation applying an improved protocol was >99.5% for most peptides investigated. The accuracy, reproducibility, and linear dynamic range of quantification were further assessed based on known ratios of standard proteins spiked into the labeled mouse plasma reference. Reliable quantification was observed with high reproducibility (i.e. coefficient of variance <10%) for analyte concentrations that were set at 100-fold higher or lower than those of the GIS based on the light ((16)O)/heavy ((18)O) peak area ratios. The utility of (18)O-labeled GIS was further illustrated by accurate relative quantification of 45 major human plasma proteins. Moreover, quantification of the concentrations of C-reactive protein and prostate-specific antigen was illustrated by coupling the GIS with standard additions of purified protein standards. Collectively, our results demonstrated that the use of (18)O-labeled proteome reference as GIS provides a convenient, low cost, and effective strategy for relative quantification of a large number of candidate proteins in biological or clinical samples using SRM.

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

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

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE PAGES

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.; ...

2017-03-06

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Standard line slopes as a measure of a relative matrix effect in quantitative HPLC-MS bioanalysis.

PubMed

Matuszewski, B K

2006-01-18

A simple experimental approach for studying and identifying the relative matrix effect (for example "plasma-to-plasma" and/or "urine-to-urine") in quantitative analyses by HPLC-MS/MS is described. Using as a database a large number of examples of methods developed in recent years in our laboratories, the relationship between the precision of standard line slopes constructed in five different lots of a biofluid (for example plasma) and the reliability of determination of concentration of an analyte in a particular plasma lot (or subject) was examined. In addition, the precision of standard line slopes was compared when stable isotope-labeled analytes versus analogs were used as internal standards (IS). Also, in some cases, a direct comparison of standard line slopes was made when different HPLC-MS interfaces (APCI versus ESI) were used for the assay of the same compound, using the same IS and the same sample preparation and chromatographic separation conditions. In selected cases, the precision of standard line slopes in five different lots of a biofluid was compared with precision values determined five times in a single lot. The results of these studies indicated that the variability of standard line slopes in different lots of a biofluid [precision of standard line slopes expressed as coefficient of variation, CV (%)] may serve as a good indicator of a relative matrix effect and, it is suggested, this precision value should not exceed 3-4% for the method to be considered reliable and free from the relative matrix effect liability. Based on the results presented, in order to assess the relative matrix effect in bioanalytical methods, it is recommended to perform assay precision and accuracy determination in five different lots of a biofluid, instead of repeat (n=5) analysis in the same, single biofluid lot, calculate standard line slopes and precision of these slopes, and to use <3-4% slope precision value as a guide for method applicability to support clinical studies. It was also demonstrated that when stable isotope-labeled analytes were used as internal standards, the precision of standard line slopes in five different lots of a biofluid was

Diode laser based resonance ionization mass spectrometric measurement of strontium-90

NASA Astrophysics Data System (ADS)

Bushaw, B. A.; Cannon, B. D.

1997-10-01

A diode laser based scheme for the isotopically selective excitation and ionization of strontium is presented. The double-resonance excitation 5s 21S 0→5s5p 3P 1→5s6s 3S 1 is followed by photoionization at 488 nm. The isotope shifts and hyperfine structure in the resonance transitions have been accurately measured for the stable isotopes and 90Sr, with the measurement of the 90Sr shifts using sub-pg samples. Analytical tests, using graphite crucible atomization, demonstrated 90Sr detection limits of 0.8 fg and overall (optical+mass spectrometer) isotopic selectivity of >10 10 against stable strontium.

Vibronic origin of sulfur mass-independent isotope effect in photoexcitation of SO2 and the implications to the early earth’s atmosphere

PubMed Central

Whitehill, Andrew R.; Xie, Changjian; Hu, Xixi; Xie, Daiqian; Guo, Hua; Ono, Shuhei

2013-01-01

Signatures of mass-independent isotope fractionation (MIF) are found in the oxygen (16O,17O,18O) and sulfur (32S, 33S, 34S, 36S) isotope systems and serve as important tracers of past and present atmospheric processes. These unique isotope signatures signify the breakdown of the traditional theory of isotope fractionation, but the physical chemistry of these isotope effects remains poorly understood. We report the production of large sulfur isotope MIF, with Δ33S up to 78‰ and Δ36S up to 110‰, from the broadband excitation of SO2 in the 250–350-nm absorption region. Acetylene is used to selectively trap the triplet-state SO2 (3B1), which results from intersystem crossing from the excited singlet (1A2/1B1) states. The observed MIF signature differs considerably from that predicted by isotopologue-specific absorption cross-sections of SO2 and is insensitive to the wavelength region of excitation (above or below 300 nm), suggesting that the MIF originates not from the initial excitation of SO2 to the singlet states but from an isotope selective spin–orbit interaction between the singlet (1A2/1B1) and triplet (3B1) manifolds. Calculations based on high-level potential energy surfaces of the multiple excited states show a considerable lifetime anomaly for 33SO2 and 36SO2 for the low vibrational levels of the 1A2 state. These results demonstrate that the isotope selectivity of accidental near-resonance interactions between states is of critical importance in understanding the origin of MIF in photochemical systems. PMID:23836655

USING MUSSEL ISTOPE RATIOS TO ASSESS ANTHROPOGENIC NITROGEN INPUTS TO FRESHWATER ECOSYSTEMS

EPA Science Inventory

Stable nitrogen isotope ratios ( 15N) of freshwater mussels from a series of lakes and ponds were related to watershed land use characteristics to assess their utility in determining the source of nitrogen inputs to inland water bodies. Nitrogen isotope ratios measured in freshwa...

STABLE CARBON ISOTOPE EVIDENCE FOR COUPLING BETWEEN SEDIMENTARY BACTERIA AND SEAGRASSES IN A SUB-TROPICAL LAGOON

EPA Science Inventory

We measured stable carbon isotope ratios (d13C) in phospholipid fatty acids (PLFAs) to identify the primary carbon source utilized by sedimentary bacteria in Lower Laguna Madre, Texas, which is a seagrass dominated lagoon. Comparisons were made between three differing habitat ty...

A novel upgrade to Helsinki AMS: Fast switching of isotopes with electrostatic deflectors

NASA Astrophysics Data System (ADS)

Palonen, V.; Tikkanen, P.

2015-10-01

We have developed and installed electrostatic deflectors at the injection magnet entrance and exit to enable fast switching between isotopes in AMS measurements. The fast selection of the injected isotope, stable isotope current measurements, and rare isotope detection are all performed with three synchronized real-time NI-PXI computers. With the improvements, we are able to attain a precision of better than 0.2% for the 14C/13C ratio of modern samples.

Stable isotopes differentiate bottlenose dolphins off west-central Florida

USGS Publications Warehouse

Barros, Nélio B.; Ostrom, P. H.; Stricker, Craig A.; Wells, R.S.

2010-01-01

Distinguishing discrete population units among continuously distributed coastal small cetaceans is challenging and crucial to conservation. We evaluated the utility of stable isotopes in assessing group membership in bottlenose dolphins (Tursiops truncatus) off west-central Florida by analyzing carbon, nitrogen, and sulfur isotope values (δ13C, δ15N, and δ34S) of tooth collagen from stranded dolphins. Individuals derived from three putative general population units: Sarasota Bay (SB), nearshore Gulf of Mexico (GULF), and offshore waters (OFF). Animals of known history (SB) served to ground truth the approach against animals of unknown history from the Gulf of Mexico (GULF, OFF). Dolphin groups differed significantly for each isotope. Average δ13C values from SB dolphins (−10.6‰) utilizing sea grass ecosystems differed from those of GULF (−11.9‰) and OFF (−11.9‰). Average δ15N values of GULF (12.7‰) and OFF (13.2‰) were higher than those of SB dolphins (11.9‰), consistent with differences in prey trophic levels. δ34S values showed definitive differences among SB (7.1‰), GULF (11.3‰), and OFF (16.5‰) dolphins. This is the first application of isotopes to population assignment of bottlenose dolphins in the Gulf of Mexico and results suggest that isotopes may provide a powerful tool in the conservation of small cetaceans.

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

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

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

1992-01-01

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

Quantitative Determination of Isotope Ratios from Experimental Isotopic Distributions

PubMed Central

Kaur, Parminder; O’Connor, Peter B.

2008-01-01

Isotope variability due to natural processes provides important information for studying a variety of complex natural phenomena from the origins of a particular sample to the traces of biochemical reaction mechanisms. These measurements require high-precision determination of isotope ratios of a particular element involved. Isotope Ratio Mass Spectrometers (IRMS) are widely employed tools for such a high-precision analysis, which have some limitations. This work aims at overcoming the limitations inherent to IRMS by estimating the elemental isotopic abundance from the experimental isotopic distribution. In particular, a computational method has been derived which allows the calculation of 13C/12C ratios from the whole isotopic distributions, given certain caveats, and these calculations are applied to several cases to demonstrate their utility. The limitations of the method in terms of the required number of ions and S/N ratio are discussed. For high-precision estimates of the isotope ratios, this method requires very precise measurement of the experimental isotopic distribution abundances, free from any artifacts introduced by noise, sample heterogeneity, or other experimental sources. PMID:17263354

Minimization of transverse beam-emittance growth in the 90-degree bending section of the RAON rare-isotope accelerator

NASA Astrophysics Data System (ADS)

Oh, B. H.; Yoon, M.

2016-11-01

The major contribution of the transverse beam emittance growth (EG) in a RAON heavy-ion accelerator comes from the bending section, which consists of a charge-stripping section, a matching section, and a charge-selection section in sequence. In this paper, we describe our research to minimize the two-dimensional EG in the 90-degree bending section of the RAON currently being developed in Korea. The EG minimization was achieved with the help of multi-objective genetic algorithms and the simplex method. We utilized those algorithms to analyze the 90-degree bending section in a driver linac for the in-flight fragmentation system. Horizontal and vertical EGs were limited to below 10 % in the bending section by adjustment of the transverse beam optics upstream from the charge-stripping section, redesign of the charge-selection section, and optimization of the vertical beam optics at the entrance of a charge-selection section.

Selective Detection of Peptide-Oligonucleotide Heteroconjugates Utilizing Capillary HPLC-ICPMS

NASA Astrophysics Data System (ADS)

Catron, Brittany; Caruso, Joseph A.; Limbach, Patrick A.

2012-06-01

A method for the selective detection and quantification of peptide:oligonucleotide heteroconjugates, such as those generated by protein:nucleic acid cross-links, using capillary reversed-phase high performance liquid chromatography (cap-RPHPLC) coupled with inductively coupled plasma mass spectrometry detection (ICPMS) is described. The selective detection of phosphorus as 31P+, the only natural isotope, in peptide-oligonucleotide heteroconjugates is enabled by the elemental detection capabilities of the ICPMS. Mobile phase conditions that allow separation of heteroconjugates while maintaining ICPMS compatibility were investigated. We found that trifluoroacetic acid (TFA) mobile phases, used in conventional peptide separations, and hexafluoroisopropanol/triethylamine (HFIP/TEA) mobile phases, used in conventional oligonucleotide separations, both are compatible with ICPMS and enable heteroconjugate separation. The TFA-based separations yielded limits of detection (LOD) of ~40 ppb phosphorus, which is nearly seven times lower than the LOD for HFIP/TEA-based separations. Using the TFA mobile phase, 1-2 pmol of a model heteroconjugate were routinely separated and detected by this optimized capLC-ICPMS method.

Cadmium-isotopic evidence for increasing primary productivity during the Late Permian anoxic event

NASA Astrophysics Data System (ADS)

Georgiev, Svetoslav V.; Horner, Tristan J.; Stein, Holly J.; Hannah, Judith L.; Bingen, Bernard; Rehkämper, Mark

2015-01-01

Earth's most extreme extinction event near the end of the Late Permian decimated more than 90% of all extant marine species. Widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe, though the driving mechanisms that sustained such conditions are still debated. Of particular interest is whether water column anoxia was a consequence of a 'stagnant ocean', or if it was controlled by increases in nutrient supply, primary productivity, and subsequent heterotrophic respiration. Testing these competing hypotheses requires deconvolving sedimentary/bottom water redox conditions from changes in surface water productivity in marine sediments. We address this issue by studying marine shales from East Greenland and the mid-Norwegian shelf and combining sedimentary redox proxies with cadmium-isotopic analyses. Sedimentary nitrogen-isotopic data, pyrite framboid analyses, and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling, and increasingly anoxic conditions with a strengthening upwelling in the Greenland and Norwegian sections, respectively. Detailed analysis of sedimentary metal budgets illustrates that Cd is primarily associated with organic carbon and records primary geochemical signatures, thus enabling reconstruction of surface water nutrient utilization. Cadmium-isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average δ114Cd110 of + 0.15 ± 0.01 ‰ (2 SE, n = 12; rel. NIST SRM 3108), indicative of incomplete surface water nutrient utilization up-section. The constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity - and not oceanic stagnation - to balance the larger nutrient fluxes to both study sites during the development of the Late Permian water column anoxia. Overall, our data illustrate that if bottom water redox and upwelling can be adequately constrained, Cd-isotopic analyses of organic-rich sediments can be used to provide valuable information on nutrient utilization and therefore past productivity.

A Noninvasive Isotopic Approach to Estimate the Bone Lead Contribution to Blood in Children: Implications for Assessing the Efficacy of Lead Abatement

PubMed Central

Gwiazda, Roberto; Campbell, Carla; Smith, Donald

2005-01-01

Lead hazard control measures to reduce children’s exposure to household lead sources often result in only limited reductions in blood lead levels. This may be due to incomplete remediation of lead sources and/or to the remobilization of lead stores from bone, which may act as an endogenous lead source that buffers reductions in blood lead levels. Here we present a noninvasive isotopic approach to estimate the magnitude of the bone lead contribution to blood in children following household lead remediation. In this approach, lead isotopic ratios of a child’s blood and 5-day fecal samples are determined before and after a household intervention aimed at reducing the child’s lead intake. The bone lead contribution to blood is estimated from a system of mass balance equations of lead concentrations and isotopic compositions in blood at the different times of sample collection. The utility of this method is illustrated with three cases of children with blood lead levels in the range of 18–29 μg/dL. In all three cases, the release of lead from bone supported a substantial fraction of the measured blood lead level postintervention, up to 96% in one case. In general, the lead isotopic compositions of feces matched or were within the range of the lead isotopic compositions of the household dusts with lead loadings exceeding U.S. Environmental Protection Agency action levels. This isotopic agreement underscores the utility of lead isotopic measurements of feces to identify household sources of lead exposure. Results from this limited number of cases support the hypothesis that the release of bone lead into blood may substantially buffer the decrease in blood lead levels expected from the reduction in lead intake. PMID:15626656

Comprehensive Gas-Phase Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 2. Gas-Phase Hydrogen/Deuterium Exchange for Ion Population Estimation.

PubMed

Khakinejad, Mahdiar; Ghassabi Kondalaji, Samaneh; Tafreshian, Amirmahdi; Valentine, Stephen J

2017-05-01

Gas-phase hydrogen/deuterium exchange (HDX) using D 2 O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions. Graphical Abstract ᅟ.

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

NASA Astrophysics Data System (ADS)

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

2016-01-01

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

Isotope-abundance variations and atomic weights of selected elements: 2016 (IUPAC Technical Report)

USGS Publications Warehouse

Coplen, Tyler B.; Shrestha, Yesha

2016-01-01

There are 63 chemical elements that have two or more isotopes that are used to determine their standard atomic weights. The isotopic abundances and atomic weights of these elements can vary in normal materials due to physical and chemical fractionation processes (not due to radioactive decay). These variations are well known for 12 elements (hydrogen, lithium, boron, carbon, nitrogen, oxygen, magnesium, silicon, sulfur, chlorine, bromine, and thallium), and the standard atomic weight of each of these elements is given by IUPAC as an interval with lower and upper bounds. Graphical plots of selected materials and compounds of each of these elements have been published previously. Herein and at the URL http://dx.doi.org/10.5066/F7GF0RN2, we provide isotopic abundances, isotope-delta values, and atomic weights for each of the upper and lower bounds of these materials and compounds.

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

Application of stable isotope ratio analysis for biodegradation monitoring in groundwater

USGS Publications Warehouse

Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.

2013-01-01

Stable isotope ratio analysis is increasingly being applied as a tool to detect, understand, and quantify biodegradation of organic and inorganic contaminants in groundwater. An important feature of this approach is that it allows degradative losses of contaminants to be distinguished from those caused by non-destructive processes such as dilution, dispersion, and sorption. Recent advances in analytical techniques, and new approaches for interpreting stable isotope data, have expanded the utility of this method while also exposing complications and ambiguities that must be considered in data interpretations. Isotopic analyses of multiple elements in a compound, and multiple compounds in the environment, are being used to distinguish biodegradative pathways by their characteristic isotope effects. Numerical models of contaminant transport, degradation pathways, and isotopic composition are improving quantitative estimates of in situ contaminant degradation rates under realistic environmental conditions.

Lead isotope database of unpublished results from sulfide mineral occurrences-California, Idaho, Oregon, and Washington

USGS Publications Warehouse

Church, S.E.

2010-01-01

The Pb isotope database for sulfide deposits and occurrences in the Western United States was funded by the Mineral Resources Program, U.S. Geological Survey (USGS). Reports on Pb isotope data from Alaska were published in Church and others (1987a) and Gaccetta and Church (1989). The primary objectives of the project were three-fold: * To utilize Pb isotope signatures, in conjunction with the regional mapping, to assess the relative ages and to categorize the types of deposits studied, * To relate the Pb isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and * To use the Pb isotope data to correlate lithotectonic terranes within the northern Cordillera. The report by Church and others (1987b) shows how this fingerprinting methodology can be applied to trace the offset of lithostratigraphic terranes

Implementation of a solid target production facility

NASA Astrophysics Data System (ADS)

Tochon-Danguy, H. J.; Poniger, S. S.; Sachinidis, J. I.; Panopoulos, H. P.; Scott, A. M.

2012-12-01

The desire to utilize long-lived PET isotopes in Australia has significantly increased over the years and several research projects for labelling of peptides, proteins and biomolecules, including labelling of recombinant antibodies has been restricted due to the limited availability of suitable isotopes. This need has led to the recent installation and commissioning of a new facility dedicated to fully automated solid target isotope production, including 24I, 64Cu, 89Zr and 86Y at the Austin Health Centre for PET.

CORRESPONDENCE OF STABLE ISOTOPE AND GUT CONTENTS ANALYSES IN DETERMINING TROPHIC POSITION OF STREAM FISHES

EPA Science Inventory

It is generally accepted that both stable isotope analysis (SIA) and gut contents analysis (GCA) be used in food web studies; however, few researchers have analyzed these data in concert. We utilized SIA and GCA to determine if longitudinal and seasonal variation in diet affects...

UTILIZATION OF THE CARBON AND HYDROGEN ISOTOPIC COMPOSITION OF INDIVIDUAL COMPOUNDS IN REFINED HYDROCARBON PRODUCTS TO MONITOR THEIR FATE IN THE ENVIRONMENT

EPA Science Inventory

Isotope effects resulting from biodegradation of MTBE
To conduct the microcosm biodegradation study, sediment samples were collected from sites offering high potential of MTBE biodegradation. Sites where sediment samples were collected for the MTBE microcosm c...

High-sensitivity stable-isotope probing by a quantitative terminal restriction fragment length polymorphism protocol.

PubMed

Andeer, Peter; Strand, Stuart E; Stahl, David A

2012-01-01

Stable-isotope probing (SIP) has proved a valuable cultivation-independent tool for linking specific microbial populations to selected functions in various natural and engineered systems. However, application of SIP to microbial populations with relatively minor buoyant density increases, such as populations that utilize compounds as a nitrogen source, results in reduced resolution of labeled populations. We therefore developed a tandem quantitative PCR (qPCR)-TRFLP (terminal restriction fragment length polymorphism) protocol that improves resolution of detection by quantifying specific taxonomic groups in gradient fractions. This method combines well-controlled amplification with TRFLP analysis to quantify relative taxon abundance in amplicon pools of FAM-labeled PCR products, using the intercalating dye EvaGreen to monitor amplification. Method accuracy was evaluated using mixtures of cloned 16S rRNA genes, DNA extracted from low- and high-G+C bacterial isolates (Escherichia coli, Rhodococcus, Variovorax, and Microbacterium), and DNA from soil microcosms amended with known amounts of genomic DNA from bacterial isolates. Improved resolution of minor shifts in buoyant density relative to TRFLP analysis alone was confirmed using well-controlled SIP analyses.

Method of enhancing selective isotope desorption from metals

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1984-01-01

A method of enhancing the thermal desorption of a first isotope of a diatomic gas from a metal comprises the steps of (a) establishing a partial pressure of a second isotope of the diatomic gas in vicinity of the metal; heating the metal to a temperature such that the first isotope is desorbed from the metal; and reducing the partial pressure of the desorbed first isotope while maintaining the partial pressure of the second isotope substantially constant. The method is especially useful for enhancing the desorption of tritium from the Zr-Al getter in a plasma confinement device.

[Determination of endogenous agmatine in rat plasma by isotope dilution-gas chromatography-mass spectrometry].

PubMed

Qiu, Zhongli; Lin, Ying; Xiong, Zhili; Xie, Jianwei

2014-07-01

A method for the determination of endogenous agmatine in rat plasma was developed by isotope dilution-gas chromatography-negative chemical ionization mass spectrometry (GC-NCI/MS). The plasma samples were analyzed after protein precipitation, evaporation, derivatization by hexafluoroacetone (HFAA), and clean-up on a Florisil SPE column. The GC-MS analysis utilized stable isotope d8-agmatine as internal standard. The samples after treatme were tested by negative chemical ionization with selected ion monitoring (SIM) which was set at m/z 492 (molecular ion of agmatine) and m/z 500 (molecular ion of internal standard). The limit of detection (LOD) of agmatine standard solution was 0.005 7 ng/mL. The calibration curve of the agmatine spiked in rat plasma showed a good linear relationship at the range of 1.14-57.0 ng/mL (r = 0.997). The recoveries of agmatine spiked in rat plasma ranged from 92.3% to 109.8%. Inter-day and intra-day precisions were less than 15%. The average concentration level of agmatine in rat plasma was (22 +/- 9) ng/mL, and there was no significant difference between male and female SD rats (p > 0.05). The method is high sensitive and specific, and can be used for the determination of endogenous agmatine in plasma. It provides a strong support for the subsequent research of agmatine.

Environmental site description for a Uranium Atomic Vapor Laser Isotope Separation (U-AVLIS) production plant at the Paducah Gaseous Diffusion Plant site

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

Marmer, G.J.; Dunn, C.P.; Moeller, K.L.

Uranium enrichment in the United States has utilized a diffusion process to preferentially enrich the U-235 isotope in the uranium product. The U-AVLIS process is based on electrostatic extraction of photoionized U-235 atoms from an atomic vapor stream created by electron-beam vaporization of uranium metal alloy. The U-235 atoms are ionized when precisely tuned laser light -- of appropriate power, spectral, and temporal characteristics -- illuminates the uranium vapor and selectively photoionizes the U-235 isotope. A programmatic document for use in screening DOE site to locate a U-AVLIS production plant was developed and implemented in two parts. The first partmore » consisted of a series of screening analyses, based on exclusionary and other criteria, that identified a reasonable number of candidate sites. These sites were subjected to a more rigorous and detailed comparative analysis for the purpose of developing a short list of reasonable alternative sites for later environmental examination. This environmental site description (ESD) provides a detailed description of the PGDP site and vicinity suitable for use in an environmental impact statement (EIS). The report is based on existing literature, data collected at the site, and information collected by Argonne National Laboratory (ANL) staff during a site visit. 65 refs., 15 tabs.« less

Hybrid isotope separation scheme

DOEpatents

Maya, Jakob

1991-01-01

A method of yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus.

Ionization enhancement in atmospheric pressure chemical ionization and suppression in electrospray ionization between target drugs and stable-isotope-labeled internal standards in quantitative liquid chromatography/tandem mass spectrometry.

PubMed

Liang, H R; Foltz, R L; Meng, M; Bennett, P

2003-01-01

The phenomena of ionization suppression in electrospray ionization (ESI) and enhancement in atmospheric pressure chemical ionization (APCI) were investigated in selected-ion monitoring and selected-reaction monitoring modes for nine drugs and their corresponding stable-isotope-labeled internal standards (IS). The results showed that all investigated target drugs and their co-eluting isotope-labeled IS suppress each other's ionization responses in ESI. The factors affecting the extent of suppression in ESI were investigated, including structures and concentrations of drugs, matrix effects, and flow rate. In contrast to the ESI results, APCI caused seven of the nine investigated target drugs and their co-eluting isotope-labeled IS to enhance each other's ionization responses. The mutual ionization suppression or enhancement between drugs and their isotope-labeled IS could possibly influence assay sensitivity, reproducibility, accuracy and linearity in quantitative liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, calibration curves were linear if an appropriate IS concentration was selected for a desired calibration range to keep the response factors constant. Copyright 2003 John Wiley & Sons, Ltd.

Reusable rocket engine turbopump condition monitoring

NASA Technical Reports Server (NTRS)

Hampson, M. E.; Barkhoudarian, S.

1985-01-01

Significant improvements in engine readiness with attendant reductions in maintenance costs and turnaround times can be achieved with an engine condition monitoring system (CMS). The CMS provides real time health status of critical engine components, without disassembly, through component monitoring with advanced sensor technologies. Three technologies were selected to monitor the rotor bearings and turbine blades: the isotope wear detector and fiber optic deflectometer (bearings), and the fiber optic pyrometer (blades). Signal processing algorithms were evaluated and ranked for their utility in providing useful component health data to unskilled maintenance personnel. Design modifications to current configuration Space Shuttle Main Engine (SSME) high pressure turbopumps and the MK48-F turbopump were developed to incorporate the sensors.

Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters--An Experimental and Theoretical Study on Directing Group Chemoselectivity.

PubMed

Devlin, Jennifer; Kerr, William J; Lindsay, David M; McCabe, Timothy J D; Reid, Marc; Tuttle, Tell

2015-06-25

Herein we report a combined experimental and theoretical study on the deuterium labelling of benzoate ester derivatives, utilizing our developed iridium N-heterocyclic carbene/phosphine catalysts. A range of benzoate esters were screened, including derivatives with electron-donating and -withdrawing groups in the para- position. The substrate scope, in terms of the alkoxy group, was studied and the nature of the catalyst counter-ion was shown to have a profound effect on the efficiency of isotope exchange. Finally, the observed chemoselectivity was rationalized by rate studies and theoretical calculations, and this insight was applied to the selective labelling of benzoate esters bearing a second directing group.

Using Oxygen and Carbon Isotopic Signatures in Order to Infer Climatic and Dietary Information in Roman Edessa, Greece

NASA Astrophysics Data System (ADS)

Michael, Dimitra-Ermioni; Dotsika, Elissavet

2017-12-01

Even though many isotopic studies have been conducted on ancient populations from Greece for the purpose of dietary reconstruction; mostly through carbon and nitrogen isotopic signals of bone collagen, less attention has been given to the utility of apatite signatures (oxygen and carbon) as dietary and palaeoenvironmental tools. Moreover, until recently the isotopic signal of tooth enamel for both the purposes of environmental and dietary reconstructions has been rarely assessed in ancient Greek societies. Therefore, the present study aims to provide with novel isotopic information regarding Edessa; a town in Northern Greece, during the Roman period. The current study primarily aims to explore the possible differentiation between the present climatic conditions in Edessa in relation to those occurring at the Roman period. Secondly, this study aims to reveal the significant utility of enamel isotopic signatures (carbon and oxygen) in palaeoenvironmental and palaeodietary studies regarding ancient human remains. The isotopic analyses have been conducted at the Stable Isotope and Radiocarbon Unit of INN, NCSR “Demokritos”. The population of Roman Edessa (2nd-4th c. AD) consists of 22 individuals, providing with 19 bone samples and 16 enamel ones. The mean enamel oxygen value is at -7.7 ±1.1 %0, the bone apatite mean oxygen value at -9.2 ±1.9 %0, and finally the mean carbon enamel value is at -11.7 ±1.2 %0. Oxygen values probably indicate that Edessa had a cooler climate during the Roman times in relation to present conditions, even though more research should be carried out in order to be more certain. In addition, the possible existence of non-local individuals has been revealed through the oxygen teeth enamel-bone apatite spacing. Finally, the carbon enamel signature has pointed out possible differentiations between the adult and the juvenile diet. Based on Edessa’s findings, the stated study strongly encourages the enamel oxygen and carbon isotopic signals as palaeoclimatological and palaeodietary tools respectively.

Assessing Precipitation Isotope Variations during Atmospheric River Events to Reveal Dominant Atmospheric/Hydrologic Processes

NASA Astrophysics Data System (ADS)

McCabe-Glynn, S. E.; Johnson, K. R.; Yoshimura, K.; Buenning, N. H.; Welker, J. M.

2015-12-01

Extreme precipitation events across the Western US commonly associated with atmospheric rivers (ARs), whereby extensive fluxes of moisture are transported from the subtropics, can result in major damage and are projected by most climate models to increase in frequency and severity. However, they are difficult to project beyond ~ten days and the location of landfall and topographically induced precipitation is even more uncertain. Water isotopes, often used to reconstruct past rainfall variability, are useful natural tracers of atmospheric hydrologic processes. Because of the typical tropical and sub-tropical origins, ARs can carry unique water isotope (δ18O and δ2H, d-excess) signatures that can be utilized to provide source and process information that can lead to improving AR predictions. Recent analysis of the top 10 weekly precipitation total samples from Sequoia National Park, CA, of which 9 contained AR events, shows a high variability in the isotopic values. NOAA Hysplit back trajectory analyses reveals a variety of trajectories and varying latitudinal source regions contributed to moisture delivered to this site, which may explain part of the high variability (δ2H = -150.03 to -49.52 ‰, δ18O = -19.27 to -7.20 ‰, d-excess = 4.1 to 25.8). Here we examine the top precipitation totals occurring during AR events and the associated isotopic composition of precipitation samples from several sites across the Western US. We utilize IsoGSM, an isotope-enabled atmospheric general circulation model, to characterize the hydrologic processes and physical dynamics contributing to the observed isotopic variations. We investigate isotopic influences from moisture source location, AR speed, condensation height, and associated temperature. We explore the dominant controls on spatial and temporal variations of the isotopic composition of AR precipitation which highlights different physical processes for different AR events.

Mercury in gray wolves (Canis lupus) in Alaska: Increased exposure through consumption of marine prey

USGS Publications Warehouse

McGrew, Ashley K.; Ballweber, Lora R.; Moses, Sara K.; Stricker, Craig A.; Beckmen, Kimberlee B.; Salman, Mo D.; O’Hara, Todd M.

2013-01-01

Mercury (Hg) bioaccumulates in the tissues of organismsand biomagnifies within food-webs. Graywolves (Canis lupus) in Alaska primarily acquire Hg through diet; therefore, comparing the extent of Hg exposure inwolves, in conjunction with stable isotopes, from interior and coastal regions of Alaska offers important insight into their feeding ecology. Liver, kidney, and skeletal muscle samples from 162 graywolves were analyzed for total mercury (THg) concentrations and stable isotopic signatures (δ13C, δ15N, and δ34S).Median hepatic THg concentrations were significantly higher in wolves with coastal access compared to wolves from interior Alaska. Stable isotope ratios, in conjunction with THg concentrations, provide strong evidence that coastal wolves are utilizing marine prey representing several trophic levels. The utilization of cross-ecosystem food resources by coastal wolves is clearly contributing to increased THg exposure, and may ultimately have negative health implications for these animals.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1987-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C. Paul; Rockwood, Stephen D.; Jensen, Reed J.; Lyman, John L.; Aldridge, III, Jack P.

1977-01-01

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, in the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO.sub.2 laser light may be used to highly enrich .sup.34 S in natural SF.sub.6 and .sup.11 B in natural BCl.sub.3.

Carbon isotope fractionation during microbial methane oxidation

NASA Astrophysics Data System (ADS)

Barker, James F.; Fritz, Peter

1981-09-01

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

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

PubMed Central

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

2017-01-01

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

Discrimination of ginseng cultivation regions using light stable isotope analysis.

PubMed

Kim, Kiwook; Song, Joo-Hyun; Heo, Sang-Cheol; Lee, Jin-Hee; Jung, In-Woo; Min, Ji-Sook

2015-10-01

Korean ginseng is considered to be a precious health food in Asia. Today, thieves frequently compromise ginseng farms by pervasive theft. Thus, studies regarding the characteristics of ginseng according to growth region are required in order to deter ginseng thieves and prevent theft. In this study, 6 regions were selected on the basis of Korea regional criteria (si, gun, gu), and two ginseng-farms were randomly selected from each of the 6 regions. Then 4-6 samples of ginseng were acquired from each ginseng farm. The stable isotopic compositions of H, O, C, and N of the collected ginseng samples were analyzed. As a result, differences in the hydrogen isotope ratios could be used to distinguish regional differences, and differences in the nitrogen isotope ratios yielded characteristic information regarding the farms from which the samples were obtained. Thus, stable isotope values could be used to differentiate samples according to regional differences. Therefore, stable isotope analysis serves as a powerful tool to discriminate the regional origin of Korean ginseng samples from across Korea. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

An interactive code (NETPATH) for modeling NET geochemical reactions along a flow PATH, version 2.0

USGS Publications Warehouse

Plummer, Niel; Prestemon, Eric C.; Parkhurst, David L.

1994-01-01

NETPATH is an interactive Fortran 77 computer program used to interpret net geochemical mass-balance reactions between an initial and final water along a hydrologic flow path. Alternatively, NETPATH computes the mixing proportions of two to five initial waters and net geochemical reactions that can account for the observed composition of a final water. The program utilizes previously defined chemical and isotopic data for waters from a hydrochemical system. For a set of mineral and (or) gas phases hypothesized to be the reactive phases in the system, NETPATH calculates the mass transfers in every possible combination of the selected phases that accounts for the observed changes in the selected chemical and (or) isotopic compositions observed along the flow path. The calculations are of use in interpreting geochemical reactions, mixing proportions, evaporation and (or) dilution of waters, and mineral mass transfer in the chemical and isotopic evolution of natural and environmental waters. Rayleigh distillation calculations are applied to each mass-balance model that satisfies the constraints to predict carbon, sulfur, nitrogen, and strontium isotopic compositions at the end point, including radiocarbon dating. DB is an interactive Fortran 77 computer program used to enter analytical data into NETPATH, and calculate the distribution of species in aqueous solution. This report describes the types of problems that can be solved, the methods used to solve problems, and the features available in the program to facilitate these solutions. Examples are presented to demonstrate most of the applications and features of NETPATH. The codes DB and NETPATH can be executed in the UNIX or DOS1 environment. This report replaces U.S. Geological Survey Water-Resources Investigations Report 91-4078, by Plummer and others, which described the original release of NETPATH, version 1.0 (dated December, 1991), and documents revisions and enhancements that are included in version 2.0. 1 The use of trade, brand or product names in this report is for identification purposes only and does not constitute endorsement by the U.S. Geological Survey.

Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

PubMed

Le, Phuong-Mai; Ding, Jianfu; Leek, Donald M; Mester, Zoltan; Robertson, Gilles; Windust, Anthony; Meija, Juris

2016-10-01

In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity). The isotopic purity of all three standards was also assessed by NMR from the carbon-13 satellite signals. The standards are non-hygroscopic, high-purity (ca. 0.99 g/g), and the carbon-13 enrichment for both isotopic standards is x((13)C)≈0.99. These standards are designed for use as primary calibrators for mass spectrometric determination of arsenobetaine in environmental samples.

Hybrid isotope separation scheme

DOEpatents

Maya, J.

1991-06-18

A method is described for yielding selectively a desired enrichment in a specific isotope including the steps of inputting into a spinning chamber a gas from which a scavenger, radiating the gas with a wave length or frequency characteristic of the absorption of a particular isotope of the atomic or molecular gas, thereby inducing a photochemical reaction between the scavenger, and collecting the specific isotope-containing chemical by using a recombination surface or by a scooping apparatus. 2 figures.

Isotopic analysis of N and O in nitrite and nitrate by sequential selective bacterial reduction to N2O

USGS Publications Warehouse

Böhlke, J.K.; Smith, R.L.; Hannon, J.E.

2007-01-01

Nitrite is an important intermediate species in the biogeochemical cycling of nitrogen, but its role in natural aquatic systems is poorly understood. Isotopic data can be used to study the sources and transformations of NO2- in the environment, but methods for independent isotopic analyses of NO2- in the presence of other N species are still new and evolving. This study demonstrates that isotopic analyses of N and O in NO2- can be done by treating whole freshwater or saltwater samples with the denitrifying bacterium Stenotrophomonas nitritireducens, which selectively reduces NO2- to N2O for isotope ratio mass spectrometry. When calibrated with solutions containing NO2- with known isotopic compositions determined independently, reproducible δ15N and δ18O values were obtained at both natural-abundance levels (±0.2−0.5‰ for δ15N and ±0.4−1.0‰ for δ18O) and moderately enriched 15N tracer levels (±20−50‰ for δ15N near 5000‰) for 5−20 nmol of NO2- (1−20 μmol/L in 1−5 mL aliquots). This method is highly selective for NO2-and was used for mixed samples containing both NO2- and NO3- with little or no measurable cross-contamination. In addition, mixed samples that were analyzed with S. nitritireducens were treated subsequently with Pseudomonas aureofaciens to reduce the NO3- in the absence of NO2-, providing isotopic analyses of NO2- and NO3- separately in the same aliquot. Sequential bacterial reduction methods like this one should be useful for a variety of isotopic studies aimed at understanding nitrogen cycling in aquatic environments. A test of these methods in an agricultural watershed in Indiana provides isotopic evidence for both nitrification and denitrification as sources of NO2- in a small stream.

Stable isotopic composition of deep sea gorgonian corals (Primnoa spp.): a new archive of surface processes.

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

Sherwood, O A; Heikoop, J M; Scott, D B

2005-02-03

The deep-sea gorgonian coral Primnoa spp. lives in the Atlantic and Pacific Oceans at depths of 65-3200 m. This coral has an arborescent growth form with a skeletal axis composed of annual rings made from calcite and gorgonin. It has a lifespan of at least several hundred years. It has been suggested that isotopic profiles from the gorgonin fraction of the skeleton could be used to reconstruct long-term, annual-scale variations in surface productivity. We tested assumptions about the trophic level, intra-colony isotopic reproducibility, and preservation of isotopic signatures in a suite of modern and fossil specimens. Measurements of gorgonin {Delta}{supmore » 14}C and {delta}{sup 15}N indicate that Primnoa spp. feed mainly on zooplankton and/or sinking particulate organic matter (POM{sub SINK}), and not on suspended POM (POM{sub SUSP}) or dissolved organic carbon (DOC). Gorgonin {delta}{sup 13}C and {delta}{sup 15}N in specimens from NE Pacific shelf waters, NW Atlantic slope waters, the Sea of Japan, and a South Pacific (Southern Ocean sector) seamount were strongly correlated with Levitus 1994 surface apparent oxygen utilization (AOU; the best available measure of surface productivity), demonstrating coupling between skeletal isotopic ratios and biophysical processes in surface water. Time-series isotopic profiles from different sections along the same colony were identical for {delta}{sup 13}C, while {delta}{sup 15}N profiles became more dissimilar with increasing separation along the colony axis. Similarity in C:N, {delta}{sup 13}C and {delta}{sup 15}N between modern and fossil specimens suggest that isotopic signatures are preserved over millennial timescales. Finally, the utility of this new archive was demonstrated by reconstruction of 20th century bomb radiocarbon.« less

Electrical Engineering in Los Alamos Neutron Science Center Accelerator

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

Silva, Michael James

The field of electrical engineering plays a significant role in particle accelerator design and operations. Los Alamos National Laboratories LANSCE facility utilizes the electrical energy concepts of power distribution, plasma generation, radio frequency energy, electrostatic acceleration, signals and diagnostics. The culmination of these fields produces a machine of incredible potential with uses such as isotope production, neutron spallation, neutron imaging and particle analysis. The key isotope produced in LANSCE isotope production facility is Strontium-82 which is utilized for medical uses such as cancer treatment and positron emission tomography also known as PET scans. Neutron spallation is one of the verymore » few methods used to produce neutrons for scientific research the other methods are natural decay of transuranic elements from nuclear reactors. Accelerator produce neutrons by accelerating charged particles into neutron dense elements such as tungsten imparting a neutral particle with kinetic energy, this has the benefit of producing a large number of neutrons as well as minimizing the waste generated. Utilizing the accelerator scientist can gain an understanding of how various particles behave and interact with matter to better understand the natural laws of physics and the universe around us.« less

Preliminary assessment of rover power systems for the Mars Rover Sample Return Mission

NASA Technical Reports Server (NTRS)

Bents, D. J.

1989-01-01

Four isotope power system concepts were presented and compared on a common basis for application to on-board electrical prime power for an autonomous planetary rover vehicle. A representative design point corresponding to the Mars Rover Sample Return (MRSR) preliminary mission requirements (500 W) was selected for comparison purposes. All systems concepts utilize the General Purpose Heat Source (GPHS) isotope heat source developed by DOE. Two of the concepts employ thermoelectric (TE) conversion: one using the GPHS Radioisotope Thermoelectric Generator (RTG) used as a reference case, the other using an advanced RTG with improved thermoelectric materials. The other two concepts employed are dynamic isotope power systems (DIPS): one using a closed Brayton cycle (CBC) turboalternator, and the other using a free piston Stirling cycle engine/linear alternator (FPSE) with integrated heat source/heater head. Near-term technology levels have been assumed for concept characterization using component technology figure-of-merit values taken from the published literature. For example, the CBC characterization draws from the historical test database accumulated from space Brayton cycle subsystems and components from the NASA B engine through the mini-Brayton rotating unit. TE system performance is estimated from Voyager/multihundred Watt (MHW)-RTG flight experience through Mod-RTG performance estimates considering recent advances in TE materials under the DOD/DOE/NASA SP-100 and NASA Committee on Scientific and Technological Information programs. The Stirling DIPS system is characterized from scaled-down Space Power Demonstrator Engine (SPDE) data using the GPHS directly incorporated into the heater head. The characterization/comparison results presented here differ from previous comparison of isotope power (made for LEO applications) because of the elevated background temperature on the Martian surface compared to LEO, and the higher sensitivity of dynamic systems to elevated s

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Quantification of in Situ Biodegradation Rate Constants Using a Novel Combined Isotope Approach

NASA Astrophysics Data System (ADS)

Blum, P.; Sültenfuß, J.; Martus, P.

2014-12-01

Numerous studies have shown the enormous potential of the compound-specific isotope analysis (CSIA) for studying the biodegradation of organic compounds such as monoaromatic hydrocarbons (BTEX), polyaromatic hydrocarbons (PAH), chlorinated solvents and other organic contaminants and environmental transformation mechanisms in groundwater. In addition, two-dimensional isotope analysis such as carbon and hydrogen have been successfully studied indicating the potential to also investigate site-specific reaction mechanisms. The main objective of the current study however is to quantify real effective in situ biodegradation rate constants in a coal-tar contaminated aquifer by combining compound-specific isotope analysis (CSIA) and tracer-based (3H-3He) ground-water dating (TGD). Hence, groundwater samples are used to determine groundwater residence times, and carbon and hydrogen stable isotopes are analyzed for selected BTEX and PAH. The results of the hydrogen stable isotopes surprisingly indicate no isotope fractionation and therefore no biodegradation. In contrast, for stable carbon isotopes of selected BTEX such as o-xylene and toluene, isotope shifts are detected indicating active biodegradation under sulfate-reducing conditions. These and previous results of stable carbon isotopes show that only for o-xylene a clear evidence for biodegradation is possible for the studied site. Nevertheless, in combining these results with the groundwater residence times, which range between 1 year for the shallow wells (20 m below surface) and 41 years for the deeper wells (40 m below surface), it is feasible to effectively determine in situ biodegradation rate constants for o-xylene. Conversely, the outcome also evidently demonstrate the major limitations of the novel combined isotope approach for a successful implementation of monitored natural attenuation (MNA) at such field sites.

Inter-laboratory comparison of elemental analysis and gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS). Part I: delta13C measurements of selected compounds for the development of an isotopic Grob-test.

PubMed

Serra, F; Janeiro, A; Calderone, G; Rojas, J M Moreno; Rhodes, C; Gonthier, L A; Martin, F; Lees, M; Mosandl, A; Sewenig, S; Hener, U; Henriques, B; Ramalho, L; Reniero, F; Teixeira, A J; Guillou, C

2007-03-01

This study was directed towards investigating suitable compounds to be used as stable isotope reference materials for gas chromatography combustion isotope ratio mass spectrometry (GC-C-IRMS) calibration. Several compounds were selected from those used in the 'Grob-test' mixture. Oxygen- and nitrogen-containing substances were added to these compounds to allow the mixture to be used as a possible multi-isotopic calibration tool for 2H/1H, 13C/12C, 15N/14N and 18O/16O ratio determinations. In this paper we present the results of delta13C measurements performed by the consortium of the five laboratories taking part in this inter-calibration exercise. All the compounds were individually assessed for homogeneity, short-term stability and long-term stability by means of EA-IRMS, as required by the bureau communitaire de reference (BCR) Guide for Production of Certified Reference Materials. The results were compared then with the GC-C-IRMS measurements using both polar and non-polar columns, and the final mixture of selected compounds underwent a further certification exercise assessing limits of accuracy and reproducibility under specified GC-C-IRMS conditions. Copyright 2007 John Wiley & Sons, Ltd.

Natural Isotope Abundance in Metabolites: Techniques and Kinetic Isotope Effect Measurement in Plant, Animal, and Human Tissues.

PubMed

Tea, Illa; Tcherkez, Guillaume

2017-01-01

The natural isotope abundance in bulk organic matter or tissues is not a sufficient base to investigate physiological properties, biosynthetic mechanisms, and nutrition sources of biological systems. In fact, isotope effects in metabolism lead to a heterogeneous distribution of 2 H, 18 O, 13 C, and 15 N isotopes in metabolites. Therefore, compound-specific isotopic analysis (CSIA) is crucial to biological and medical applications of stable isotopes. Here, we review methods to implement CSIA for 15 N and 13 C from plant, animal, and human samples and discuss technical solutions that have been used for the conversion to CO 2 and N 2 for IRMS analysis, derivatization and isotope effect measurements. It appears that despite the flexibility of instruments used for CSIA, there is no universal method simply because the chemical nature of metabolites of interest varies considerably. Also, CSIA methods are often limited by isotope effects in sample preparation or the addition of atoms from the derivatizing reagents, and this implies that corrections must be made to calculate a proper δ-value. Therefore, CSIA has an enormous potential for biomedical applications, but its utilization requires precautions for its successful application. © 2017 Elsevier Inc. All rights reserved.

Nondispersive infrared spectrometry for 13CO2/12CO2-measurements: a clinically feasible analyzer for stable isotope breath tests in gastroenterology.

PubMed

Braden, B; Caspary, W F; Lembcke, B

1999-06-01

13C-urea breath tests have become clinical routine for the diagnosis of Helicobacter pylori infection and other isotope breath tests have been invented e.g. for gastric emptying or quantitative liver function testing. Recently, isotope-selective nondispersive infrared spectrometers (NDIRS) have been developed for the analysis of the 13CO2/12CO2-enrichment in breath. In this study, we prospectively tested the validity of a newly developed NDIRS in comparison to isotope ratio mass spectrometry (IRMS). 142 patients with dyspeptic symptoms were tested for Helicobacter pylori infection using the 13C-urea breath test. The isotope ratio analysis of the breath samples was performed in duplicate both using IRMS and NDIRS. The results of the baseline-corrected 13CO2-exhalation values between IRMS and NDIRS were in excellent agreement. The mean difference between both methods was 0.28 +/- 1.93 delta/1000. Evaluating the qualitative urea breath test results in reference to IRMS as the reference the NDIRS had a sensitivity of 97.8% and a specificity of 98.9%. The isotope-selective nondispersive infrared spectroscopy is going to become a reliable, but low-cost and easy-to-operate alternative to expensive isotope ratio mass spectrometry in the analysis of 13C-breath tests.

Laser isotope separation by multiple photon absorption

DOEpatents

Robinson, C.P.; Rockwood, S.D.; Jensen, R.J.; Lyman, J.L.; Aldridge, J.P. III.

1987-04-07

Multiple photon absorption from an intense beam of infrared laser light may be used to induce selective chemical reactions in molecular species which result in isotope separation or enrichment. The molecular species must have a sufficient density of vibrational states in its vibrational manifold that, is the presence of sufficiently intense infrared laser light tuned to selectively excite only those molecules containing a particular isotope, multiple photon absorption can occur. By this technique, for example, intense CO[sub 2] laser light may be used to highly enrich [sup 34]S in natural SF[sub 6] and [sup 11]B in natural BCl[sub 3]. 8 figs.

Using Stable Isotopes of Carbon and Nitrogen to Evaluate Trophic Interactions in Aquatic Environments

ERIC Educational Resources Information Center

Christensen, David R.; LaRoche, Andrew

2012-01-01

This paper describes a series of laboratory exercises for upper level biology courses, independent research and/or honors programs. Students sampled fish from a local water body with the assistance of a local fish and wildlife agency. Tissue samples from collected fish were utilized to obtain estimates of the stable isotopes delta[superscript 13]C…

A target for production of radioxenons

NASA Technical Reports Server (NTRS)

Blue, J. W.; Leonard, R.; Jha, S.; Sodd, V. J.; Vincent, J. S.

1976-01-01

A liquid cesium target has been developed which allows the production and separate identification of the neutron deficient isotopes of xenon. The present report describes irradiations utilizing 34 to 41 MeV protons to produce millicurie quantities of Xe-127 and Xe-129m. At higher energies, however, the target could be used without modification to produce xenon isotopes as light as 119.

Correction for isotopic interferences between analyte and internal standard in quantitative mass spectrometry by a nonlinear calibration function.

PubMed

Rule, Geoffrey S; Clark, Zlatuse D; Yue, Bingfang; Rockwood, Alan L

2013-04-16

Stable isotope-labeled internal standards are of great utility in providing accurate quantitation in mass spectrometry (MS). An implicit assumption has been that there is no "cross talk" between signals of the internal standard and the target analyte. In some cases, however, naturally occurring isotopes of the analyte do contribute to the signal of the internal standard. This phenomenon becomes more pronounced for isotopically rich compounds, such as those containing sulfur, chlorine, or bromine, higher molecular weight compounds, and those at high analyte/internal standard concentration ratio. This can create nonlinear calibration behavior that may bias quantitative results. Here, we propose the use of a nonlinear but more accurate fitting of data for these situations that incorporates one or two constants determined experimentally for each analyte/internal standard combination and an adjustable calibration parameter. This fitting provides more accurate quantitation in MS-based assays where contributions from analyte to stable labeled internal standard signal exist. It can also correct for the reverse situation where an analyte is present in the internal standard as an impurity. The practical utility of this approach is described, and by using experimental data, the approach is compared to alternative fits.

Digestive selection underlies differential utilization of phytoplankton and sedimentary organics by infaunal bivalves: Experiments with cockles (Cerastoderma edule) using cross-labelled mixed diets.

PubMed

Navarro, Enrique; Méndez, Soco; Urrutia, Miren Begoñe; Arambalza, Udane; Ibarrola, Irrintzi

2016-09-01

Differential utilization of phytoplankton and detrital particles present in natural sediments of mud-flats was studied in a series of experiments performed on the infaunal bivalve Cerastoderma edule. In order to assess digestive selection, parameters of food processing (organic ingestion rate: OIR, gross absorption efficiency: GAE and gut passage time: GPT) were recorded for each organic component in different combinations of food particles radio-labelled with (14)C. Experimental design included the use of both labelled diets of a sole organic component and cross-labelled diets; i.e., mixed suspensions presenting alternatively labelled one of the various components tested: phytoplankton cells, sedimentary organic particles and particulate detritus from vascular salt-marsh plants. Preferential absorption of phytoplankton was accounted for by absorption efficiency values that were two-fold those for sedimentary detritus when recorded with mixed diets of both organic components. Two factors contributed to this difference: a) higher digestibility of microalgae, measured as the ratio of GAE to GPT, and b) faster gut passage of detrital particles that results from digestive selection likely involving the preferential incorporation of phytoplankton into the digestive gland. However, when diets based on a sole organic component (either phytoplankton or detritus) were compared, larger GPT were recorded for detrital particles that enabled improving GAE of this rather refractory food. Overall results of these experiments are consistent with most studies in trophic ecology based on stable isotopes enrichment, concerning both the diversity of trophic sources used by marine bivalves and its preferential utilization of phytoplankton over phyto-detritus. Copyright © 2016 Elsevier Ltd. All rights reserved.

The O and H stable isotope composition of freshwaters in the British Isles. 2. Surface waters and groundwater

NASA Astrophysics Data System (ADS)

Darling, W. G.; Bath, A. H.; Talbot, J. C.

The utility of stable isotopes as tracers of the water molecule has a long pedigree. The study reported here is part of an attempt to establish a comprehensive isotopic "baseline" for the British Isles as background data for a range of applications. Part 1 of this study (Darling and Talbot, 2003) considered the isotopic composition of rainfall in Britain and Ireland. The present paper is concerned with the composition of surface waters and groundwater. In isotopic terms, surface waters (other than some upland streams) are poorly characterised in the British Isles; their potential variability has yet to be widely used as an aid in hydrological research. In what may be the first study of a major British river, a monthly isotopic record of the upper River Thames during 1998 was obtained. This shows high damping of the isotopic variation compared to that in rainfall over most of the year, though significant fluctuations were seen for the autumn months. Smaller rivers such as the Stour and Darent show a more subdued response to the balance between runoff and baseflow. The relationship between the isotopic composition of rainfall and groundwater is also considered. From a limited database, it appears that whereas Chalk groundwater is a representative mixture of weighted average annual rainfall, for Triassic sandstone groundwater there is a seasonal selection of rainfall biased towards isotopically-depleted winter recharge. This may be primarily the result of physical differences between the infiltration characteristics of rock types, though other factors (vegetation, glacial history) could be involved. In the main, however, groundwaters appear to be representative of bulk rainfall within an error band of 0.5‰ δ18O. Contour maps of the δ18O and δ2H content of recent groundwaters in the British Isles show a fundamental SW-NE depletion effect modified by topography. The range of measured values, while much smaller than those for rainfall, still covers some ‰ for δ18O and 30‰ for δ2H. Over lowland areas the "altitude effect" is of little significance, but in upland areas is consistent with a range of -0.2 to -0.3‰ per 100 m increase in altitude. Groundwaters dating from the late Pleistocene are usually modified in δ18O and δ2H owing to the effects of climate change on the isotopic composition of rainfall and thus of recharge. Contour maps of isotopic variability prior to 10 ka BP, based on the relatively limited information available from the British Isles, allow a first comparison between groundwaters now and at the end of the last Ice Age. The position of the British Isles in the context of the stable isotope systematics of NW Europe is reviewed briefly.

Quantum Dynamics Study of the Isotopic Effect on Capture Reactions: HD, D2 + CH3

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

Time-dependent wave-packet-propagation calculations are reported for the isotopic reactions, HD + CH3 and D2 + CH3, in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probabilities for different initial rotational-vibrational states are presented in this study. This study shows that excitations of the HD(D2) enhances the reactivities; whereas the excitations of the CH3 umbrella mode have the opposite effects. This is consistent with the reaction of H2 + CH3. The comparison of these three isotopic reactions also shows the isotopic effects in the initial-state-selected reaction probabilities. The cumulative reaction probabilities (CRP) are obtained by summing over initial-state-selected reaction probabilities. The energy-shift approximation to account for the contribution of degrees of freedom missing in the six dimensionality calculation is employed to obtain approximate full-dimensional CRPs. The rate constant comparison shows H2 + CH3 reaction has the biggest reactivity, then HD + CH3, and D2 + CH3 has the smallest.

Disk mass determination through CO isotopologues

NASA Astrophysics Data System (ADS)

Miotello, Anna; Kama, Mihkel; van Dishoeck, Ewine

2015-08-01

One of the key properties for understanding how disks evolve to planetary systems is their overall mass, combined with their surface density distribution. So far, virtually all disk mass determinations are based on observations of the millimeter continuum dust emission.To derive the total gas + dust disk mass from these data involves however several big assumptions. The alternative method is to directly derive the gas mass through the detection of carbon monoxide (CO) and its less abundant isotopologues. CO chemistry is well studied and easily implemented in chemical models, provided that isotope-selective processes are properly accounted for.CO isotope-selective photodissociation was implemented for the first time in a full physical-chemical code in Miotello et al. (2014). The main result is that if isotope-selective effects are not considered in the data analysis, disk masses can be underestimated by an order of magnitude or more. For example, the mass discrepancy found for the renowned TW Hya disk may be explained or at least mitigated by this implementation. In this poster, we present new results for a large grid of disk models. We derive mass correction factors for different disk, stellar and grain properties in order to account for isotope-selective effects in analyzing ALMA data of CO isotopologues (Miotello et al., in prep.).

Redefining the utility of the three-isotope method

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Bao, Huiming

2017-09-01

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

Improved efficiency of selective photoionization of palladium isotopes via autoionizing Rydberg states

NASA Astrophysics Data System (ADS)

Locke, Clayton R.; Kobayashi, Tohru; Midorikawa, Katsumi

2017-01-01

Odd-mass-selective ionization of palladium for purposes of resource recycling and management of long-lived fission products can be achieved by exploiting transition selection rules in a well-established three-step excitation process. In this conventional scheme, circularly polarized lasers of the same handedness excite isotopes via two intermediate 2D5/2 core states, and a third laser is then used for ionization via autoionizing Rydberg states. We propose an alternative excitation scheme via intermediate 2D3/2 core states before the autoionizing Rydberg state, improving ionization efficiency by over 130 times. We confirm high selectivity and measure odd-mass isotopes of >99.7(3)% of the total ionized product. We have identified and measured the relative ionization efficiency of the series of Rydberg states that converge to upper ionization limit of the 4 d 9(2D3/2) level, and identify the most efficient excitation is via the Rydberg state at 67668.18(10) cm-1.

Time-series Oxygen-18 Precipitation Isoscapes for Canada and the Northern United States

NASA Astrophysics Data System (ADS)

Delavau, Carly J.; Chun, Kwok P.; Stadnyk, Tricia A.; Birks, S. Jean; Welker, Jeffrey M.

2014-05-01

The present and past hydrological cycle from the watershed to regional scale can be greatly enhanced using water isotopes (δ18O and δ2H), displayed today as isoscapes. The development of water isoscapes has both hydrological and ecological applications, such as ground water recharge and food web ecology, and can provide critical information when observations are not available due to spatial and temporal gaps in sampling and data networks. This study focuses on the creation of δ18O precipitation (δ18Oppt) isoscapes at a monthly temporal frequency across Canada and the northern United States (US) utilizing CNIP (Canadian Network for Isotopes in Precipitation) and USNIP (United States Network for Isotopes in Precipitation) measurements. Multiple linear stepwise regressions of CNIP and USNIP observations alongside NARR (North American Regional Reanalysis) climatological variables, teleconnection indices, and geographic indicators are utilized to create empirical models that predict the δ18O of monthly precipitation across Canada and the northern US. Pooling information from nearby locations within a region can be useful due to the similarity of processes and mechanisms controlling the variability of δ18O. We expect similarity in the controls on isotopic composition to strengthen the correlation between δ18Oppt and predictor variables, resulting in model simulation improvements. For this reason, three different regionalization approaches are used to separate the study domain into 'isotope zones' to explore the effect of regionalization on model performance. This methodology results in 15 empirical models, five within each regionalization. A split sample calibration and validation approach is employed for model development, and parameter selection is based on demonstrated improvement of the Akaike Information Criteria (AIC). Simulation results indicate the empirical models are generally able to capture the overall monthly variability in δ18Oppt. For the three regionalizations, average adjusted-R2 and RMSE (weighted to number of observations within each isotope zone) range from 0.70 - 0.72 and 2.76 - 2.91, respectively, indicating that on average the different spatial groupings perform comparably. Validation weighted R2and RMSE show a larger spread between models and poorer performance, ranging from 0.45 - 0.59 and 3.28 - 3.39, respectively. Additional evaluation of simulated δ18Oppt at each station and inter/intra-annually is conducted to evaluate model performance over various space and time scales. Stepwise regression derived parameterizations indicate the significance of precipitable water content and latitude as predictor variables for all regionalizations. Long-term (1981-2010) annual average δ18Oppt isoscapes are produced for Canada and the northern US, highlighting the differences between regionalization approaches. 95% confidence interval maps are generated to provide an estimate of the uncertainty associated with long-term δ18Oppt simulations. This is the first ever time-series empirical modelling of δ18Oppt for Canada utilizing CNIP data, as well as the first modelling collaboration between the CNIP and USNIP networks. This study is the initial step towards empirically derived time-series δ18Oppt for use in iso-hydrological modelling studies. Methods and results from this research are equally applicable to ecology and forensics as the simulated δ18Oppt isoscapes provide the primary oxygen source for many plants and foodwebs at refined temporal and spatial scales across Canada and the northern US.

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

Mirjankar, Nikhil S.; Fraga, Carlos G.; Carman, April J.

Chemical attribution signatures (CAS) for chemical threat agents (CTAs) are being investigated to provide an evidentiary link between CTAs and specific sources to support criminal investigations and prosecutions. In a previous study, anionic impurity profiles developed using high performance ion chromatography (HPIC) were demonstrated as CAS for matching samples from eight potassium cyanide (KCN) stocks to their reported countries of origin. Herein, a larger number of solid KCN stocks (n = 13) and, for the first time, solid sodium cyanide (NaCN) stocks (n = 15) were examined to determine what additional sourcing information can be obtained through anion, carbon stablemore » isotope, and elemental analyses of cyanide stocks by HPIC, isotope ratio mass spectrometry (IRMS), and inductively coupled plasma optical emission spectroscopy (ICP-OES), respectively. The HPIC anion data was evaluated using the variable selection methods of Fisher-ratio (F-ratio), interval partial least squares (iPLS), and genetic algorithm-based partial least squares (GAPLS) and the classification methods of partial least squares discriminate analysis (PLSDA), K nearest neighbors (KNN), and support vector machines discriminate analysis (SVMDA). In summary, hierarchical cluster analysis (HCA) of anion impurity profiles from multiple cyanide stocks from six reported country of origins resulted in cyanide samples clustering into three groups: Czech Republic, Germany, and United States, independent of the associated alkali metal (K or Na). The three country groups were independently corroborated by HCA of cyanide elemental profiles and corresponded to countries with known solid cyanide factories. Both the anion and elemental CAS are believed to originate from the aqueous alkali hydroxides used in cyanide manufacture. Carbon stable isotope measurements resulted in two clusters: Germany and United States (the single Czech stock grouped with United States stocks). The carbon isotope CAS is believed to originate from the carbon source and process used to make the HCN utilized in cyanide synthesis. Classification errors for two validation studies using anion impurity profiles collected over five years on different instruments were as low as zero for KNN and SVMDA, demonstrating the excellent reliability (so far) of using anion impurities for matching a cyanide sample to its country of manufacture (i.e., factory). Variable selection reduced errors for those classification methods having errors greater than zero with iPLS-forward selection, and F-ratio typically providing the lowest errors. Finally, using anion profiles to match cyanides to a specific stock or stock group resulted in cross-validation errors ranging from zero to 5.3%.« less

Tap water isotopes reveal the San Francisco Bay Area's plumbing and responses to a major drought

NASA Astrophysics Data System (ADS)

Tipple, B. J.; Jameel, M. Y.; Chau, T. H.; Mancuso, C. J.; Bowen, G. J.; Dufour, A.; Chesson, L. A.; Ehleringer, J. R.

2016-12-01

Water availability and sustainability in the Western United States is a major flashpoint among expanding communities, growing industries, and productive agricultural lands. This issue came to a head in 2015 in the State of California, when the State mandated a 25% reduction in urban water use following a multi-year drought that significantly depleted water resources. The demands for and challenges in supplying water are only expected to intensify as climate perturbations, such as the 2012-2015 California Drought, become more common. As a consequence, there is an increased need to understand linkages between population centers, water transport and usage, and the impacts of climate change on water resources and infrastructure. To better understand these relationships within a megalopolis in the Western United States, we collected and analyzed 723 tap waters from the San Francisco Bay Area during seven collection campaigns across 21 months during 2013-2015. San Francisco Bay Area was selected as it has well-known water management strategies and its water resources were dramatically affected by the 2012-2105 drought. Consistent with known water management strategies and previous reports of tap water isotope values, we found large spatiotemporal variations in the δ2H and δ18O values of tap waters, indicative of complex water transport systems and municipality-scale management decisions. We observed δ2H and δ18O values of tap water consistent with waters originating from snowmelt from the Sierra Nevada Mountains, local precipitation, ground water, and partially evaporated reservoir sources. A cluster analysis of measured tap water data grouped waters from 43 static sampling sites that were associated with specific water utility providers within the San Francisco Bay Area and known management practices. Water management responses to the drought, such as source switching, bringing in new sources, and conservation, could be observed within the isotope data from each of collection campaigns. Finally, we used a modified Craig-Gordon model of evaporative loss from one utility's reservoir system during the 2015 water year to estimate the consequences of the drought on this resource. Using these isotope methods, we estimated that approximately 10% of the water in this reservoir system was lost to evaporation.

Nitrogen Isotope Composition of Thermally Produced NOx from Various Fossil-Fuel Combustion Sources.

PubMed

Walters, Wendell W; Tharp, Bruce D; Fang, Huan; Kozak, Brian J; Michalski, Greg

2015-10-06

The nitrogen stable isotope composition of NOx (δ(15)N-NOx) may be a useful indicator for NOx source partitioning, which would help constrain NOx source contributions in nitrogen deposition studies. However, there is large uncertainty in the δ(15)N-NOx values for anthropogenic sources other than on-road vehicles and coal-fired energy generating units. To this end, this study presents a broad analysis of δ(15)N-NOx from several fossil-fuel combustion sources that includes: airplanes, gasoline-powered vehicles not equipped with a three-way catalytic converter, lawn equipment, utility vehicles, urban buses, semitrucks, residential gas furnaces, and natural-gas-fired power plants. A relatively large range of δ(15)N-NOx values was measured from -28.1‰ to 8.5‰ for individual exhaust/flue samples that generally tended to be negative due to the kinetic isotope effect associated with thermal NOx production. A negative correlation between NOx concentrations and δ(15)N-NOx for fossil-fuel combustion sources equipped with selective catalytic reducers was observed, suggesting that the catalytic reduction of NOx increases δ(15)N-NOx values relative to the NOx produced through fossil-fuel combustion processes. Combining the δ(15)N-NOx measured in this study with previous published values, a δ(15)N-NOx regional and seasonal isoscape was constructed for the contiguous U.S., which demonstrates seasonal and regional importance of various NOx sources.

Infrared Lasers in Chemistry.

ERIC Educational Resources Information Center

John, Phillip

1982-01-01

Selected infrared laser chemistry topics are discussed including carbon dioxide lasers, infrared quanta and molecules, laser-induced chemistry, structural isomerization (laser purification, sensitized reactions, and dielectric breakdown), and fundamental principles of laser isotope separation, focusing on uranium isotope separation. (JN)

Laurentide Ice-Sheet Meltwater Sources to the Gulf of Mexico During the Last Deglaciation: Assessing Data Reconstructions Using Water Isotope Enabled Simulations

NASA Astrophysics Data System (ADS)

Vetter, L.; LeGrande, A. N.; Ullman, D. J.; Carlson, A. E.

2017-12-01

Sediment cores from the Gulf of Mexico show evidence of meltwater derived from the Laurentide Ice Sheet during the last deglaciation. Recent studies using geochemical measurements of individual foraminifera suggest changes in the oxygen isotopic composition of the meltwater as deglaciation proceeded. Here we use the water isotope enabled climate model simulations (NASA GISS ModelE-R) to investigate potential sources of meltwater within the ice sheet. We find that initial melting of the ice sheet from the southern margin contributed an oxygen isotope value reflecting a low-elevation, local precipitation source. As deglacial melting proceeded, meltwater delivered to the Gulf of Mexico had a more negative oxygen isotopic value, which the climate model simulates as being sourced from the high-elevation, high-latitude interior of the ice sheet. This study demonstrates the utility of combining stable isotope analyses with climate model simulations to investigate past changes in the hydrologic cycle.

Utilizing Stable Isotopes and Isotopic Anomalies to Study Early Solar System Formation Processes

NASA Technical Reports Server (NTRS)

Simon, Justin

2017-01-01

Chondritic meteorites contain a diversity of particle components, i.e., chondrules and calcium-, aluminum-rich refractory inclusions (CAIs), that have survived since the formation of the Solar System. The chemical and isotopic compositions of these materials provide a record of the conditions present in the protoplanetary disk where they formed and can aid our understanding of the processes and reservoirs in which solids formed in the solar nebula, an important step leading to the accretion of planetesimals. Isotopic anomalies associated with nucleosynthetic processes are observed in these discrete materials, and can be compared to astronomical observations and astrophysical formation models of stars and more recently proplyds. The existence and size of these isotopic anomalies are typically thought to reflect a significant state of isotopic heterogeneity in the earliest Solar System, likely left over from molecular cloud heterogeneities on the grain scale, but some could also be due to late stellar injection. The homogenization of these isotopic anomalies towards planetary values can be used to track the efficiency and timescales of disk wide mixing,

Compound-Specific Isotopic Analysis of Meteoritic Amino Acids as a Tool for Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Burton, Aaron S.; Callahan, Michael C.; Charnley, Steven B.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Measurements of stable hydrogen, carbon, and nitrogen isotopic ratios (delta D, delta C-13, delta N-15) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may point towards the most likely of these proposed pathways. The technique of gas chromatography coupled with mass spectrometry and isotope ratio mass spectrometry provides compound-specific structural and isotopic information from a single splitless injection, enhancing the amount of information gained from small amounts of precious samples such as carbonaceous chondrites. We have applied this technique to measure the compound-specific C, N, and H isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites. We are using these measurements to evaluate predictions of expected isotopic enrichments from potential formation pathways and environments, leading to a better understanding of the origin of these compounds.

Mercury in gray wolves (Canis lupus) in Alaska: increased exposure through consumption of marine prey.

PubMed

McGrew, Ashley K; Ballweber, Lora R; Moses, Sara K; Stricker, Craig A; Beckmen, Kimberlee B; Salman, Mo D; O'Hara, Todd M

2014-01-15

Mercury (Hg) bioaccumulates in the tissues of organisms and biomagnifies within food-webs. Gray wolves (Canis lupus) in Alaska primarily acquire Hg through diet; therefore, comparing the extent of Hg exposure in wolves, in conjunction with stable isotopes, from interior and coastal regions of Alaska offers important insight into their feeding ecology. Liver, kidney, and skeletal muscle samples from 162 gray wolves were analyzed for total mercury (THg) concentrations and stable isotopic signatures (δ(13)C, δ(15)N, and δ(34)S). Median hepatic THg concentrations were significantly higher in wolves with coastal access compared to wolves from interior Alaska. Stable isotope ratios, in conjunction with THg concentrations, provide strong evidence that coastal wolves are utilizing marine prey representing several trophic levels. The utilization of cross-ecosystem food resources by coastal wolves is clearly contributing to increased THg exposure, and may ultimately have negative health implications for these animals. © 2013 Elsevier B.V. All rights reserved.

A strategy for intensive production of molybdenum-99 isotopes for nuclear medicine using CANDU reactors.

PubMed

Morreale, A C; Novog, D R; Luxat, J C

2012-01-01

Technetium-99m is an important medical isotope utilized worldwide in nuclear medicine and is produced from the decay of its parent isotope, molybdenum-99. The online fueling capability and compact fuel of the CANDU(®)(1) reactor allows for the potential production of large quantities of (99)Mo. This paper proposes (99)Mo production strategies using modified target fuel bundles loaded into CANDU fuel channels. Using a small group of channels a yield of 89-113% of the weekly world demand for (99)Mo can be obtained. Copyright © 2011 Elsevier Ltd. All rights reserved.

Stable isotopes in mid-ocean ridge hydrothermal systems: Interactions between fluids, minerals, and organisms

NASA Astrophysics Data System (ADS)

Shanks, W. C., III; Böhlke, J. K.; Seal, R. R., II

Studies of abundance variations of light stable isotopes in nature have had a tremendous impact on all aspects of geochemistry since the development, in 1947, of a gas source isotope ratio mass spectrometer capable of measuring small variations in stable isotope ratios [Nier, 1947] Stable isotope geochemistry is now a mature field, as witnessed by the proliferation of commercially available mass spectrometers installed at virtually every major academic, government, and private-sector research geochemistry laboratory. A recent search of a literature database revealed over 3,000 articles that utilized stable isotope geochemistry over the last 20 years. Nonetheless, many exciting new technical developments are leading to exciting new discoveries and applications. In particular, micro analytical techniques involving new generations of laser- and ion-microprobes are revolutionizing the types of analyses that can be done on spot sizes as small as a few tens of micrometers [Shanks and Criss, 1989]. New generations of conventional gas source and thermal ionization mass spectrometers, with high levels of automation and increased sensitivity and precision, are allowing analyses of large numbers of samples, like those needed for stable isotope stratigraphy in marine sediments, and are enabling the development and application of new isotopic systems.

Stable isotopes in mid-ocean ridge hydrothermal systems: Interactions between fluids, minerals, and organisms

USGS Publications Warehouse

Shanks, Wayne C.; Böhlke, John Karl; Seal, Robert R.; Humphries, S.D.; Zierenberg, Robert A.; Mullineaux, Lauren S.; Thomson, Richard E.

1995-01-01

Studies of abundance variations of light stable isotopes in nature have had a tremendous impact on all aspects of geochemistry since the development, in 1947, of a gas source isotope ratio mass spectrometer capable of measuring small variations in stable isotope ratios (Nice, 1947]. Stable isotope geochemistry is now a mature field, as witnessed by the proliferation of commercially available mass spectrometers installed at virtually every major academic, government, and private-sector research geochemistry laboratory. A recent search of a literature database revealed over 3,000 articles that utilized stable isotope geochemistry over the last 20 years. Nonetheless, many exciting new technical developments are leading to exciting new discoveries and applications. In particular, micro-analytical techniques involving new generations of laser- and ion-microprobes are revolutionizing the types of analyses that can be done on spot sizes as small as a few tens of micrometers [Shanks and Criss, 1989]. New generations of conventional gas source and thermal ionization mass spectrometers, with high levels of automation and increased sensitivity and precision, are allowing analyses of large numbers of samples, like those needed for stable isotope stratigraphy in marine sediments, and are enabling the development and application of new isotopic systems.

Production of highly-enriched 134Ba for a reference material for isotope dilution mass spectrometry measurements

DOE PAGES

Horkley, J. J.; Carney, K. P.; Gantz, E. M.; ...

2015-03-17

Isotope dilution mass spectrometry (IDMS) is an analytical technique capable of providing accurate and precise quantitation of trace isotope abundance and assay providing measurement uncertainties below 1 %. To achieve these low uncertainties, the IDMS method ideally utilizes chemically pure “spike” solutions that consist of a single highly enriched isotope that is well-characterized relating to the abundance of companion isotopes and concentration in solution. To address a current demand for accurate 137Cs/137Ba ratio measurements for “age” determination of radioactive 137Cs sources, Idaho National Laboratory (INL) is producing enriched 134Ba isotopes that are tobe used for IDMS spikes to accurately determinemore » 137Ba accumulation from the decay of 137Cs. The final objective of this work it to provide a homogenous set of reference materials that the National Institute of Standards and Technology can certify as standard reference materials used for IDMS. The process that was developed at INL for the separation and isolation of Ba isotopes, chemical purification of the isotopes in solution, and the encapsulation of the materials will be described.« less

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

Treesearch

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

2014-01-01

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

Carbon isotope effects associated with autotrophic acetogenesis

NASA Technical Reports Server (NTRS)

Gelwicks, J. T.; Risatti, J. B.; Hayes, J. M.

1989-01-01

The carbon kinetic isotope effects associated with synthesis of acetate from CO2 and H2 during autotrophic growth of Acetobacterium woodii at 30 degrees C have been measured by isotopic analyses of CO2, methyl-carbon, and total acetate. Closed systems allowing construction of complete mass balances at varying stages of growth were utilized, and the effects of the partitioning of carbon between CO2 and HCO3- were taken account. For the overall reaction, total carbonate --> total acetate, isotope effects measured in replicate experiments ranged from -59.0 +/- 0.9% to -57.2 +/- 2.3%. Taking into account all measurements, the weighted mean and standard deviation are -58.6 +/- 0.7%. There is no evidence for intramolecular ordering in the acetate. The carbon isotopic composition of sedimentary acetate, otherwise expected to be near that of sedimentary organic carbon, is likely to be depleted in environments in which autotrophic acetogenesis is occurring.

A novel method for determination of the (15) N isotopic composition of Rubisco in wheat plants exposed to elevated atmospheric carbon dioxide.

PubMed

Aranjuelo, Iker; Molero, Gemma; Avice, Jean Christophe; Bourguignon, Jacques

2015-02-01

Although ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) is mostly known as a key enzyme involved in CO2 assimilation during the Calvin cycle, comparatively little is known about its role as a pool of nitrogen storage in leaves. For this purpose, we developed a protocol to purify Rubisco that enables later analysis of its (15) N isotope composition (δ(15) N) at the natural abundance and (15) N-labeled plants. In order to test the utility of this protocol, durum wheat (Triticum durum var. Sula) exposed to an elevated CO2 concentration (700 vs 400 µmol mol(-1) ) was labeled with K(15) NO3 (enriched at 2 atom %) during the ear development period. The developed protocol proves to be selective, simple, cost effective and reproducible. The study reveals that (15) N labeling was different in total organic matter, total soluble protein and the Rubisco fraction. The obtained data suggest that photosynthetic acclimation in wheat is caused by Rubisco depletion. This depletion may be linked to preferential nitrogen remobilization from Rubisco toward grain filling. © 2014 Scandinavian Plant Physiology Society.

The synthesis of tritium, carbon-14 and stable isotope labelled selective estrogen receptor degraders.

PubMed

Bragg, Ryan A; Bushby, Nick; Ericsson, Cecilia; Kingston, Lee P; Ji, Hailong; Elmore, Charles S

2016-09-01

As part of a Medicinal Chemistry program aimed at developing an orally bioavailable selective estrogen receptor degrader, a number of tritium, carbon-14, and stable isotope labelled (E)-3-[4-(2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-1-yl)phenyl]prop-2-enoic acids were required. This paper discusses 5 synthetic approaches to this compound class. Copyright © 2016 John Wiley & Sons, Ltd.

Isotope separation apparatus and method

DOEpatents

Feldman, Barry J.

1985-01-01

The invention relates to an improved method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferably substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. Because the molecules in the beam occupy various degenerate energy levels, if the laser beam comprises chirped pulses comprising selected wavelengths, the laser beam will very efficiently excite substantially all unexcited molecules and will cause stimulated emission of substantially all excited molecules of a selected one of the isotopes in the beam which such pulses encounter. Excitation caused by first direction chirped pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning chirped pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement of essentially all the molecules containing the one isotope is accomplished by a large number of chirped pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

Highly effective hydrogen isotope separation in nanoporous metal-organic frameworks with open metal sites: direct measurement and theoretical analysis.

PubMed

Oh, Hyunchul; Savchenko, Ievgeniia; Mavrandonakis, Andreas; Heine, Thomas; Hirscher, Michael

2014-01-28

Separating gaseous mixtures that consist of very similar size is one of the critical issues in modern separation technology. Especially, the separation of the isotopes hydrogen and deuterium requires special efforts, even though these isotopes show a very large mass ratio. Conventionally, H/D separation can be realized through cryogenic distillation of the molecular species or the Girdler-sulfide process, which are among the most energy-intensive separation techniques in the chemical industry. However, costs can be significantly reduced by using highly mass-selective nanoporous sorbents. Here, we describe a hydrogen isotope separation strategy exploiting the strongly attractive open metal sites present in nanoporous metal-organic frameworks of the CPO-27 family (also referred to as MOF-74). A theoretical analysis predicts an outstanding hydrogen isotopologue separation at open metal sites due to isotopal effects, which has been directly observed through cryogenic thermal desorption spectroscopy. For H2/D2 separation of an equimolar mixture at 60 K, the selectivity of 12 is the highest value ever measured, and this methodology shows extremely high separation efficiencies even above 77 K. Our theoretical results imply also a high selectivity for HD/H2 separation at similar temperatures, and together with catalytically active sites, we propose a mechanism to produce D2 from HD/H2 mixtures with natural or enriched deuterium content.

Isotopic insights into biological regulation of zinc in contaminated systems

USGS Publications Warehouse

Wanty, Richard B.; Balistrieri, Laurie S.; Wesner, Jeff S.; Walters, David; Schmidt, Travis S.; Podda, Francesca; De Giudici, G.; Stricker, Craig A.; Kraus, Johanna M.; Lattanzi, Pierfranco; Wolf, Ruth E.; Cidu, R.

2015-01-01

Aquatic organisms use a variety of biogeochemical reactions to regulate essential and non-essential trace metals. Many of these mechanisms can lead to isotopic fractionation, thus measurement of metal isotopes may yield insights into the processes by which organisms respond to metal exposure. We illustrate these concepts with two case studies, one involving an intra- and the other an extra-cellular mechanism of Zn sequestration. In the first study, the mayfly Neocloeon triangulifer was grown in the laboratory, and fed a diet of Zn-doped diatoms at Zn levels exceeding the requirements for normal mayfly life functions. The N. triangulifer larvae consumed the diatoms and retained their Zn isotopic signature. Upon metamorphosis, the subimago life stage lost Zn mass either in the exuvia or by excretion, and the Zn retained was isotopically enriched. Thus, Zn uptake is nonfractionating, but Zn regulation favors the lighter isotope. Thus the Zn remaining in the subimago was isotopically heavier. In the second study, Zn was adsorbed on the cell walls and exopolysaccharide secretions of cyanobacteria, which favored the heavier Zn isotope. Continued adsorption eventually resulted in nucleation and biomineralization of hydrozincite {Zn5(CO3)2(OH)6}. These case studies demonstrate the utility of Zn isotopes to provide insights into how aquatic insects respond to metal exposure.

Microbially Mediated Kinetic Sulfur Isotope Fractionation: Reactive Transport Modeling Benchmark

NASA Astrophysics Data System (ADS)

Wanner, C.; Druhan, J. L.; Cheng, Y.; Amos, R. T.; Steefel, C. I.; Ajo Franklin, J. B.

2014-12-01

Microbially mediated sulfate reduction is a ubiquitous process in many subsurface systems. Isotopic fractionation is characteristic of this anaerobic process, since sulfate reducing bacteria (SRB) favor the reduction of the lighter sulfate isotopologue (S32O42-) over the heavier isotopologue (S34O42-). Detection of isotopic shifts have been utilized as a proxy for the onset of sulfate reduction in subsurface systems such as oil reservoirs and aquifers undergoing uranium bioremediation. Reactive transport modeling (RTM) of kinetic sulfur isotope fractionation has been applied to field and laboratory studies. These RTM approaches employ different mathematical formulations in the representation of kinetic sulfur isotope fractionation. In order to test the various formulations, we propose a benchmark problem set for the simulation of kinetic sulfur isotope fractionation during microbially mediated sulfate reduction. The benchmark problem set is comprised of four problem levels and is based on a recent laboratory column experimental study of sulfur isotope fractionation. Pertinent processes impacting sulfur isotopic composition such as microbial sulfate reduction and dispersion are included in the problem set. To date, participating RTM codes are: CRUNCHTOPE, TOUGHREACT, MIN3P and THE GEOCHEMIST'S WORKBENCH. Preliminary results from various codes show reasonable agreement for the problem levels simulating sulfur isotope fractionation in 1D.

Do deposit-feeders compete? Isotopic niche analysis of an invasion in a species-poor system

PubMed Central

Karlson, Agnes M. L.; Gorokhova, Elena; Elmgren, Ragnar

2015-01-01

Successful establishment of invasive species is often related to the existence of vacant niches. Competition occurs when invaders use the same limiting resources as members of the recipient community, which will be reflected in some overlap of their trophic niches. The concept of isotopic niche has been used to study trophic niche partitioning among species. Here, we present a two-year field study comparing isotopic niches of the deposit-feeding community in a naturally species-poor system. The isotopic niche analyses showed no overlap between a recent polychaete invader and any of the native species suggesting that it has occupied a vacant niche. Its narrow isotopic niche suggests specialized feeding, however, the high δ15N values compared to natives are most likely due to isotope fractionation effects related to nitrogen recycling and a mismatch between biological stoichiometry of the polychaete and the sediment nitrogen content. Notably, highly overlapping isotopic niches were inferred for the native species, which is surprising in a food-limited system. Therefore, our results demonstrate that invaders may broaden the community trophic diversity and enhance resource utilization, but also raise questions about the congruence between trophic and isotopic niche concepts and call for careful examination of assumptions underlying isotopic niche interpretation. PMID:25988260

Capillary Absorption Spectrometer for 13C Isotopic Composition of Pico to Subpico Molar Sample Quantities

NASA Astrophysics Data System (ADS)

Moran, J.; Kelly, J.; Sams, R.; Newburn, M.; Kreuzer, H.; Alexander, M.

2011-12-01

Quick incorporation of IR spectroscopy based isotope measurements into cutting edge research in biogeochemical cycling attests to the advantages of a spectroscopy versus mass spectrometry method for making some 13C measurements. The simple principles of optical spectroscopy allow field portability and provide a more robust general platform for isotope measurements. We present results with a new capillary absorption spectrometer (CAS) with the capability of reducing the sample size required for high precision isotopic measurements to the picomolar level and potentially the sub-picomolar level. This work was motivated by the minute sample size requirements for laser ablation isotopic studies of carbon cycling in microbial communities but has potential to be a valuable tool in other areas of biological and geological research. The CAS instrument utilizes a capillary waveguide as a sample chamber for interrogating CO2 via near IR laser absorption spectroscopy. The capillary's small volume (~ 0.5 mL) combined with propagation and interaction of the laser mode with the entire sample reduces sample size requirements to a fraction of that accessible with commercially available IR absorption including those with multi-pass or ring-down cavity systems. Using a continuous quantum cascade laser system to probe nearly adjacent rovibrational transitions of different isotopologues of CO2 near 2307 cm-1 permits sample measurement at low analyte pressures (as low as 2 Torr) for further sensitivity improvement. A novel method to reduce cw-fringing noise in the hollow waveguide is presented, which allows weak absorbance features to be studied at the few ppm level after averaging 1,000 scans in 10 seconds. Detection limits down to the 20 picomoles have been observed, a concentration of approximately 400 ppm at 2 Torr in the waveguide with precision and accuracy at or better than 1 %. Improvements in detection and signal averaging electronics and laser power and mode quality are anticipated to reduce the required samples size to a 100-200 femtomoles of carbon. We report the application of the CAS system to a Laser Ablation-Catalytic-Combustion (LA-CC) micro-sampler system for selectively harvesting detailed sections of a solid surface for 13C analysis. This technique results in a three order of magnitude sensitivity improvement reported for our isotope measurement system compared to typical IRMS, providing new opportunities for making detailed investigations into wide ranges of microbial, physical, and chemical systems. The CAS is interfaced directly to the LA CC system currently operating at a 50 μm spatial resolution. We demonstrate that particulates produced by a Nd:YAG laser (λ=266nm) are isotopically homogenous with the parent material as measured by both IRMS and the CAS system. An improved laser ablation system operating at 193 nm with a spatial resolution of 2 microns or better is under development which will demonstrate the utility of the CAS system for sample sizes too low for IRMS. The improved sensitivities and optimized spatial targeting of such a system could interrogate targets as detailed as small cell clusters or intergrain organic deposits and could enhance ability to track biogeochemical carbon cycling.

Global isotope metabolomics reveals adaptive strategies for nitrogen assimilation

DOE PAGES

Kurczy, Michael E.; Forsberg, Erica M.; Thorgersen, Michael P.; ...

2016-04-05

Nitrogen cycling is a microbial metabolic process essential for global ecological/agricultural balance. To investigate the link between the well-established ammonium and the alternative nitrate assimilation metabolic pathways, global isotope metabolomics was employed to examine three nitrate reducing bacteria using 15NO 3 as a nitrogen source. In contrast to a control ( Pseudomonas stutzeri RCH2), the results show that two of the isolates from Oak Ridge, Tennessee ( Pseudomonas N2A2 and N2E2) utilize nitrate and ammonia for assimilation concurrently with differential labeling observed across multiple classes of metabolites including amino acids and nucleotides. The data reveal that the N2A2 and N2E2more » strains conserve nitrogen-containing metabolites, indicating that the nitrate assimilation pathway is a conservation mechanism for the assimilation of nitrogen. Co-utilization of nitrate and ammonia is likely an adaption to manage higher levels of nitrite since the denitrification pathways utilized by the N2A2 and N2E2 strains from the Oak Ridge site are predisposed to the accumulation of the toxic nitrite. In conclusion, the use of global isotope metabolomics allowed for this adaptive strategy to be investigated, which would otherwise not have been possible to decipher.« less

Global isotope metabolomics reveals adaptive strategies for nitrogen assimilation

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

Kurczy, Michael E.; Forsberg, Erica M.; Thorgersen, Michael P.

Nitrogen cycling is a microbial metabolic process essential for global ecological/agricultural balance. To investigate the link between the well-established ammonium and the alternative nitrate assimilation metabolic pathways, global isotope metabolomics was employed to examine three nitrate reducing bacteria using 15NO 3 as a nitrogen source. In contrast to a control ( Pseudomonas stutzeri RCH2), the results show that two of the isolates from Oak Ridge, Tennessee ( Pseudomonas N2A2 and N2E2) utilize nitrate and ammonia for assimilation concurrently with differential labeling observed across multiple classes of metabolites including amino acids and nucleotides. The data reveal that the N2A2 and N2E2more » strains conserve nitrogen-containing metabolites, indicating that the nitrate assimilation pathway is a conservation mechanism for the assimilation of nitrogen. Co-utilization of nitrate and ammonia is likely an adaption to manage higher levels of nitrite since the denitrification pathways utilized by the N2A2 and N2E2 strains from the Oak Ridge site are predisposed to the accumulation of the toxic nitrite. In conclusion, the use of global isotope metabolomics allowed for this adaptive strategy to be investigated, which would otherwise not have been possible to decipher.« less

A stable isotope ( δ13C, δ15N) model for the North Water food web: implications for evaluating trophodynamics and the flow of energy and contaminants

NASA Astrophysics Data System (ADS)

Hobson, Keith A.; Fisk, Aaron; Karnovsky, Nina; Holst, Meike; Gagnon, Jean-Marc; Fortier, Martin

The North Water Polynya is an area of high biological activity that supports large numbers of higher trophic-level organisms such as seabirds and marine mammals. An overall objective of the Upper Trophic-Level Group of the International North Water Polynya Study (NOW) was to evaluate carbon and contaminant flux through these high trophic-level (TL) consumers. Crucial to an evaluation of the role of such consumers, however, was the establishment of primary trophic linkages within the North Water food web. We used δ15N values of food web components from particulate organic matter (POM) through polar bears ( Ursus maritimus) to create a trophic-level model based on the assumptions that Calanus hyperboreus occupies TL 2.0 and there is a 2.4‰ trophic enrichment in 15N between birds and their diets, and a 3.8‰ trophic enrichment for all other components. This model placed the planktivorous dovekie ( Alle alle) at TL 3.3, ringed seal ( Phoca hispida) at TL 4.5, and polar bear at TL 5.5. The copepods C. hyperboreus, Chiridius glacialis and Euchaeta glacialis formed a trophic continuum (TL 2.0-3.0) from primary herbivore through omnivore to primary carnivore. Invertebrates were generally sorted according to planktonic, benthic and epibenthic feeding groups. Seabirds formed three trophic groups, with dovekie occupying the lowest, black-legged kittiwake ( Rissa tridactyla), northern fulmar ( Fulmarus glacialis), thick-billed murre ( Uria aalge), and ivory gull ( Pagophilia eburnea) intermediate (TL 3.9-4.0), and glaucous gull ( Larus hyperboreus) the highest (TL 4.6) trophic positions. Among marine mammals, walrus ( Odobenus rosmarus) occupied the lowest (TL 3.2) and bearded seal ( Erignathus barbatus), ringed seal, beluga whale ( Delphinapterus leucas), and narwhal ( Monodon monoceros) intermediate positions (TL 4.1-4.6). In addition to arctic cod ( Boreogadus saida), we suggest that lower trophic-level prey, in particular the amphipod Themisto libellula, contribute fundamentally in transferring energy and carbon flux to higher trophic-level seabirds and marine mammals. We measured PCB 153 among selected organisms to investigate the behavior of bioaccumulating contaminants within the food web. Our isotopic model confirmed the trophic magnification of PCB 153 in this high-Arctic food web due to a strong correlation between contaminant concentration and organism δ15N values, demonstrating the utility of combining isotopic and contaminant approaches to food-web studies. Stable-carbon isotope analysis confirmed an enrichment in 13C between POM and ice algae (-22.3 vs. -17.7‰). Benthic organisms were generally enriched in 13C compared to pelagic species. We discuss individual species isotopic data and the general utility of our stable isotope model for defining carbon flux and contaminant flow through the North Water food web.

PepArML: A Meta-Search Peptide Identification Platform

PubMed Central

Edwards, Nathan J.

2014-01-01

The PepArML meta-search peptide identification platform provides a unified search interface to seven search engines; a robust cluster, grid, and cloud computing scheduler for large-scale searches; and an unsupervised, model-free, machine-learning-based result combiner, which selects the best peptide identification for each spectrum, estimates false-discovery rates, and outputs pepXML format identifications. The meta-search platform supports Mascot; Tandem with native, k-score, and s-score scoring; OMSSA; MyriMatch; and InsPecT with MS-GF spectral probability scores — reformatting spectral data and constructing search configurations for each search engine on the fly. The combiner selects the best peptide identification for each spectrum based on search engine results and features that model enzymatic digestion, retention time, precursor isotope clusters, mass accuracy, and proteotypic peptide properties, requiring no prior knowledge of feature utility or weighting. The PepArML meta-search peptide identification platform often identifies 2–3 times more spectra than individual search engines at 10% FDR. PMID:25663956

Selective consumption and metabolic allocation of terrestrial and algal carbon determine allochthony in lake bacteria.

PubMed

Guillemette, François; Leigh McCallister, S; Del Giorgio, Paul A

2016-06-01

Here we explore strategies of resource utilization and allocation of algal versus terrestrially derived carbon (C) by lake bacterioplankton. We quantified the consumption of terrestrial and algal dissolved organic carbon, and the subsequent allocation of these pools to bacterial growth and respiration, based on the δ(13)C isotopic signatures of bacterial biomass and respiratory carbon dioxide (CO2). Our results confirm that bacterial communities preferentially remove algal C from the terrestrially dominated organic C pool of lakes, but contrary to current assumptions, selectively allocate this autochthonous substrate to respiration, whereas terrestrial C was preferentially allocated to biosynthesis. The results provide further evidence of a mechanism whereby inputs of labile, algal-derived organic C may stimulate the incorporation of a more recalcitrant, terrestrial C pool. This mechanism resulted in a counterintuitive pattern of high and relatively constant levels of allochthony (~76%) in bacterial biomass across lakes that otherwise differ greatly in productivity and external inputs.

Selective consumption and metabolic allocation of terrestrial and algal carbon determine allochthony in lake bacteria

PubMed Central

Guillemette, François; Leigh McCallister, S; del Giorgio, Paul A

2016-01-01

Here we explore strategies of resource utilization and allocation of algal versus terrestrially derived carbon (C) by lake bacterioplankton. We quantified the consumption of terrestrial and algal dissolved organic carbon, and the subsequent allocation of these pools to bacterial growth and respiration, based on the δ13C isotopic signatures of bacterial biomass and respiratory carbon dioxide (CO2). Our results confirm that bacterial communities preferentially remove algal C from the terrestrially dominated organic C pool of lakes, but contrary to current assumptions, selectively allocate this autochthonous substrate to respiration, whereas terrestrial C was preferentially allocated to biosynthesis. The results provide further evidence of a mechanism whereby inputs of labile, algal-derived organic C may stimulate the incorporation of a more recalcitrant, terrestrial C pool. This mechanism resulted in a counterintuitive pattern of high and relatively constant levels of allochthony (~76%) in bacterial biomass across lakes that otherwise differ greatly in productivity and external inputs. PMID:26623544

Sensing site-specific structural characteristics and chirality using vibrational circular dichroism of isotope labeled peptides.

PubMed

Keiderling, Timothy A

2017-12-01

Isotope labeling has a long history in chemistry as a tool for probing structure, offering enhanced sensitivity, or enabling site selection with a wide range of spectroscopic tools. Chirality sensitive methods such as electronic circular dichroism are global structural tools and have intrinsically low resolution. Consequently, they are generally insensitive to modifications to enhance site selectivity. The use of isotope labeling to modify vibrational spectra with unique resolvable frequency shifts can provide useful site-specific sensitivity, and these methods have been recently more widely expanded in biopolymer studies. While the spectral shifts resulting from changes in isotopic mass can provide resolution of modes from specific parts of the molecule and can allow detection of local change in structure with perturbation, these shifts alone do not directly indicate structure or chirality. With vibrational circular dichroism (VCD), the shifted bands and their resultant sign patterns can be used to indicate local conformations in labeled biopolymers, particularly if multiple labels are used and if their coupling is theoretically modeled. This mini-review discusses selected examples of the use of labeling specific amides in peptides to develop local structural insight with VCD spectra. © 2017 Wiley Periodicals, Inc.

Fast, low-level detection of strontium-90 and strontium-89 in environmental samples by collinear resonance ionization spectroscopy

NASA Astrophysics Data System (ADS)

Monz, L.; Hohmann, R.; Kluge, H.-J.; Kunze, S.; Lantzsch, J.; Otten, E. W.; Passler, G.; Senne, P.; Stenner, J.; Stratmann, K.; Swendt, K.; Zimmer, K.; Herrmann, G.; Trautmann, N.; Walter, K.

1993-12-01

Environmental assessment in the wake of a nuclear accident requires the rapid determination of the radiotoxic isotopes 89Sr and 90Sr. Useful measurements must be able to detect 10 8 atoms in the presence of about 10 18 atoms of the stable, naturally occurring isotopes. This paper describes a new approach to this problem using resonance ionization spectroscopy in collinear geometry, combined with classical mass separation. After collection and chemical separation, the strontium from a sample is surface-ionized and the ions are accelerated to an energy of about 30 keV. Initially, a magnetic mass separator provides an isotopic selectivity of about 10 6. The ions are then neutralized by charge exchange and the resulting fast strontium atoms are selectively excited into high-lying atomic Rydberg states by narrow-band cw laser light in collinear geometry. The Rydberg atoms are then field-ionized and detected. Thus far, a total isotopic selectivity of S > 10 10 and an overall efficiency of ξ = 5 × 10 -6 have been achieved. The desired detection limit of 10 8 atoms 90Sr has been demonstrated with synthetic samples.

Non-Chondritic Ni Isotope Composition of the Bulk Silicate Earth

NASA Astrophysics Data System (ADS)

Klaver, M.; Elliott, T.

2018-05-01

We present high-precision Ni isotope data of chondritic meteorites and carefully selected mantle peridotites. These data show that the Bulk Silicate Earth is ca. 90 ppm lighter than chondritic meteorites, possibly as the result of core formation.

New developments of the in-source spectroscopy method at RILIS/ISOLDE

NASA Astrophysics Data System (ADS)

Marsh, B. A.; Andel, B.; Andreyev, A. N.; Antalic, S.; Atanasov, D.; Barzakh, A. E.; Bastin, B.; Borgmann, Ch.; Capponi, L.; Cocolios, T. E.; Day Goodacre, T.; Dehairs, M.; Derkx, X.; De Witte, H.; Fedorov, D. V.; Fedosseev, V. N.; Focker, G. J.; Fink, D. A.; Flanagan, K. T.; Franchoo, S.; Ghys, L.; Huyse, M.; Imai, N.; Kalaninova, Z.; Köster, U.; Kreim, S.; Kesteloot, N.; Kudryavtsev, Yu.; Lane, J.; Lecesne, N.; Liberati, V.; Lunney, D.; Lynch, K. M.; Manea, V.; Molkanov, P. L.; Nicol, T.; Pauwels, D.; Popescu, L.; Radulov, D.; Rapisarda, E.; Rosenbusch, M.; Rossel, R. E.; Rothe, S.; Schweikhard, L.; Seliverstov, M. D.; Sels, S.; Sjödin, A. M.; Truesdale, V.; Van Beveren, C.; Van Duppen, P.; Wendt, K.; Wienholtz, F.; Wolf, R. N.; Zemlyanoy, S. G.

2013-12-01

At the CERN ISOLDE facility, long isotope chains of many elements are produced by proton-induced reactions in target materials such as uranium carbide. The Resonance Ionization Laser Ion Source (RILIS) is an efficient and selective means of ionizing the reaction products to produce an ion beam of a chosen isotope. Coupling the RILIS with modern ion detection techniques enables highly sensitive studies of nuclear properties (spins, electromagnetic moments and charge radii) along an isotope chain, provided that the isotope shifts and hyperfine structure splitting of the atomic transitions can be resolved. At ISOLDE the campaign to measure the systematics of isotopes in the lead region (Pb, Bi, Tl and Po) has been extended to include the gold and astatine isotope chains. Several developments were specifically required for the feasibility of the most recent measurements: new ionization schemes (Po, At); a remote controlled narrow line-width mode of operation for the RILIS Ti:sapphire laser (At, Au, Po); isobar free ionization using the Laser Ion Source Trap, LIST (Po); isobar selective particle identification using the multi-reflection time-of-flight mass separator (MR-ToF MS) of ISOLTRAP (Au, At). These are summarized as part of an overview of the current status of the in-source resonance ionization spectroscopy setup at ISOLDE.

A procedural manual for measurement of uranium and thorium isotopes utilizing the USGS-Stanford Finnegan Mat 262

USGS Publications Warehouse

Shamp, Donald D.

2001-01-01

Over the past several decades investigators have extensively examined the 238U-234U- 230Th systematics of a variety of geologic materials using alpha spectroscopy. Analytical uncertainty for 230Th by alpha spectroscopy has been limited to about 2% (2σ). The advantage of thermal ionization mass spectroscopy (TIMS), introduced by Edwards and co-workers in the late 1980’s is the increased detectability of these isotopes by a factor of ~200, and decreases in the uncertainty for 230Th to about 5‰ (2σ) error. This report is a procedural manual for using the USGS-Stanford Finnegan-Mat 262 TIMS to collect and isolate Uranium and Thorium isotopic ratio data. Chemical separation of Uranium and Thorium from the sample media is accomplished using acid dissolution and then processed using anion exchange resins. The Finnegan-Mat262 Thermal Ionization Mass Spectrometer (TIMS) utilizes a surface ionization technique in which nitrates of Uranium and Thorium are placed on a source filament. Upon heating, positive ion emission occurs. The ions are then accelerated and focused into a beam which passes through a curved magnetic field dispersing the ions by mass. Faraday cups and/or an ion counter capture the ions and allow for quantitative analysis of the various isotopes.

Calcium Isotopes in Foraminifera Shells: Evaluation for Paleo-temperature Reconstruction

NASA Astrophysics Data System (ADS)

Paytan, A.; Revello, C. A.; Bullen, T. D.

2002-12-01

The Ca stable isotope ratio of foraminifera shells has been suggested as a potential paleo-temperature proxy and has recently been applied in several studies to reconstruct glacial interglacial fluctuations in seawater temperatures. The major advantage of using Ca isotopes for paleo-temperature reconstruction is the relatively long residence time of Ca in the ocean. Thus, no spatial or temporal change in the Ca isotopic composition of seawater is expected over time scales much shorter than a million years. Moreover, since Ca is a major constituent of carbonate, and an isotopic ratio rather than an element concentration or element-element ratio (e.g. Mg/Ca, Sr/Ca) is measured, the Ca isotope proxy is much less likely to be affected by post depositional diagenetic alteration. However, preliminary results indicate that kinetic effects might largely control the Ca isotope fractionation involved in calcite shell formation. Before this new and exciting proxy can be utilized routinely, a better understanding of the parameters controlling Ca isotope fractionation in carbonate minerals in general and in foraminifera and other carbonate-secreting organisms is required. We have measured the Ca stable isotope ratio of several foraminifera species from core top sediments from two well-studied sites to determine the inter-species and within-species variability in Ca isotopes. We assess the effects of water temperature, calcification rate, and vital effects on the Ca stable isotope ratio of modern foraminifera and evaluate the potential of this proxy for paleo-temperature reconstruction.

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.

Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

USGS Publications Warehouse

Vinson, David S.; Blair, Neal E.; Martini, Anna M.; Larter, Steve; Orem, William H.; McIntosh, Jennifer C.

2017-01-01

Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH4, δD-H2O, δ13C-CH4, and δ13C-CO2) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales.Isotopic fingerprinting techniques that combine δ13C-CH4 with δD-CH4 and/or δ13C-CO2have significant limitations: (1) The consistent ~ 160‰ offset between δD-H2O and δD-CH4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon isotope fractionation between δ13C-CH4 and δ13C-CO2(α13CCO2-CH4) to differ from the true methanogenic fractionation, complicating interpretation of methanogenic pathways. (3) Where little-fractionating non-methanogenic bacterial processes compete with highly-fractionating methanogenesis, the mass balance between CH4 and CO2 is affected. This has implications for δ13C values and provides an alternative interpretation for net C isotope signatures than solely the pathways used by active methanogens. (4) While most of the reviewed values of δD-H2O - δD-CH4 and α13CCO2-CH4 are apparently consistent with hydrogenotrophic methanogenesis as the dominant pathway in coal beds and shales, recent microbial community characterization techniques suggest a possible role for acetoclastic or methylotrophic methanogenesis in some basins.

Geochemistry of thermal water from selected wells, Boise, Idaho

USGS Publications Warehouse

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

1989-01-01

Samples of thermal water from selected wells in the Boise area were analyzed for chemical composition; stable isotopes of hydrogen, oxygen, and dissolved carbon; radioactive carbon; and dissolved-gas concentrations. Chemically, the waters are virtually identical to those of the adjacent Idaho batholith. Isotopically, the thermal waters are more depleted in deuterium and oxygen-18 than coldwater springs in the presumed recharge area. Chemical and isotopic data indicate the presence of two separate geothermal systems. Radioactive carbon and dissolved helium concentrations are interpreted to indicate recharge during the Pleistocene. Hot water in or southeast of Boise probably recharged 20,000 to 30,000 years ago, and warm water 2.5 miles northwest of Boise probably recharged at least 15,000 years ago.

Relativistic astrophysics. [design analysis and performance tests of Cerenkov counters for detection of iron isotopes

NASA Technical Reports Server (NTRS)

Price, P. B.

1976-01-01

The design, experimental testing, and calibration (error analysis) of a high resolution Cerenkov-scintillation detector is presented. The detector is capable of detecting iron isotopes and heavy ions of cosmic rays, and of performing direct measurements of individual neighboring isotopes at charge resolution 26. It utilizes Lexan (trademark) sheets, and has been used in flight packages of balloons and on the Skylab. The detector will be able to provide more information on violet astrophysical processes, such as thermonuclear reactions on neutron stars. Ground support and display equipment which are to be used in conjunction with the detector are also discussed.

Rare isotope studies involving catalytic oxidation of CO over platinum-tin oxide

NASA Technical Reports Server (NTRS)

Upchurch, Billy T.; Wood, George M., Jr.; Hess, Robert V.; Hoyt, Ronald F.

1987-01-01

Results of studies utilizing normal and rare oxygen isotopes in the catalytic oxidation of carbon monoxide over a platinum-tin oxide catalyst substrate are presented. Chemisorption of labeled carbon monoxide on the catalyst followed by thermal desorption yielded a carbon dioxide product with an oxygen-18 composition consistent with the formation of a carbonate-like intermediate in the chemisorption process. The efficacy of a method developed for the oxygen-18 labeling of the platinum-tin oxide catalyst surface for use in closed cycle pulsed care isotope carbon dioxide lasers is demonstrated for the equivalent of 10 to the 6th power pulses at 10 pulses per second.

Stable isotopes in collagen and Late Quaternary carnivore palaeoecology

NASA Astrophysics Data System (ADS)

Bocherens, Hervé

2010-05-01

Several taxa of large carnivores co-occurred during the late Pleistocene in the steppe-tundra ecosystem, such as wolf Canis lupus, cave lion Panthera leo spelaea, cave hyaena Crocuta crocuta spelaea, brown bear Ursus arctos and cave bear Ursus spelaeus and Ursus ingressus. This abundance of taxa belonging to the same guild raises questions about niche partitioning, especially in terms of dietary specialization and prey selection. Observations of the dietary ecology of the extant relatives of these late Pleistocene carnivores does not provide unambiguous answers as these populations live under very different environmental conditions where other potential prey species are present, but it appears that most of these modern large carnivores are relatively flexible in their prey selection. Palaeontological investigations dealing with faunal associations and activity marks on fossil bones also have their limitations, such as taphonomic biases (palimpsests rather than biological associations) and do not allow the quantification of consumption of various preys. In contrast, carbon and nitrogen isotopic signatures of bone collagen depend directly on those of the average diet. Since different potential prey species occurring in the steppe-tundra exhibit consistent isotopic differences for these chemical elements, it is possible to relate the carbon and nitrogen isotopic signatures measured in fossil carnivores with the preferential consumption of some prey species. Some amount of quantification can be provided using modified versions of mixing models developed for modern ecosystems. In addition, this isotopic approach is individual-based and it is therefore possible to investigate intra- and inter-population differences in prey selection, as well as possible chronological trends and differences linked to genetic differences by combining isotopic and ancient DNA studies on the same material. The isotopic approach has already shown that among the tested large carnivores, cave bears of various genetic types are overwhelmingly vegetarian while coeval brown bears are essentially carnivores, cave lions have a marked preference for reindeer, and none of the large carnivores match Neanderthals in terms of megaherbivore consumption (i.e. woolly mammoth and woolly rhinoceros).

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

NASA Astrophysics Data System (ADS)

Gövert, D.; Conrad, R.

2009-04-01

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

Application of Stable Isotope-Assisted Metabolomics for Cell Metabolism Studies

PubMed Central

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

2014-01-01

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

North Pacific barium isotope distributions illustrate importance of ocean mixing in controlling barium distributions despite weak regional circulation

NASA Astrophysics Data System (ADS)

Geyman, B.; Auro, M. E. E.; LaVigne, M.; Ptacek, J. L.; Horner, T. J.

2016-12-01

The dissolved behavior of barium in the ocean exhibits a `refractory' nutrient-type profile similar to that of silicon, which has led to the use of Ba as a proxy for paleo-productivity and carbon cycling. Marine barium cycling appears to be controlled by the precipitation of micron-scale barite crystals in the mesopelagic and their subsequent dissolution throughout the water column, which has been shown to impart an isotopic signature that may itself harbor information about ocean circulation and export production. However, the utility of Ba-based proxies in chemical and paleoceanography relies on a sound understanding of the processes governing marine barium distributions, which remain unresolved. Here, we report the first full oceanographic depth profile of barium isotopes from the North Pacific Ocean (30 N, 140 W), which offers the ability to resolve biogeochemical cycling from mixing processes in a given water mass. Our data confirm findings from other oceanographic regions showing a close coupling between increasing [Ba] and decreasing Ba-isotope compositions with depth. Unlike other profiles however, this coupling is restricted to the upper 1,000 m of the North Pacific water column, with samples from between 1,000 m and 4,500 m showing a roughly 60 % increase in [Ba] but essentially no changes in their Ba-isotope compositions (within measurement uncertainty of 15 ppm/AMU). As with Atlantic data, samples spanning the entire profile define a linear trend (R2 > 0.9) when plotted as Ba-isotope compositions against 1/[Ba], indicating that conservative mixing can account for much of the Ba-isotope variation in the North Pacific water column. Overall, these findings highlight the utility of stable isotope measurements to illuminate the processes governing nutrient cycling, and support the critical role of large-scale ocean circulation in setting `refractory' nutrient distributions. These results have particular relevance to regions with relatively weak overturning circulation, such as the North Pacific, because they elucidate the mechanistic basis that underpins Ba/Ca and other Ba-based tracers of the marine carbon cycle in paleoceanography.

A manual for a laboratory information management system (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1997-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

A manual for a Laboratory Information Management System (LIMS) for light stable isotopes

USGS Publications Warehouse

Coplen, Tyler B.

1998-01-01

The reliability and accuracy of isotopic data can be improved by utilizing database software to (i) store information about samples, (ii) store the results of mass spectrometric isotope-ratio analyses of samples, (iii) calculate analytical results using standardized algorithms stored in a database, (iv) normalize stable isotopic data to international scales using isotopic reference materials, and (v) generate multi-sheet paper templates for convenient sample loading of automated mass-spectrometer sample preparation manifolds. Such a database program is presented herein. Major benefits of this system include (i) an increase in laboratory efficiency, (ii) reduction in the use of paper, (iii) reduction in workload due to the elimination or reduction of retyping of data by laboratory personnel, and (iv) decreased errors in data reported to sample submitters. Such a database provides a complete record of when and how often laboratory reference materials have been analyzed and provides a record of what correction factors have been used through time. It provides an audit trail for stable isotope laboratories. Since the original publication of the manual for LIMS for Light Stable Isotopes, the isotopes 3 H, 3 He, and 14 C, and the chlorofluorocarbons (CFCs), CFC-11, CFC-12, and CFC-113, have been added to this program.

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

USGS Publications Warehouse

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

2006-01-01

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

Laser separation of lithium isotopes by double resonance enhanced multiphoton ionization of Li/sub 2/

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

Balz, J.G.; Bernheim, R.A.; Gold, L.P.

1987-01-01

Multiphoton ionization spectra of /sup 7/Li/sub 2/, /sup 6/Li/sub 2/, and /sup 7/Li/sup 6/Li vapors have been measured in the 570--650 nm region using a single, low resolution, multimode cw dye laser. A number of wavelengths provide selective multiphoton ionization of one isotopic species demonstrating the possibility of efficient laser-driven isotopic separation in lithium in this wavelength region.

Selected field and analytical methods and analytical results in the Dutch Flats area, western Nebraska, 1995-99

USGS Publications Warehouse

Verstraeten, Ingrid M.; Steele, G.V.; Cannia, J.C.; Bohlke, J.K.; Kraemer, T.E.; Hitch, D.E.; Wilson, K.E.; Carnes, A.E.

2001-01-01

A study of the water resources of the Dutch Flats area in the western part of the North Platte Natural Resources District, western Nebraska, was conducted from 1995 through 1999 to describe the surface water and hydrogeology, the spatial distribution of selected water-quality constituents in surface and ground water, and the surface-water/ground-water interaction in selected areas. This report describes the selected field and analytical methods used in the study and selected analytical results from the study not previously published. Specifically, dissolved gases, age-dating data, and other isotopes collected as part of an intensive sampling effort in August and November 1998 and all uranium and uranium isotope data collected through the course of this study are included in the report.

Isotope ratio analysis of individual sub-micrometer plutonium particles with inductively coupled plasma mass spectrometry.

PubMed

Esaka, Fumitaka; Magara, Masaaki; Suzuki, Daisuke; Miyamoto, Yutaka; Lee, Chi-Gyu; Kimura, Takaumi

2010-12-15

Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. Copyright © 2010 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Geospatial modeling of plant stable isotope ratios - the development of isoscapes

NASA Astrophysics Data System (ADS)

West, J. B.; Ehleringer, J. R.; Hurley, J. M.; Cerling, T. E.

2007-12-01

Large-scale spatial variation in stable isotope ratios can yield critical insights into the spatio-temporal dynamics of biogeochemical cycles, animal movements, and shifts in climate, as well as anthropogenic activities such as commerce, resource utilization, and forensic investigation. Interpreting these signals requires that we understand and model the variation. We report progress in our development of plant stable isotope ratio landscapes (isoscapes). Our approach utilizes a GIS, gridded datasets, a range of modeling approaches, and spatially distributed observations. We synthesize findings from four studies to illustrate the general utility of the approach, its ability to represent observed spatio-temporal variability in plant stable isotope ratios, and also outline some specific areas of uncertainty. We also address two basic, but critical questions central to our ability to model plant stable isotope ratios using this approach: 1. Do the continuous precipitation isotope ratio grids represent reasonable proxies for plant source water?, and 2. Do continuous climate grids (as is or modified) represent a reasonable proxy for the climate experienced by plants? Plant components modeled include leaf water, grape water (extracted from wine), bulk leaf material ( Cannabis sativa; marijuana), and seed oil ( Ricinus communis; castor bean). Our approaches to modeling the isotope ratios of these components varied from highly sophisticated process models to simple one-step fractionation models to regression approaches. The leaf water isosocapes were produced using steady-state models of enrichment and continuous grids of annual average precipitation isotope ratios and climate. These were compared to other modeling efforts, as well as a relatively sparse, but geographically distributed dataset from the literature. The latitudinal distributions and global averages compared favorably to other modeling efforts and the observational data compared well to model predictions. These results yield confidence in the precipitation isoscapes used to represent plant source water, the modified climate grids used to represent leaf climate, and the efficacy of this approach to modeling. Further work confirmed these observations. The seed oil isoscape was produced using a simple model of lipid fractionation driven with the precipitation grid, and compared well to widely distributed observations of castor bean oil, again suggesting that the precipitation grids were reasonable proxies for plant source water. The marijuana leaf δ2H observations distributed across the continental United States were regressed against the precipitation δ2H grids and yielded a strong relationship between them, again suggesting that plant source water was reasonably well represented by the precipitation grid. Finally, the wine water δ18O isoscape was developed from regressions that related precipitation isotope ratios and climate to observations from a single vintage. Favorable comparisons between year-specific wine water isoscapes and inter-annual variations in previous vintages yielded confidence in the climate grids. Clearly significant residual variability remains to be explained in all of these cases and uncertainties vary depending on the component modeled, but we conclude from this synthesis that isoscapes are capable of representing real spatial and temporal variability in plant stable isotope ratios.

Triple Oxygen and Clumped Isotopes in Synthetic and Natural Carbonates: Implications for Paleoclimate and Paleohydrology Studies

NASA Astrophysics Data System (ADS)

Laskar, A. H.; Rangarajan, R.; Liang, M. C.

2016-12-01

Conventional oxygen isotope (δ18O) has widely been used for paleoclimate studies. However, multiple influencing factors such as temperature, precipitation and kinetic effects during carbonate precipitation complicate the interpretation of δ18O data sometimes. Triple oxygen isotope (Δ17O) in carbonates could be sensitive to kinetic effect occur during its precipitation in water. Carbonates may also record the Δ17O signature of the parent waters, providing a basis in the natural carbonates for identifying kinetic processes such as rapid degassing at lower relative humidity inside a cave during speleothem deposition. Clumped isotopes (Δ47) in carbonates give the formation temperatures of the carbonates if precipitated under isotopic equilibrium. The first goal of the study is to explore the applicability of Δ17O for paleohydrolocial studies. The second is to reconstruct paleotemperature with suitable natural carbonates using Δ47values. This is a rare paleoclimate study utilizing two sophisticated new tools. CO2 produced from carbonates by acid digestion was used for both Δ47 and Δ17O analysis. Purified CO2 samples were directly introduced into the Mass spectrometer (MAT 253) for clumped isotope analysis [1] and CO2-O2 exchange method in presence of platinum for Δ17O analysis [2,3]. We measured Δ47 and Δ17O values in synthetic carbonates precipitated at different temperatures (10-90 oC) and Δ17O values in the water from which the carbonate precipitated. We observed consistent Δ47 values in the carbonates while Δ17O were found to vary. Probably a proper slope (between δ18O and δ17O) selection for carbonates would give consistent results. We also measured Δ47 and Δ17O in modern and well dated speleothems from Chinese and Indian caves to study the paleohydrology and paleotemperature. Δ47 and Δ17O were also measured in modern natural carbonate depositions such as corals, foraminifer and marbles to explore their potentials for paleoclimate studies. Implications of the results will be presented and discussed. [1] Laskar, A. H., et al. Terra Nova, 28, 265-270, 2016. [2] Mahata, S., et al. Analytical Chemistry, 85, 6894-6901, 2013. [3] Mahata, S. et al. Rapid. Comm. Mass Spect., 30, 119-131, 2016.

Observation of the 162Dy-164Dy Isotope Shift for the 0 → 16 717.79 cm-1 Optical Transition.

PubMed

Nardin Barreta, Luiz Felipe; Victor, Alessandro Rogério; Bueno, Patrícia; Dos Santos, Jhonatha Ricardo; da Silveira, Carlos Alberto Barbosa; Neri, José Wilson; Neto, Jonas Jakutis; Sbampato, Maria Esther; Destro, Marcelo Geraldo

2017-08-01

In this work, we report a newly observed isotope shift between 162 Dy and 164 Dy isotopes for the 0 → 16 717.79 cm -1 (598.003 nm) optical transition. We compared the newly observed results against two other lines (597.452 nm and 598.859 nm), which we measured in this work, and were already reported in the literature. The newly observed 162-164 Dy isotope shift, shows at least a 20% larger isotope shift than the isotope shifts for the other two lines investigated. The larger 162-164 isotope shift observed for the 598.003 nm line could lead to an increased isotope selectivity for atomic vapor laser isotope separation (AVLIS). Hence, this line could be a good choice for application in AVLIS. Experimental data available in the literature for the 597.452 nm and 598.859 nm lines, enabled us to perform simulations of spectra for both lines, in order to confirm the accuracy of our experimental measurements.

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.

Molecular isotopic engineering (MIE): industrial manufacture of naproxen of predetermined stable carbon-isotopic compositions for authenticity and security protection and intellectual property considerations

NASA Astrophysics Data System (ADS)

Jasper, J. P.; Farina, P.; Pearson, A.; Mezes, P. S.; Sabatelli, A. D.

2016-05-01

Molecular Isotopic Engineering (MIE) is the directed stable-isotopic synthesis of chemical products for reasons of product identification and of product security, and also for intellectual property considerations. We report here a generally excellent correspondence between the observed and predicted stable carbon-isotopic (δ13C) results for a successful directed synthesis of racemic mixture from its immediate precursors. The observed results are readily explained by the laws of mass balance and isotope mass balance. Oxygen- and hydrogen isotopic results which require an additional assessment of the effects of O and H exchange, presumably due to interaction with water in the reaction solution, are addressed elsewhere. A previous, cooperative study with the US FDA-DPA showed that individual manufacturers of naproxen could readily be differentiated by their stable-isotopic provenance (δ13C, δ18O, and δD ref. 1). We suggest that MIE can be readily employed in the bio/pharmaceutical industry without alteration of present manufacturing processes other than isotopically selecting and/or monitoring reactants and products.

2007 California Aerosol Study: Evaluation of δ15N as a Tracer Of NOx Sources and Chemsitry

NASA Astrophysics Data System (ADS)

Katzman, T. L.

2017-12-01

Although stable isotopes of N are commonly used as a source tracer, how this tracer is applied is a point of contention. The "source" hypothesis argues that the δ15N value of NO3- reflects the δ15N value of NOx source inputs into the environment, and any observed variation is solely the result of differences in source contributions. Conversely, the "chemistry" hypothesis argues that N isotopes are influenced by chemical reactions, atmospheric or biologic processing, and post-depositional effects. Previous studies often apply the source hypothesis, writing off the chemistry hypothesis as "minor," but others have noted the impact chemistry should has on δ15N values. Given the known complications, this work seeks to assess the use of stable isotopes as tracers, specifically, the assumption that the δ15N value is a tracer of source alone without significant influence from chemical reactions. If the "source" hypothesis is correct, source emission data, known source δ15N values, and isotope mass balance should be able to approximate measured δ15NNO3 values and determine the δ15N value associated with wildfire derived NOx, which is currently unknown. Significant deviations from observed values would support the significance of equilibrium and kinetic isotope effects associated with chemical reactions and processing in the atmosphere. Aerosols collected in during 2007, emission data, and isotopic analysis were utilized to determine the utility of δ15N as tracer of NOx sources. San Diego, California is a coastal urban area influenced by sea salt aerosols, anthropogenic combustion emissions, and seasonal wildfires. Wildfires also have a significant influence on local atmospheric chemistry and 2007 was notable for being one of the worst fire seasons in the San Diego region on record. Isotopic analysis of collected NO3- has suggested that source δ15N values are likely not conserved as NOx is oxidized into NO3-. Given known source contributions and known δ15N values of NOx sources, isotope mass balance predicts that a NOx source with highly positive δ15N value must exist for the source hypothesis to be valid. Furthermore, isotopic analysis has also suggested that wildfire emissions may produce a depleted δ15N, disagreeing with previously predicted δ15N values.

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

DOE PAGES

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.; ...

2017-12-04

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

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

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Stable Isotope Quantitative N-Glycan Analysis by Liquid Separation Techniques and Mass Spectrometry.

PubMed

Mittermayr, Stefan; Albrecht, Simone; Váradi, Csaba; Millán-Martín, Silvia; Bones, Jonathan

2017-01-01

Liquid phase separation analysis and subsequent quantitation remains a challenging task for protein-derived oligosaccharides due to their inherent structural complexity and diversity. Incomplete resolution or co-detection of multiple glycan species complicates peak area-based quantitation and associated statistical analysis when optical detection methods are used. The approach outlined herein describes the utilization of stable isotope variants of commonly used fluorescent tags that allow for mass-based glycan identification and relative quantitation following separation by liquid chromatography (LC) or capillary electrophoresis (CE). Comparability assessment of glycoprotein-derived oligosaccharides is performed by derivatization with commercially available isotope variants of 2-aminobenzoic acid or aniline and analysis by LC- and CE-mass spectrometry. Quantitative information is attained from the extracted ion chromatogram/electropherogram ratios generated from the light and heavy isotope clusters.

Unexpected hydrogen isotope variation in oceanic pelagic seabirds

USGS Publications Warehouse

Ostrom, Peggy H.; Wiley, Anne E.; Rossman, Sam; Stricker, Craig A.; James, Helen F.

2014-01-01

Hydrogen isotopes have significantly enhanced our understanding of the biogeography of migratory animals. The basis for this methodology lies in predictable, continental patterns of precipitation δD values that are often reflected in an organism's tissues. δD variation is not expected for oceanic pelagic organisms whose dietary hydrogen (water and organic hydrogen in prey) is transferred up the food web from an isotopically homogeneous water source. We report a 142% range in the δD values of flight feathers from the Hawaiian petrel (Pterodroma sandwichensis), an oceanic pelagic North Pacific species, and inquire about the source of that variation. We show δD variation between and within four other oceanic pelagic species: Newell's shearwater (Puffinus auricularis newellii), Black-footed albatross (Phoebastria nigripes), Laysan albatross (Phoebastria immutabilis) and Buller's shearwater (Puffinus bulleri). The similarity between muscle δD values of hatch-year Hawaiian petrels and their prey suggests that trophic fractionation does not influence δD values of muscle. We hypothesize that isotopic discrimination is associated with water loss during salt excretion through salt glands. Salt load differs between seabirds that consume isosmotic squid and crustaceans and those that feed on hyposmotic teleost fish. In support of the salt gland hypothesis, we show an inverse relationship between δD and percent teleost fish in diet for three seabird species. Our results demonstrate the utility of δD in the study of oceanic consumers, while also contributing to a better understanding of δD systematics, the basis for one of the most commonly utilized isotope tools in avian ecology.

Evaluation of UV-fs-LA-MC-ICP-MS for precise in situ copper isotopic microanalysis of cubanite.

PubMed

Ikehata, Kei; Hirata, Takafumi

2013-01-01

We evaluated the capabilities of an in situ method for measuring copper isotopes of cubanite using UV-fs-LA-MC-ICP-MS. A comparison of the UV-fs laser results with those obtained from the NIR-fs laser system shows that there is obviously an improvement in the precision (<0.10‰, 2SE) when using the UV-fs laser. In both wavelength modes, matrix-matched standards are required for reliable in situ copper isotope analysis of cubanite. This method was applied to determinations for copper isotopes of minute cubanite grains in a skarn ore. Copper isotopic ratios of cubanite grains near a weathered surface of the sample are lower than those of intact cubanite grains within the sample, suggesting that selective leaching of heavier copper isotope in primary minerals occurred during weathering.

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

NASA Technical Reports Server (NTRS)

Delionback, L. M.

1976-01-01

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

Isotope-dilution gas chromatography-mass spectrometry coupled with injection-port butylation for the determination of 4-t-octylphenol, 4-nonylphenols and bisphenol A in human urine.

PubMed

Chung, Shuang-Hung; Ding, Wang-Hsien

2018-02-05

An analytical method that utilizes isotope-dilution gas chromatography-mass spectrometry (ID-GC-MS) coupled with injection-port butylation was developed. The method was validated, and confirmed to be able to determine the presence of three commonly detected endocrine-disrupting chemicals (EDCs: 4-tert-octylphenol (4-t-OP), 4-nonylphenols (4-NPs) and bisphenol A (BPA)) in human urine with high precision and accuracy. After sample preparation by solid-phase extraction, the extract was introduced into GC-MS via injection-port butylation. The butylated target analytes were identified and quantified by using ion-trap mass spectrometry operating in the selected-ion-storage mode, and employing the measurement of peak area ratios of the butylated target analytes and labeled-analogues in the samples and calibration standards. The labeled-analogues were also used to correct the variations associated with the analysis and matrix effect. The limits of quantitation (LOQs) ranged from 0.1 to 0.3ng/mL. High precisions for both intra- and inter-day analysis ranged from 1 to 6%, and excellent accuracy (mean recovery) ranged from 92 to 105% on two concentration levels. In human urine, the total concentrations of three selected EDCs varied from 1.28 to 7.14ng/mL. 4-NPs were detected within all collected samples. The developed method allows accurate analysis of trace-level of EDCs in urine, and these target EDCs could act as useful biomarkers to assess exposure in biomonitoring studies and programs. Copyright © 2017 Elsevier B.V. All rights reserved.

Infrared laser system

DOEpatents

Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph S.

1977-01-01

An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

Infrared laser system

DOEpatents

Cantrell, Cyrus D.; Carbone, Robert J.; Cooper, Ralph

1982-01-01

An infrared laser system and method for isotope separation may comprise a molecular gas laser oscillator to produce a laser beam at a first wavelength, Raman spin flip means for shifting the laser to a second wavelength, a molecular gas laser amplifier to amplify said second wavelength laser beam to high power, and optical means for directing the second wavelength, high power laser beam against a desired isotope for selective excitation thereof in a mixture with other isotopes. The optical means may include a medium which shifts the second wavelength high power laser beam to a third wavelength, high power laser beam at a wavelength coincidental with a corresponding vibrational state of said isotope and which is different from vibrational states of other isotopes in the gas mixture.

Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts

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

Ojeda, Manuel; Li, Anwu; Nabar, Rahul P.

2010-11-25

H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes onmore » both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.« less

Design of a Fission 99 Mo Recovery Process and Implications toward Mo Adsorption Mechanism on Titania and Alumina Sorbents

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

Stepinski, Dominique C.; Youker, Amanda J.; Krahn, Elizabeth O.

2017-03-01

Molybdenum-99 is a parent of the most widely used medical isotope technetium-99m. Proliferation concerns have prompted development of alternative Mo production methods utilizing low enriched uranium. Alumina and titania sorbents were evaluated for separation of Mo from concentrated uranyl nitrate solutions. System, mass transfer, and isotherm parameters were determined to enable design of Mo separation processes under a wide range of conditions. A model-based approach was utilized to design representative commercial-scale column processes. The designs and parameters were verified with bench-scale experiments. The results are essential for design of Mo separation processes from irradiated uranium solutions, selection of support materialmore » and process optimization. Mo uptake studies show that adsorption decreases with increasing concentration of uranyl nitrate; howeveL, examination of Mo adsorption as a function of nitrate ion concentration shows no dependency, indicating that uranium competes with Mo for adsorption sites. These results are consistent with reports indicating that Mo forms inner-sphere complexes with titania and alumina surface groups.« less

Mass, charge, and energy separation by selective acceleration with a traveling potential hill

NASA Astrophysics Data System (ADS)

Tung, L. Schwager; Barr, W. L.; Lowder, R. S.; Post, R. F.

1996-10-01

A traveling electric potential hill has been used to generate an ion beam with an energy distribution that is mass dependent from a monoenergetic ion beam of mixed masses. This effect can be utilized as a novel method for mass separation applied to identification or enrichment of ions (e.g., of elements, isotopes, or molecules). This theory for mass-selective acceleration is presented here and is shown to be confirmed by experiment and by a time-dependent particle-in-cell computer simulation. Results show that monoenergetic ions with the particular mass of choice are accelerated by controlling the hill potential and the hill velocity. The hill velocity is typically 20%-30% faster than the ions to be accelerated. The ability of the hill to pickup a particular mass uses the fact that small kinetic energy differences in the lab frame appear much larger in the moving hill frame. Ions will gain energy from the approaching hill if their relative energy in the moving hill frame is less than the peak potential of the hill. The final energy of these accelerated ions can be several times the source energy, which facilitates energy filtering for mass purification or identification. If the hill potential is chosen to accelerate multiple masses, the heaviest mass will have the greatest final energy. Hence, choosing the appropriate hill potential and collector retarding voltage will isolate ions with the lightest, heaviest, or intermediate mass. In the experimental device, called a Solitron, purified 20Ne and 22Ne are extracted from a ribbon beam of neon that is originally composed of 20Ne:22Ne in the natural ratio of 91:9. The isotopic content of the processed beam is determined by measuring the energy distribution of the detected current. These results agree with the theory. In addition to mass selectivity, our theory can also be applied to the filtration of an ion beam according to charge state or energy. Because of this variety of properties, the Solitron is envisioned to have broad applications. The primary application is for the enrichment of stable isotopes for medical and industrial tracers. Other applications include mass analysis of unknown gases (atomic and molecular) and metals, extracting single charge states from a multiply charged beam, accelerating the high energy tail in a beam or plasma with a velocity distribution, and beam bunching.

Intracellular Cadmium Isotope Fractionation

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B.; Henderson, G. M.; Rickaby, R. E.

2011-12-01

Recent stable isotope studies into the biological utilization of transition metals (e.g. Cu, Fe, Zn, Cd) suggest several stepwise cellular processes can fractionate isotopes in both culture and nature. However, the determination of fractionation factors is often unsatisfactory, as significant variability can exist - even between different organisms with the same cellular functions. Thus, it has not been possible to adequately understand the source and mechanisms of metal isotopic fractionation. In order to address this problem, we investigated the biological fractionation of Cd isotopes within genetically-modified bacteria (E. coli). There is currently only one known biological use or requirement of Cd, a Cd/Zn carbonic anhydrase (CdCA, from the marine diatom T. weissfloggii), which we introduce into the E. coli genome. We have also developed a cleaning procedure that allows for the treating of bacteria so as to study the isotopic composition of different cellular components. We find that whole cells always exhibit a preference for uptake of the lighter isotopes of Cd. Notably, whole cells appear to have a similar Cd isotopic composition regardless of the expression of CdCA within the E. coli. However, isotopic fractionation can occur within the genetically modified E. coli during Cd use, such that Cd bound in CdCA can display a distinct isotopic composition compared to the cell as a whole. Thus, the externally observed fractionation is independent of the internal uses of Cd, with the largest Cd isotope fractionation occurring during cross-membrane transport. A general implication of these experiments is that trace metal isotopic fractionation most likely reflects metal transport into biological cells (either actively or passively), rather than relating to expression of specific physiological function and genetic expression of different metalloenzymes.

Sulfur isotope dynamics in a high-elevation catchment, West Glacier Lake, Wyoming

Treesearch

J. B. Finley; J. I. Drever; J. T. Turk

1995-01-01

Stable isotopes of S are used in conjunction with dissolved SO2-|4 concentrations to evaluate the utility of ä34S ratios in tracing contributions of bedrock-derived S to SO2-|4 in runoff. Water samples were collected over the annual hydrograph from two tributaries in the West Glacier Lake, Wyoming, catchment. Concentrations of SO2-|4 ranged from 12.6 to 43.0 Ìeq L-1;...

Preliminary assessment of rover power systems for the Mars Rover Sample Return Mission

NASA Technical Reports Server (NTRS)

Bents, David J.

1989-01-01

Four isotope power system concepts were presented and compared on a common basis for application to on-board electrical prime power for an autonomous planetary rover vehicle. A representative design point corresponding to the Mars Rover Sample Return (MRSR) preliminary mission requirements (500 W) was selected for comparison purposes. All systems concepts utilize the General Purpose Heat Source (GPHS) isotope heat source developed by DOE. Two of the concepts employ thermoelectric (TE) conversion: one using the GPHS Radioisotope Thermoelectric Generator (RTG) used as a reference case, the other using an advanced RTG with improved thermoelectric materials. The other two concepts employed are dynamic isotope power systems (DIPS): one using a closed Brayton cycle (CBC) turboalternator, and the other using a free piston Stirling cycle engine/linear alternator (FPSE) with integrated heat source/heater head. Near term technology levels have been assumed for concept characterization using component technology figure-of-merit values taken from the published literature. For example, the CBC characterization draws from the historical test database accumulated from space Brayton cycle subsystems and components from the NASA B engine through the mini-Brayton rotating unit. TE system performance is estimated from Voyager/multihundred Watt (MHW)-RTG flight experience through Mod-RTG performance estimates considering recent advances in TE materials under the DOD/DOE/NASA SP-100 and NASA Committee on Scientific and Technological Information programs. The Stirling DIPS system is characterized from scaled-down Space Power Demonstrator Engine (SPDE) data using the GPHS directly incorporated into the heater head. The characterization/comparison results presented here differ from previous comparison of isotope power (made for Low Earth Orbit (LEO) applications) because of the elevated background temperature on the Martian surface compared to LEO, and the higher sensitivity of dynamic systems to elevated sink temperature. The mass advantage of dynamic systems is significantly reduced for this application due to Mars' elevated background temperature.

Lineage-Specific Responses of Tooth Shape in Murine Rodents (Murinae, Rodentia) to Late Miocene Dietary Change in the Siwaliks of Pakistan

PubMed Central

Kimura, Yuri; Jacobs, Louis L.; Flynn, Lawrence J.

2013-01-01

Past ecological responses of mammals to climate change are recognized in the fossil record by adaptive significance of morphological variations. To understand the role of dietary behavior on functional adaptations of dental morphology in rodent evolution, we examine evolutionary change of tooth shape in late Miocene Siwalik murine rodents, which experienced a dietary shift toward C4 diets during late Miocene ecological change indicated by carbon isotopic evidence. Geometric morphometric analysis in the outline of upper first molars captures dichotomous lineages of Siwalik murines, in agreement with phylogenetic hypotheses of previous studies (two distinct clades: the Karnimata and Progonomys clades), and indicates lineage-specific functional responses to mechanical properties of their diets. Tooth shapes of the two clades are similar at their sympatric origin but deviate from each other with decreasing overlap through time. Shape change in the Karnimata clade is associated with greater efficiency of propalinal chewing for tough diets than in the Progonomys clade. Larger body mass in Karnimata may be related to exploitation of lower-quality food items, such as grasses, than in smaller-bodied Progonomys. The functional and ecophysiological aspects of Karnimata exploiting C4 grasses are concordant with their isotopic dietary preference relative to Progonomys. Lineage-specific selection was differentially greater in Karnimata, and a faster rate of shape change toward derived Karnimata facilitated inclusion of C4 grasses in the diet. Sympatric speciation in these clades is most plausibly explained by interspecific competition on resource utilization between the two, based on comparisons of our results with the carbon isotope data. Interspecific competition with Karnimata may have suppressed morphological innovation of the Progonomys clade. Pairwise analyses of morphological and carbon isotope data can uncover ecological causes of sympatric speciation and define functional adaptations of teeth to resources. PMID:24155885

Lineage-specific responses of tooth shape in murine rodents (murinae, rodentia) to late Miocene dietary change in the Siwaliks of Pakistan.

PubMed

Kimura, Yuri; Jacobs, Louis L; Flynn, Lawrence J

2013-01-01

Past ecological responses of mammals to climate change are recognized in the fossil record by adaptive significance of morphological variations. To understand the role of dietary behavior on functional adaptations of dental morphology in rodent evolution, we examine evolutionary change of tooth shape in late Miocene Siwalik murine rodents, which experienced a dietary shift toward C4 diets during late Miocene ecological change indicated by carbon isotopic evidence. Geometric morphometric analysis in the outline of upper first molars captures dichotomous lineages of Siwalik murines, in agreement with phylogenetic hypotheses of previous studies (two distinct clades: the Karnimata and Progonomys clades), and indicates lineage-specific functional responses to mechanical properties of their diets. Tooth shapes of the two clades are similar at their sympatric origin but deviate from each other with decreasing overlap through time. Shape change in the Karnimata clade is associated with greater efficiency of propalinal chewing for tough diets than in the Progonomys clade. Larger body mass in Karnimata may be related to exploitation of lower-quality food items, such as grasses, than in smaller-bodied Progonomys. The functional and ecophysiological aspects of Karnimata exploiting C4 grasses are concordant with their isotopic dietary preference relative to Progonomys. Lineage-specific selection was differentially greater in Karnimata, and a faster rate of shape change toward derived Karnimata facilitated inclusion of C4 grasses in the diet. Sympatric speciation in these clades is most plausibly explained by interspecific competition on resource utilization between the two, based on comparisons of our results with the carbon isotope data. Interspecific competition with Karnimata may have suppressed morphological innovation of the Progonomys clade. Pairwise analyses of morphological and carbon isotope data can uncover ecological causes of sympatric speciation and define functional adaptations of teeth to resources.

Image fusion of Secondary Ion Mass Spectrometry and Energy-dispersive X-Ray Spectroscopy data for the characterization of uranium-molybdenum fuel foils

NASA Astrophysics Data System (ADS)

Willingham, David; Naes, Benjamin E.; Tarolli, Jay G.; Schemer-Kohrn, Alan; Rhodes, Mark; Dahl, Michael; Guzman, Anthony; Burkes, Douglas E.

2018-01-01

Uranium-molybdenum (U-Mo) monolithic fuels represent one option for converting civilian research and test reactors operating with high enriched uranium (HEU) to low enriched uranium (LEU), effectively reducing the threat of nuclear proliferation world-wide. However, processes associated with fabrication of U-Mo monolithic fuels result in regions of elemental heterogeneity, observed as bands traversing the cross-section of representative samples. Isotopic variations (e.g., 235U and 238U) could also be introduced because of associated processing steps, particularly since HEU feedstock is melted with natural or depleted uranium diluent to produce LEU. This study demonstrates the utility of correlative analysis of Energy-Dispersive X-ray Spectroscopy (EDS) and Secondary Ion Mass Spectrometry (SIMS) with their image data streams using image fusion, resulting in a comprehensive microanalytical characterization toolbox. Elemental and isotopic measurements were made on a sample from the Advanced Test Reactor (ATR) Full-sized plate In-center flux trap Position (AFIP)-7 experiment and compared to previous optical and electron microscopy results. The image fusion results are characteristic of SIMS isotopic maps, but with the spatial resolution of EDS images and, therefore, can be used to increase the effective spatial resolution of the SIMS imaging results to better understand homogeneity or heterogeneity that persists because of processing selections. Visual inspection using the image fusion methodology indicated slight variations in the 235U/238U ratio and quantitative analysis using the image intensities across several FoVs revealed an average 235U atom percent value of 17.9 ± 2.4%, which was indicative of a non-uniform U isotopic distribution in the area sampled. Further development of this capability is useful for understanding the connections between the properties of LEU fuel alternatives and the ability to predict performance under irradiation.

Advances in the Metrology of Absolute Value Assignments to Isotopic Reference Materials: Consequences from the Avogadro Project

NASA Astrophysics Data System (ADS)

Vocke, Robert; Rabb, Savelas

2015-04-01

All isotope amount ratios (hereafter referred to as isotope ratios) produced and measured on any mass spectrometer are biased. This unfortunate situation results mainly from the physical processes in the source area where ions are produced. Because the ionized atoms in poly-isotopic elements have different masses, such processes are typically mass dependent and lead to what is commonly referred to as mass fractionation (for thermal ionization and electron impact sources) and mass bias (for inductively coupled plasma sources.) This biasing process produces a measured isotope ratio that is either larger or smaller than the "true" ratio in the sample. This has led to the development of numerous fractionation "laws" that seek to correct for these effects, many of which are not based on the physical processes giving rise to the biases. The search for tighter and reproducible precisions has led to two isotope ratio measurement systems that exist side-by-side. One still seeks to measure "absolute" isotope ratios while the other utilizes an artifact based measurement system called a delta-scale. The common element between these two measurement systems is the utilization of isotope reference materials (iRMs). These iRMs are used to validate a fractionation "law" in the former case and function as a scale anchor in the latter. Many value assignments of iRMs are based on "best measurements" by the original groups producing the reference material, a not entirely satisfactory approach. Other iRMs, with absolute isotope ratio values, have been produced by calibrated measurements following the Atomic Weight approach (AW) pioneered by NBS nearly 50 years ago. Unfortunately, the AW is not capable of calibrating the new generation of iRMs to sufficient precision. So how do we get iRMs with isotope ratios of sufficient precision and without bias? Such a focus is not to denigrate the extremely precise delta-scale measurements presently being made on non-traditional and tradition stable isotope systems. But even absolute isotope ratio measurements have an important role to play in delta-scale schemes. Highly precise and unbiased measurements of the artifact anchor for any scale facilitates the replacement of that scale's anchor once the initial supply of the iRM is exhausted. Absolute isotope ratio measurements of artifacts at the positive and negative extremes of a delta-scale will allow the appropriate assignment of delta-values to these normalizing iRMs, thereby minimizing any scale contractions or expansions to either side of the anchor artifact. And finally, absolute values for critical iRMs with also allow delta-scale results to be used in other scientific disciplines that employ other units of measure. Precise absolute isotope ratios of Si has been one of the consequences of the Avogadro Project (an international effort to replace the original kilogram artifact with a natural constant, the Planck constant.) We will present the results of applying such measurements to the principal iRMs for the Si isotope system (SRM 990, Big Batch and Diatomite) and its consequences for their delta-Si29 and delta-Si30 values.

Fabrication of 12% {sup 240}Pu calorimetry standards

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

Long, S.M.; Hildner, S.; Gutierrez, D.

1995-08-01

Throughout the DOE complex, laboratories are performing calorimetric assays on items containing high burnup plutonium. These materials contain higher isotopic range and higher wattages than materials previously encountered in vault holdings. Currently, measurement control standards have been limited to utilizing 6% {sup 240}Pu standards. The lower isotopic and wattage value standards do not complement the measurement of the higher burnup material. Participants of the Calorimetry Exchange (CALEX) Program have identified the need for new calorimetric assay standards with a higher wattage and isotopic range. This paper describes the fabrication and verification measurements of the new CALEX standard containing 12% {supmore » 240}Pu oxide with a wattage of about 6 to 8 watts.« less

Selected isotope ratio measurements of light metallic elements (Li, Mg, Ca, and Cu) by multiple collector ICP-MS

PubMed Central

Platzner, Thomas I.; Segal, Irina

2007-01-01

The unique capabilities of multiple collector inductively coupled mass spectrometry (MC-ICP-MS) for high precision isotope ratio measurements in light elements as Li, Mg, Ca, and Cu are reviewed in this paper. These elements have been intensively studied at the Geological Survey of Israel (GSI) and other laboratories over the past few years, and the methods used to obtain high precision isotope analyses are discussed in detail. The scientific study of isotopic fractionation of these elements is significant for achieving a better understanding of geochemical and biochemical processes in nature and the environment. PMID:17962922

Can the waiting-point nucleus 78Ni be studied at an on-line mass-separator?

NASA Astrophysics Data System (ADS)

Wöhr, A.; Andreyev, A.; Bijnens, N.; Breitenbach, J.; Franchoo, S.; Huyse, M.; Kudryavtsev, Y. A.; Piechaczek, A.; Raabe, R. R.; Reusen, I.; Vermeeren, L.; Van Duppen, P.

1997-02-01

Short-lived nickel isotopes have been studied using a chemically selective Ion Guide Laser Ion Source (IGLIS) based on resonance ionisation of atoms at the Leuven Isotope Separator On-Line (LISOL) separator. The decay properties of different Ni isotopes have been studied using β-γ-coincidences. Experimental production rates of proton induced fission of 238U are obtained for 69,71Ni. These numbers are in a strong disagreement with Silberg-Tsao calculations.

Isotope separation by photodissociation of Van der Waal's molecules

DOEpatents

Lee, Yuan T.

1977-01-01

A method of separating isotopes based on the dissociation of a Van der Waal's complex. A beam of molecules of a Van der Waal's complex containing, as one partner of the complex, a molecular species in which an element is present in a plurality of isotopes is subjected to radiation from a source tuned to a frequency which will selectively excite vibrational motion by a vibrational transition or through electronic transition of those complexed molecules of the molecular species which contain a desired isotope. Since the Van der Waal's binding energy is much smaller than the excitational energy of vibrational motion, the thus excited Van der Waal's complex dissociate into molecular components enriched in the desired isotope. The recoil velocity associated with vibrational to translational and rotational relaxation will send the separated molecules away from the beam whereupon the product enriched in the desired isotope can be separated from the constituents of the beam.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS

NASA Technical Reports Server (NTRS)

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

2011-01-01

One possible process responsible for methane generation on Mars is abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions. Measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane by tracing the geochemical pathway during formation. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible hydrogen isotope measurements. Reported here are results of experiments to characterize the hydrogen isotope composition of low molecular weight organic acids and alcohols. The presence of these organic compounds has been suggested by others as intermeadiary products made during mineral surface catalyzed reactions. This work compliments our previous study characterizing the carbon isotope composition of similar low molecular weight intermediary organic compounds (Socki, et al, American Geophysical Union Fall meeting, Abstr. #V51B-2189, Dec., 2010). Our hydrogen isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). Our technique is unique in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II? quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Characterization of dicarboxylic naphthenic acid fraction compounds utilizing amide derivatization: Proof of concept.

PubMed

Kovalchik, Kevin A; MacLennan, Matthew S; Peru, Kerry M; Ajaero, Chukwuemeka; McMartin, Dena W; Headley, John V; Chen, David D Y

2017-12-30

The characterization of naphthenic acid fraction compounds (NAFCs) in oil sands process affected water (OSPW) is of interest for both toxicology studies and regulatory reasons. Previous studies utilizing authentic standards have identified dicarboxylic naphthenic acids using two-dimensional gas chromatography hyphenated to time-of-flight mass spectrometry (GC × GC/TOFMS). The selective derivatization of hydroxyl groups has also recently aided in the characterization of oxy-NAFCs, and indirectly the characterization of dicarboxylic NAFCs. However, there has been no previous report of derivatization being used to directly aid in the standard-free characterization of NAFCs with multiple carboxylic acid functional groups. Herein we present proof-of-concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization. Carboxylic acid groups in OSPW extract and in a dicarboxylic acidstandard were derivatized to amides using a previously described method. The derivatized extract and derivatized standard were analyzed by direct-injection positive-mode electrospray ionization ((+)ESI) high-resolution mass spectrometry (HRMS), and the underivatized extract was analyzed by (-)ESI MS. Tandem mass spectrometry (MS/MS) was carried out on selected ions of the derivatized standard and derivatized OSPW. Data analysis was carried out using the Python programming language. The distribution of monocarboxylic NAFCs observed in the amide-derivatized OSPW sample by (+)ESI-MS was generally similar to that seen in underivatized OSPW by (-)ESI-MS. The dicarboxylic acid standard shows evidence of being doubly derivatized, although the second derivatization appears to be inefficient. Furthermore, a spectrum of potential diacid NAFCs is presented, identified by both charge state and derivatization mass. Interference due to the presence of multiple derivatization products is noted, but can be eliminated using on-line separation or an isotopically labelled derivatization reagent. Proof of concept for the characterization of dicarboxylic NAFCs utilizing amide derivatization is demonstrated. Furthermore, (+)ESI-HRMS of the derivatized monocarboxylic NAFCS yields similar information to (-)ESI-MS analysis of underivatized NAFCs, with the benefit of added selectivity for carboxylic acid species and the characterization of diacids. Copyright © 2017 John Wiley & Sons, Ltd.

Metabolomics of Clostridial Biofuel Production

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

Rabinowitz, Joshua D; Aristilde, Ludmilla; Amador-Noguez, Daniel

2015-09-08

Members of the genus Clostridium collectively have the ideal set of the metabolic capabilities for fermentative biofuel production: cellulose degradation, hydrogen production, and solvent excretion. No single organism, however, can effectively convert cellulose into biofuels. Here we developed, using metabolomics and isotope tracers, basic science knowledge of Clostridial metabolism of utility for future efforts to engineer such an organism. In glucose fermentation carried out by the biofuel producer Clostridium acetobutylicum, we observed a remarkably ordered series of metabolite concentration changes as the fermentation progressed from acidogenesis to solventogenesis. In general, high-energy compounds decreased while low-energy species increased during solventogenesis. Thesemore » changes in metabolite concentrations were accompanied by large changes in intracellular metabolic fluxes, with pyruvate directed towards acetyl-CoA and solvents instead of oxaloacetate and amino acids. Thus, the solventogenic transition involves global remodeling of metabolism to redirect resources from biomass production into solvent production. In contrast to C. acetobutylicum, which is an avid fermenter, C. cellulolyticum metabolizes glucose only slowly. We find that glycolytic intermediate concentrations are radically different from fast fermenting organisms. Associated thermodynamic and isotope tracer analysis revealed that the full glycolytic pathway in C. cellulolyticum is reversible. This arises from changes in cofactor utilization for phosphofructokinase and an alternative pathway from phosphoenolpyruvate to pyruvate. The net effect is to increase the high-energy phosphate bond yield of glycolysis by 150% (from 2 to 5) at the expense of lower net flux. Thus, C. cellulolyticum prioritizes glycolytic energy efficiency over speed. Degradation of cellulose results in other sugars in addition to glucose. Simultaneous feeding of stable isotope-labeled glucose and unlabeled pentose sugars (xylose or arabinose) to C. acetobutylicum revealed that, as expected, glucose was preferred, with the pentose sugar selectively assimilated into the pentose phosphate pathway (PPP). Simultaneous feeding of xylose and arabinose revealed an unexpected hierarchy among these pentose sugars, with arabinose utilized preferentially over xylose. Pentose catabolism occurred via the phosphoketolase pathway (PKP), an alternative route of pentose catabolism that directly converts xylulose-5-phosphate into acetyl-phosphate and glyceraldehyde-3-phosphate. Taken collectively, these findings reveal two hierarchies in Clostridial pentose metabolism: xylose is subordinate to arabinose, and the PPP is used less than the PKP. Thus, in addition to massively expanding the available data on Clostridial metabolism, we identified three key regulatory points suitable for targeting in future bioengineering efforts: phosphofructokinase for enhancing fermentation, the pyruvate-oxaloacetate node for controlling solventogenesis, and the phosphoketolase reaction for driving pentose catabolism.« less

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain).

PubMed

Garcia, Nuria; Feranec, Robert S; Passey, Benjamin H; Cerling, Thure E; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors.

Applications of Cavity Ring-Down Spectroscopy (CRDS) to Analysis of Carbon Stable Isotope Composition of Groundwater

NASA Astrophysics Data System (ADS)

Jeong, T.; Woo, N. C.; Choi, H.

2014-12-01

Carbon Capture and Storage (CCS) has been considered as an effective strategy to reduce atmospheric carbon dioxide (CO2) concentration. However, unintended leakage of CO2 leakage from storage sites could occur through highly permeable conduits such as fractures in low-K formations during the injection and storage of SCCO2 (supercritical phase CO2). Therefore, prediction and detection of CO2 leakage and relevant analysis of carbon isotope are crucial to assure environmental and public safety. Until recently, Isotope Ratio Mass Spectrometry (IRMS) has been utilized to measure the stable isotope ratio of water. However, IRMS is time-consuming operation due to complicated pretreatment, and thus not a practical methodology under field conditions. Carbon Isotope Analyzer (CCIA), which is a kind of Cavity Ring-Down Spectroscopy (CRDS) and has a wide measurement range from 300 to 25000 ppmv, can facilitate the rate of measurements up to 1 Hz by using continuous flow method so that it can be readily applied to field. In this study, carbon stable isotope ratio of groundwater will be analyzed using CCIA. Then, the CCIA results will be compared with IRMS to validate its accuracy and stability. This research will provide an appropriate method for analyzing carbon stable isotope in groundwater, using a continuous flow mode.

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

NASA Astrophysics Data System (ADS)

Bauer, A.; Horstwood, M. S.

2016-12-01

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

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

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

PubMed

O'Connell, T C

2017-06-01

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

Characterization of extreme ultraviolet laser ablation mass spectrometry for actinide trace analysis and nanoscale isotopic imaging

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

Green, Tyler; Kuznetsov, Ilya; Willingham, David

The purpose of this research was to characterize Extreme Ultraviolet Time-of-Flight (EUV TOF) Laser Ablation Mass Spectrometry for high spatial resolution elemental and isotopic analysis. We compare EUV TOF results with Secondary Ionization Mass Spectrometry (SIMS) to orient the EUV TOF method within the overall field of analytical mass spectrometry. Using the well-characterized NIST 61x glasses, we show that the EUV ionization approach produces relatively few molecular ion interferences in comparison to TOF SIMS. We demonstrate that the ratio of element ion to element oxide ion is adjustable with EUV laser pulse energy and that the EUV TOF instrument hasmore » a sample utilization efficiency of 0.014%. The EUV TOF system also achieves a lateral resolution of 80 nm and we demonstrate this lateral resolution with isotopic imaging of closely spaced particles or uranium isotopic standard materials.« less

Isotopic fractionation of oxygen and carbon in decomposed lower-mantle inclusions in diamond

DOE PAGES

Kaminsky, Felix; Matzel, Jennifer; Jacobsen, Ben; ...

2015-07-25

Two carbonatitic mineral assemblages, calcite + wollastonite and calcite + monticellite, which are encapsulated in two diamond grains from the Rio Soriso basin in the Juina area, Mato Grosso State, Brazil, were studied utilizing the NanoSIMS technique. The assemblages were formed as the result of the decomposition of the lower-mantle assemblage calcite + CaSi-perovskite + volatile during the course of the diamond ascent under pressure conditions from 15 to less than 0.8 GPa. The oxygen and carbon isotopic compositions of the studied minerals are inhomogeneous. They fractionated during the process of the decomposition of primary minerals to very varying values:more » δ 18O from –3.3 to +15.4 ‰ SMOW and δ 13C from –2.8 to +9.3 ‰ VPDB. As a result, these values significantly extend the mantle values for these elements in both isotopically-light and isotopically-heavy areas.« less

Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump.

PubMed

Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi

2015-04-28

The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Campbell, Keri; Judge, Elizabeth J.; Dirmyer, Matthew R.

Surrogate nuclear explosive debris was synthesized and characterized for major, minor, and trace elemental composition as well as uranium isotopics. The samples consisted of an urban glass matrix, equal masses soda lime and cement, doped with 500 ppm uranium with varying enrichments. The surface and cross section morphology were measured with SEM, and the major elemental composition was determined by XPS. LA-ICP-MS was used to measure the uranium isotopic abundance comparing different sampling techniques. Furthermore, the results provide an example of the utility of LA-ICP-MS for forensics applications.

Stable carbon isotope fractionation in the search for life on early Mars

NASA Technical Reports Server (NTRS)

Rothschild, L. J.; Desmarais, D.

1989-01-01

The utility of measurements of C-13/C-12 ratios in organic vs inorganic deposits for searching for signs of life on early Mars is considered. It is suggested that three assumptions are necessary. First, if there was life on Mars, it caused the fractionation of carbon isotopes in analogy with past biological activity on earth. Second, the fractionation would be detectable. Third, if a fractionation would be observed, there exist no abiotic explanations for the observed fractionation pattern.

Data Reduction of Laser Ablation Split-Stream (LASS) Analyses Using Newly Developed Features Within Iolite: With Applications to Lu-Hf + U-Pb in Detrital Zircon and Sm-Nd +U-Pb in Igneous Monazite

NASA Astrophysics Data System (ADS)

Fisher, Christopher M.; Paton, Chad; Pearson, D. Graham; Sarkar, Chiranjeeb; Luo, Yan; Tersmette, Daniel B.; Chacko, Thomas

2017-12-01

A robust platform to view and integrate multiple data sets collected simultaneously is required to realize the utility and potential of the Laser Ablation Split-Stream (LASS) method. This capability, until now, has been unavailable and practitioners have had to laboriously process each data set separately, making it challenging to take full advantage of the benefits of LASS. We describe a new program for handling multiple mass spectrometric data sets collected simultaneously, designed specifically for the LASS technique, by which a laser aerosol is been split into two or more separate "streams" to be measured on separate mass spectrometers. New features within Iolite (https://iolite-software.com) enable the capability of loading, synchronizing, viewing, and reducing two or more data sets acquired simultaneously, as multiple DRSs (data reduction schemes) can be run concurrently. While this version of Iolite accommodates any combination of simultaneously collected mass spectrometer data, we demonstrate the utility using case studies where U-Pb and Lu-Hf isotope composition of zircon, and U-Pb and Sm-Nd isotope composition of monazite were analyzed simultaneously, in crystals showing complex isotopic zonation. These studies demonstrate the importance of being able to view and integrate simultaneously acquired data sets, especially for samples with complicated zoning and decoupled isotope systematics, in order to extract accurate and geologically meaningful isotopic and compositional data. This contribution provides instructions and examples for handling simultaneously collected laser ablation data. An instructional video is also provided. The updated Iolite software will help to fully develop the applications of both LASS and multi-instrument mass spectrometric measurement capabilities.

On the cross-sensitivity between water vapor mixing ratio and stable isotope measurements of in-situ analyzers

NASA Astrophysics Data System (ADS)

Parkes, Stephen; Wang, Lixin; McCabe, Matthew

2015-04-01

In recent years there has been an increasing amount of water vapor stable isotope data collected using in-situ instrumentation. A number of papers have characterized the performance of these in-situ analyzers and suggested methods for calibrating raw measurements. The cross-sensitivity of the isotopic measurements on the mixing ratio has been shown to be a major uncertainty and a variety of techniques have been suggested to characterize this inaccuracy. However, most of these are based on relating isotopic ratios to water vapor mixing ratios from in-situ analyzers when the mixing ratio is varied and the isotopic composition kept constant. An additional correction for the span of the isotopic ratio scale is then applied by measuring different isotopic standards. Here we argue that the water vapor cross-sensitivity arises from different instrument responses (span and offset) of the parent H2O isotope and the heavier isotopes, rather than spectral overlap that could cause a true variation in the isotopic ratio with mixing ratio. This is especially relevant for commercial laser optical instruments where absorption lines are well resolved. Thus, the cross-sensitivity determined using more conventional techniques is dependent on the isotopic ratio of the standard used for the characterization, although errors are expected to be small. Consequently, the cross-sensitivity should be determined by characterizing the span and zero offset of each isotope mixing ratio. In fact, this technique makes the span correction for the isotopic ratio redundant. In this work we model the impact of changes in the span and offset of the heavy and light isotopes and illustrate the impact on the cross-sensitivity of the isotopic ratios on water vapor. This clearly shows the importance of determining the zero offset for the two isotopes. The cross-sensitivity of the isotopic ratios on water vapor is then characterized by determining the instrument response for the individual isotopes for a number of different in-situ analyzers that employ different optical methods. We compare this simplified calibration technique to more conventional characterization of both the cross-sensitivity determined in isotopic ratio space and the isotopic ratio span. Utilizing this simplified calibration approach with improved software control can lead to a significant reduction in time spent calibrating in-situ instrumentation or enable an increase in calibration frequency as required to minimize measurement uncertainty.

Relationships between mercury concentration and food selectivity of many kinds of fishes in Minamata Bay

NASA Astrophysics Data System (ADS)

Mori, K.; Kanaya, G.

2016-02-01

Serious injuries occurred in residents who consumed fish and shellfishes in Minamata Bay polluted by high-concentration methyl-mercury in the 1950s. Pollution has fallen to a safe level because of the pollution prevention project (dredging etc.) carried out from 1977 to 1990. From 2010 we have been researching the bioaccumulation of mercury in several fishes in Minamata Bay and surrounding areas. We selected several sampling points that showed different environmental conditions, species composition and food web patterns. For the determination of feeding types of 60 species fishes (600 samples) sampled by gill net, we measured mercury levels of each sample and directly checked food items in gut, and distinguished carnivore, omnivore, herbivore and detritivore. At this time, we introduced a stable isotope analysis for checking the food history and feeding habits of dominant fish. In about 300 individuals of 30 species of dominant fish selected from the 600 samples, we measured the stable nitrogen and carbon isotope ratios (δ15N, δ13C) of each sample. Checking the food items in gut of fishes, more than 80% of fishes were carnivorous, and showed different selectivity of food items, such as fish, crustacean and so on. From the results of stable isotope ratios, benthic fish tended to show a higher ratio of δ13C. Usually benthic microalgae evidenced a higher ratio of δ13C than planktonic microalgae, and the ratio conservative through the food chain. In general, δ15N increases through the food chain with +3 to +4 ‰ enrichment per trophic step. In these data, carnivorous fishes of benthic and pelagic type showed medium and high ratios of δ15N. From comparing the stable isotope ratio to the mercury concentration of fishes, all of the high-mercury fishes belonged to benthic and carnivorous types. We consider the joint method of food web analysis and stable isotope analysis to be useful for understanding the mechanism of mercury bioaccumulation through the food web

Power considerations for an early manned Mars mission utilizing the space station

NASA Technical Reports Server (NTRS)

Valgora, Martin E.

1987-01-01

Power requirements and candidate electrical power sources were examined for the supporting space infrastructure for an early (2004) manned Mars mission. This two-year mission (60-day stay time) assumed a single six crew piloted vehicle with a Mars lander for four of the crew. The transportation vehicle was assumed to be a hydrogen/oxygen propulsion design with or without large aerobrakes and assembled and checked out on the LEO Space Station. The long transit time necessitated artificial gravity of the crew by rotating the crew compartments. This rotation complicates power source selection. Candidate power sources were examined for the Lander, Mars Orbiter, supporting Space Station, co-orbiting Propellant Storage Depot, and alternatively, a co-orbiting Propellant Generation (water electrolysis) Depot. Candidates considered were photovoltaics with regenerative fuel cells or batteries, solar dynamics, isotope dynamics, and nuclear power.

Radiogenic Isotopes in Weathering and Hydrology

NASA Astrophysics Data System (ADS)

Blum, J. D.; Erel, Y.

2003-12-01

There are a small group of elements that display variations in their isotopic composition, resulting from radioactive decay within minerals over geological timescales. These isotopic variations provide natural fingerprints of rock-water interactions and have been widely utilized in studies of weathering and hydrology. The isotopic systems that have been applied in such studies are dictated by the limited number of radioactive parent-daughter nuclide pairs with half-lives and isotopic abundances that result in measurable differences in daughter isotope ratios among common rocks and minerals. Prior to their application to studies of weathering and hydrology, each of these isotopic systems was utilized in geochronology and petrology. As in the case of their original introduction into geochronology and petrology, isotopic systems with the highest concentrations of daughter isotopes in common rocks and minerals and systems with the largest observed isotopic variations were introduced first and have made the largest impact on our understanding of weathering and hydrologic processes. Although radiogenic isotopes have helped elucidate many important aspects of weathering and hydrology, it is important to note that in almost every case that will be discussed in this chapter, our fundamental understanding of these topics came from studies of variations in the concentrations of major cations and anions. This chapter is a "tools chapter" and thus it will highlight applications of radiogenic isotopes that have added additional insight into a wide spectrum of research areas that are summarized in almost all of the other chapters of this volume.The first applications of radiogenic isotopes to weathering processes were based on studies that sought to understand the effects of chemical weathering on the geochronology of whole-rock samples and geochronologically important minerals (Goldich and Gast, 1966; Dasch, 1969; Blaxland, 1974; Clauer, 1979, 1981; Clauer et al., 1982); as well as on the observation that radiogenic isotopes are sometimes preferentially released compared to nonradiogenic isotopes of the same element during acid leaching of rocks ( Hart and Tilton, 1966; Silver et al., 1984; Erel et al., 1991). A major finding of these investigations was that weathering often results in anomalously young Rb-Sr isochron ages, and discordant Pb-Pb ages. Rubidium is generally retained relative to strontium in whole-rock samples, and in some cases radiogenic strontium and lead are lost preferentially to common strontium and lead from weathered minerals.The most widely utilized of these isotopic systems is Rb-Sr, followed by U-Pb. The K-Ar system is not directly applicable to most studies of rock-water interaction, because argon is a noble gas, and upon release during mineral weathering mixes with atmospheric argon, limiting its usefulness as a tracer in most weathering applications. Argon and other noble gas isotopes have, however, found important applications in hydrology (see Chapter 5.15). Three other isotopic systems commonly used in geochronology and petrology include Sm-Nd, Lu-Hf, and Re-Os. These parent and daughter elements are in very low abundance and concentrated in trace mineral phases. Sm-Nd, Lu-Hf, and Re-Os have been used in a few weathering studies but have not been utilized extensively in investigations of weathering and hydrology.The decay of 87Rb to 87Sr has a half-life of 48.8 Gyr, and this radioactive decay results in natural variability in the 87Sr/86Sr ratio in rubidium-bearing minerals (e.g., Blum, 1995). The trace elements rubidium and strontium are geochemically similar to the major elements potassium and calcium, respectively. Therefore, minerals with high K/Ca ratios develop high 87Sr/86Sr ratios over geologic timescales. Once released into the hydrosphere, strontium retains its isotopic composition without significant fractionation by geochemical or biological processes, and is therefore a good tracer for sources and cycling of calcium. The decay of 235U to 207Pb, 238U to 206Pb, and 232Th to 208Pb have half-lives of 0.704 Gyr, 4.47 Gyr, and 14.0 Gyr, respectively, and result in variations in the 207Pb/204Pb, 206Pb/204Pb, and 208Pb/204Pb ratios (e.g., Blum, 1995). Uranium-234 has a half-life of 0.25 Myr and the ratio 234U/238U approaches a constant secular equilibrium value in rocks and minerals if undisturbed for ˜1 Myr. Differences in this ratio are often observed in solutions following rock-water interaction and have been used in studies of weathering and hydrology. Uranium and thorium tend to be highly concentrated in the trace accessory minerals such as zircon, monazite, apatite, and sphene, which therefore develop high 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios. Once released into the hydrosphere, lead retains its isotopic composition without significant geochemical or biological fractionation and tends to generally follow the chemistry of iron in soils and aqueous systems (Erel and Morgan, 1992). The use of the U-Th disequilibrium series as a dating tool falls outside the scope of this chapter and is reviewed in Chapters 6.14 and 6.17 as well as Chapter 3.15. The decay of 147Sm to 143Nd, 176Lu to 176Hf, and 187Re to 187Os have half-lives of 106 Gyr, 35.7 Gyr, and 42.3 Gyr, respectively, and result in natural variability in the 144Nd/143Nd, 176Hf/177Hf, and 187Os/188Os ratios (e.g., Blum, 1995). Neodymium is a rare earth element (REE), hafnium is a transition metal with chemical similarities to zirconium, and osmium is a platinum group element. The geochemical behaviors of these elements in the hydrosphere are largely determined by these chemical affinities.

Calcium isotope analysis by mass spectrometry.

PubMed

Boulyga, Sergei F

2010-01-01

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. 2009 Wiley Periodicals, Inc.

High mass accuracy assay for trimethylamine N-oxide using stable-isotope dilution with liquid chromatography coupled to orthogonal acceleration time of flight mass spectrometry with multiple reaction monitoring.

PubMed

Heaney, Liam M; Jones, Donald J L; Mbasu, Richard J; Ng, Leong L; Suzuki, Toru

2016-01-01

Trimethylamine N-oxide (TMAO) has attracted interest as circulating levels have reported prognostic value in patients with cardiovascular conditions, such as heart failure. With continual advances in accurate mass measurements, robust methods that can employ the capabilities of time of flight mass spectrometers would offer additional utility in the analysis of complex clinical samples. A Waters Acquity UPLC was coupled to a Waters Synapt G2-S high-resolution mass spectrometer. TMAO was measured in plasma by stable-isotope dilution-hydrophilic interaction liquid chromatography-time of flight mass spectrometry with multiple reaction monitoring (LC-ToF-MRM). Two transitions were monitored: m/z 76.1 to 58.066/59.073 and m/z 85.1 to 66.116/68.130. The method was assessed for linearity, lower limits of detection and quantitation, and reproducibility. A selected cohort of patients with systolic heart failure (SHF; n = 43) and healthy controls (n = 42) were measured to verify the assay is suitable for the analysis of clinical samples. Quantitative analysis of TMAO using LC-ToF-MRM enabled linearity to be established between 0.1 and 75 μmol/L, with a lower limit of detection of 0.05 μmol/L. Relative standard deviations reported an inter-day variation of ≤20.8% and an intra-day variation of ≤11.4% with an intra-study quality control variation of 2.7%. Run times were 2.5 min. Clinical application of the method reported that TMAO in SHF was elevated compared to that of healthy controls (p < 0.0005). LC-ToF-MRM offers a highly selective method for accurate mass measurement of TMAO with rapid and reproducible results. Applicability of the method was shown in a selected cohort of patient samples.

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

VELOCITY SELECTOR METHOD FOR THE SEPARATION OF ISOTOPES

DOEpatents

Britten, R.J.

1957-12-31

A velocity selector apparatus is described for separating and collecting an enriched fraction of the isotope of a particular element. The invention has the advantage over conventional mass spectrometers in that a magnetic field is not used, doing away with the attendant problems of magnetic field variation. The apparatus separates the isotopes by selectively accelerating the ionized constituents present in a beam of the polyisotopic substance that are of uniform kinetic energy, the acceleration being applied intermittently and at spaced points along the beam and in a direction normal to the direction of the propagation of the uniform energy beam whereby a transverse displacement of the isotopic constituents of different mass is obtained.

Primary Data on U/Pb-Isotope Ages and Lu/Hf-Isotope Geochemical Systematization of Detrital Zircons from the Lopatinskii Formation (Vendian-Cambrian Transition Levels) and the Tectonic Nature of Teya-Chapa Depression (Northeastern Yenisei Ridge)

NASA Astrophysics Data System (ADS)

Kuznetsov, N. B.; Priyatkina, N. S.; Rud'ko, S. V.; Shatsillo, A. V.; Collins, W. J.; Romanyuk, T. V.

2018-03-01

The main results are presented on U/Pb-isotope dating of 100 detrital zircons and, selectively, on the Lu/Hf-isotope system of 43 grains from sandstones of the Lopatinskii formation (the lower stratigraphic level of the Chingasan group). Ages from 896 ± 51 to 2925 ± 38 Ma were obtained with a pronounced maximum of 1890 Ma in the curve of probability density, along with ɛHf estimates from +8.4 to-15.1, which allow one to throw doubt upon the molasse nature of the Lopatinskii formation.

In-Situ Geochronology: Extending Larims to Pb-Pb Isocrhons

NASA Astrophysics Data System (ADS)

Whitaker, Tom; Anderson, Scott; Levine, Jonathan

2016-04-01

Introduction: We have previously described development of Laser Ablation Resonance Ionization Mass Spectrometry (LARIMS) for in-situ determination of the radiometric age of rocks using isotope ratios of Rb and Sr [1,2]. LARIMS uses laser resonance excitation of the target elements, which provides elemental selectivity, thus eliminating isobaric interferences with little or no sample preparation and allowing thousands of samples to be measured in significantly shorter periods of time than traditional methods. We have recently begun research that aims to extend the Rb-Sr capability to include Pb-Pb measurements. Preliminary measurements of Standard Reference Material 612 (SRM-612) from the National Institute of Standards and Technology (NIST) demonstrate that resonance ionization of Pb can measure samples with as little as 0.12 ppm total Pb. Background: In-situ LARIMS will enable measurements of 1) isotope geochemistry relevant for chronology and igneous evolution, 2) light isotopes relevant for habitability, life, and climate history, as well as 3) elemental abundances relevant to understanding local and regional geology. In particular, the elemental selectivity of LARIMS makes isotopic geochronology measurements possible that heretofore required extensive sample preparation and were thought to be practically impossible for in-situ measurements. For example, we have used Rb-Sr LARIMS to analyze a piece of the Martian meteorite Zagami and the Duluth Gabbro, a lunar analogue. In these measurements, we obtained isochron ages consistent with the published ages within 200 Ma. Pb-Pb geochronology is well-suited for LARIMS analysis. The use of a single element simplifies the laser system and eliminates inter-element fractionation that can be problematic in Rb-Sr analysis or other multi-element LARIMS measurements. In general, there is less interference at masses corresponding to Pb isotopes than at lighter masses. However, there are potential interferences such as Hg and HfO2, which have been known to cause problems in Inductively Coupled Plasma Mass Spectrometry (ICPMS) of Pb isotopes [3]. LARIMS enables a simple check for interfering species by detuning the laser wavelength off the Pb resonance. The resonance ionization signal for the desired species should disappear when the resonance laser is detuned. Any residual signal is due to an interfering species. Three resonance ionization laser schemes were examined for initial LARIMS analysis of Pb: 1) a 2+1 scheme that uses λ1 = λ2 = 450.3 nm (the first transition in this scheme is a simultaneous two-photon excitation), 2) a 1+1+1 scheme using λ1 = 283.3 nm, λ2 = 600.2 nm and λ3 < 1270 nm, and 3) a 1+1 scheme that uses λ1 = λ2 = 283.3 nm. One-photon resonance excitations have cross-sections that are orders of magnitude greater than either two-photon resonance excitations or photoionization processes. Therefore, although schemes 1) and 3) have the advantage of requiring fewer lasers, they also require high-intensity blue or UV wavelengths. This adversely affects the selectivity of the resonance ionization process. Scheme 2) uses low-intensity UV and visible wavelengths and a high-intensity IR wavelength. This is the preferred scheme and was selected for our initial Pb LARIMS measurements. Preliminary Results: A laser system capable of producing the required wavelengths for scheme 2) was assembled. A Nd:YAG laser pumped dye laser produces 566.6 nm light, which is frequency-doubled in a beta barium borate crystal. A second Nd:YAG pumped dye laser produces the 600.2 nm light for the second resonance in scheme 2). The fundamental of one of the Nd:YAG lasers (1064 nm) is used for the final photoionization step. We focus the fifth harmonic (213 nm) of another Nd:YAG laser onto the sample to ablate material off the surface. Electric fields suppress the ions created in the ablation process, preventing these ions from entering the mass spectrometer. The three resonance ionization laser lasers spatially overlap the ablated plume about 1 mm off the surface. These three resonance ionization wavelengths are synchronized in time with each other but delayed with respect to the ablation laser pulse. For Pb, the resonance ionization signal peaks at about 9 μsec delay. The electric field that initially suppressed ablated ions is reversed before the resonance lasers are fired, thus extracting the ions selectively created by resonance ionization into a multi-bounce time-of-flight mass spectrometer (MBTOF-MS). The MBTOF-MS separates the isotopes in time, allowing analysis of isotope ratios. We have used this technique to analyze NIST SRM-612, a glass wafer containing 38.57 ppm Pb along with a number of other constituents. The mass spectrum shows all of the Pb isotopes, with the even isotopes in the expected ratios. However, we have found that the Pb-207 peak height is very sensitive to the exact wavelength of the 600.2 nm light used for the second excitation. The height of this odd isotope can be significantly modified with minute changes in the 600.2 nm wavelength that don't affect the peak heights of the even isotopes. This is due to the well-known odd-even isotope anomaly in resonance ionization. Because of the sensitivity of the Pb-207 peak to the exact wavelength, a standard with known Pb isotope ratios is analyzed frequently to allow calibration of the isotope ratios. In very preliminary LARIMS spectra obtained for SRM-612, the measured Pb-208 signal-to-baseline noise is over 600:1. This corresponds to a minimum detection limit of 0.12 ppm total Pb. We anticipate improving the signal-to-noise with optimization of TOF voltages and ablation laser intensity. Future Work: We are in the process of measuring an isochron for a sample of Duluth Gabbro and anticipate having results available for the conference. We are also exploring the use of fiber lasers for LARIMS analyses of Pb. Fiber lasers are small, lightweight, and extremely robust, making them ideal for space missions. We are presently developing fiber lasers for our Rb-Sr LARIMS work and we have investigated ways to efficiently combine wavelengths from Er-, Yb-, and Tm-doped fibers to generate both the 283.3 nm wavelength and 600.2 nm wavelength needed for Pb LARIMS. Concepts utilizing wavelengths readily generated in these fibers have been developed. References: F.S. Anderson, J. Levine, and T.J. Whitaker, Rapid Comm. in Mass Spect., 2015, 29, 191-204. F.S. Anderson, J. Levine, T.J. Whitaker, Rapid Comm. in Mass Spect., 2015, 29, 1457-1464. R.W. Hinton and J V Long, Earth Planet. Sci. Lett 1979, 45, 309-325.

Heterodyne laser spectroscopy system

DOEpatents

Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

1990-01-01

A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency, and provides spectral analysis of a laser beam.

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, Jr., Henry D.

1993-01-01

A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Strategy for the elucidation of elemental compositions of trace analytes based on a mass resolution of 100,000 full width at half maximum.

PubMed

Kaufmann, Anton

2010-07-30

Elemental compositions (ECs) can be elucidated by evaluating the high-resolution mass spectra of unknown or suspected unfragmented analyte ions. Classical approaches utilize the exact mass of the monoisotopic peak (M + 0) and the relative abundance of isotope peaks (M + 1 and M + 2). The availability of high-resolution instruments like the Orbitrap currently permits mass resolutions up to 100,000 full width at half maximum. This not only allows the determination of relative isotopic abundances (RIAs), but also the extraction of other diagnostic information from the spectra, such as fully resolved signals originating from (34)S isotopes and fully or partially resolved signals related to (15)N isotopes (isotopic fine structure). Fully and partially resolved peaks can be evaluated by visual inspection of the measured peak profiles. This approach is shown to be capable of correctly discarding many of the EC candidates which were proposed by commercial EC calculating algorithms. Using this intuitive strategy significantly extends the upper mass range for the successful elucidation of ECs. Copyright 2010 John Wiley & Sons, Ltd.

APPARATUS AND TECHNIC FOR THE ADMINISTRATION OF INTRACAVITARY RADIOACTIVE ISOTOPES

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

Michaud, N.J.; Liegner, L.M.

1961-08-01

The method of administration of radioactive isotopes in the treatment of pleural effusions and ascites associated with cancer will vary according to the therapeutic technic. A procedure with a suitable apparatus that utilizes an economical and sterile disposable package is described. The radioactive isotope, whether colloidal chromic phosphate (P/sup 32/) or colloidal gold (Au/sup 198/), can be obtained in th e exact amount prescribed. The entire apparatus is assembled within a few minutes under sterile conditions. Before the hypodermic needles are inserted into the radioactive isotope vial, the air is removed from the tubing by the flow of saline inmore » each segment. Each section is then clamped. The shielded radioactive isotope is then placed on a table or stand and the rubber seal of the vial is swabbed with alcohol or iodine. The inflow needle is inserted just through the rubber stopper and the outflow needle is inserted to the bottom of the vial. This procedure is carried out without removing the vial from the lead container. (auth)« less

Development of a Method to Isolate Glutamic Acid from Foodstuffs for a Precise Determination of Their Stable Carbon Isotope Ratio.

PubMed

Kobayashi, Kazuhiro; Tanaka, Masaharu; Yatsukawa, Yoichi; Tanabe, Soichi; Tanaka, Mitsuru; Ohkouchi, Naohiko

2018-01-01

Recent growing health awareness is leading to increasingly conscious decisions by consumers regarding the production and traceability of food. Stable isotopic compositions provide useful information for tracing the origin of foodstuffs and processes of food production. Plants exhibit different ratios of stable carbon isotopes (δ 13 C) because they utilized different photosynthetic (carbon fixation) pathways and grow in various environments. The origins of glutamic acid in foodstuffs can be differentiated on the basis of these photosynthetic characteristics. Here, we have developed a method to isolate glutamic acid in foodstuffs for determining the δ 13 C value by elemental analyzer-isotope-ratio mass spectrometry (EA/IRMS) without unintended isotopic fractionation. Briefly, following acid-hydrolysis, samples were defatted and passed through activated carbon and a cation-exchange column. Then, glutamic acid was isolated using preparative HPLC. This method is applicable to measuring, with a low standard deviation, the δ 13 C values of glutamic acid from foodstuffs derived from C3 and C4 plants and marine algae.

The use of lead isotope analysis to identify potential sources of lead toxicosis in a juvenile bald eagle (Haliaeetus leucocephalus) with ventricular foreign bodies

USGS Publications Warehouse

Franzen-Klein, Dana; McRuer, David; Slabe, Vincent; Katzner, Todd

2018-01-01

A male juvenile bald eagle (Haliaeetus leucocephalus) was admitted to the Wildlife Center of Virginia with a left humeral fracture a large quantity of anthropogenic debris in the ventriculus, a blood lead level of 0.616 ppm, and clinical signs consistent with chronic lead toxicosis. Because of the poor prognosis for recovery and release, the eagle was euthanatized. Lead isotope analysis was performed to identify potential anthropogenic sources of lead in this bird. The lead isotope ratios in the eagle's femur (0.8773), liver (0.8761), and kidneys (0.8686) were most closely related to lead paint (0.8925), leaded gasoline (0.8450), and zinc smelting (0.8240). The lead isotope ratios were dissimilar to lead ammunition (0.8179) and the anthropogenic debris in the ventriculus. This case report documents foreign body ingestion in a free-ranging bald eagle and demonstrates the clinical utility of lead isotope analysis to potentially identify or exclude anthropogenic sources of lead poisoning in wildlife patients.

Lead isotopes in iron and manganese oxide coatings and their use as an exploration guide for concealed mineralization

USGS Publications Warehouse

Gulson, B.L.; Church, S.E.; Mizon, K.J.; Meier, A.L.

1992-01-01

Lead isotopes from Fe and Mn oxides that coat stream pebbles from around the Mount Emmons porphyry molybdenum deposit in Colorado were studied to assess the feasibility of using Pb isotopes to detect concealed mineral deposits. The Fe/Mn oxide coatings were analyzed to determine their elemental concentrations using ICP-AES. The Pb isotope compositions of solutions from a selected suite of samples were measured, using both thermal ionization and ICP mass spectrometry, to compare results determined by the two analytical methods. Heavy mineral concentrates from the same sites were also analyzed to compare the Pb isotope compositions of the Fe/Mn coatings with those found in panned concentrates. The Fe/Mn and 206Pb/204Pb ratios of the oxide coatings are related to the lithology of the host rocks; Fe/Mn oxide coatings on pebbles of black shale have higher Fe/Mn values than do the coatings on either sandstone or igneous rocks. The shale host rocks have a more radiogenic signature (e.g. higher 206Pb/ 204Pb) than the sandstone or igneous host rocks. The Pb isotope data from sandstone and igneous hosts can detect concealed mineralized rock on both a regional and local scale, even though there are contributions from: (1) metals from the main-stage molybdenite ore deposit; (2) metals from the phyllic alteration zone which has a more radiogenic Pb isotope signature reflecting hydrothermal leaching of Pb from the Mancos Shale; (3) Pb-rich base metal veins with a highly variable Pb isotope signature; and (4) sedimentary country rocks which have a more radiogenic Pb isotope signature. An investigation of within-stream variation shows that the Pb isotope signature of the molybdenite ore zone is retained in the Fe/Mn oxide coatings and is not camouflaged by contributions from Pb-rich base-metal veins that crop out upstream. In another traverse, the Pb isotope data from Fe/Mn oxide coatings reflect a complex mixing of Pb from the molybdenite ore zone and its hornfels margin, Pb-rich base-metal veins, and sedimentary country rocks. Stream-sediment anomalies detected using oxalic acid leaches can be evaluated using Pb isotope analysesof selected geochemical anomalies. Such an evaluation procedure, given regional target Pb isotope signatures for concealed mineralization, can greatly reduce the cost of exploration for undiscovered ore deposits concealed beneath barren overburden. Lead isotope measurements on aliquots of the same solutions showed that ICP-MS determinations are of low precision and vary non-systematically when compared with the Pb isotope values of the higher precision thermal ionization method. These variations and lower precision of the ICP-MS measurements are attributed to matrix effects. ?? 1992.

Gadolinium photoionization process

DOEpatents

Paisner, J.A.; Comaskey, B.J.; Haynam, C.A.; Eggert, J.H.

1993-04-13

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

Gadolinium photoionization process

DOEpatents

Paisner, Jeffrey A.; Comaskey, Brian J.; Haynam, Christopher A.; Eggert, Jon H.

1993-01-01

A method is provided for selective photoionization of the odd-numbered atomic mass gadolinium isotopes 155 and 157. The selective photoionization is accomplished by circular or linear parallel polarized laser beam energy effecting a three-step photoionization pathway.

Evaporation loss and evaporation/transpiration partitioning from isotope-based monitoring of Canada's provincial and national river networks

NASA Astrophysics Data System (ADS)

Gibson, J. J.; Birks, S. J.; Stadnyk, T.; Delavau, C. J.

2017-12-01

Stable isotopes of water have been measured since the 1990's as part of hydrometric monitoring programs within Canada's Water Survey of Canada gauging network and Alberta's Long-Term River Network. These datasets are being applied for hydrograph separation of streamflow sources, including rain, snow, groundwater, and surface water, as well as for estimation of watershed evaporation losses and evaporation/transpiration partitioning. Here we describe an innovative isotope mass balance approach, discuss benefits and limitations of the method, and present selected results that illustrate important regional trends in the contemporary hydrology of Canada. Overall, isotopes are shown to be useful for constraining water balance variations across regions with low monitoring density. Recommendations for future activities are identified, including regional comparisons with outputs from isotope-capable distributed hydrologic models.

Fishing for isotopes in the Brookhaven Lab Isotope Producer (BLIP) cooling water

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

Fitzsimmons, Jonathan

Be-7 has been used in environmental studies; the isotope is produced during BLIP irradiations and accumulates in the 320 gallons of cooling water. Be-7 has a 53.24 day half-life, so the optimal production/purification time is at the end of the BLIP run season. To purify Be-7 fifteen to twenty gallons of BLIP cooling water are removed and pumped through ion exchange columns that retain Be-7. This labor intensive approach captures ~15 mCi of Be-7, but the solution requires further purification. The method can lead to increased radiation exposure to staff. The ideal way to capture isotopes from large volumes ismore » to reach in to the solution and selectively pull out the desired isotope. It is a lot like fishing.« less

Stable isotope composition of cocoa beans of different geographical origin.

PubMed

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

2016-09-01

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

Determination of 241Am in sediments by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS).

PubMed

Agarande, M; Benzoubir, S; Bouisset, P; Calmet, D

2001-08-01

Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry.

Carbon isotope ratios of human tooth enamel record the evidence of terrestrial resource consumption during the Jomon period, Japan.

PubMed

Kusaka, Soichiro; Uno, Kevin T; Nakano, Takanori; Nakatsukasa, Masato; Cerling, Thure E

2015-08-17

Archaeological remains strongly suggest that the Holocene Japanese hunter-gatherers, the Jomon people, utilized terrestrial plants as their primary food source. However, carbon and nitrogen isotope analysis of bone collagen indicates that they primarily exploited marine resources. We hypothesize that this inconsistency stems from the route of protein synthesis and the different proportions of protein-derived carbon in tooth enamel versus bone collagen. Carbon isotope ratios from bone collagen reflect that of dietary protein and may provide a biased signal of diet, whereas isotope ratios from tooth enamel reflect the integrated diet from all macronutrients (carbohydrates, lipids, and proteins). In order to evaluate the differences in inferred diet between the archaeological evidence and bone collagen isotope data, this study investigated carbon isotopes in Jomon tooth enamel from four coastal sites of the Middle to Late-Final Jomon period (5,000-2,300 years BP). Carbon isotope ratios of human teeth are as depleted as coeval terrestrial mammals, suggesting that C 3 plants and terrestrial mammals were major dietary resources for the Jomon people. Dietary dependence on marine resources calculated from enamel was significantly lower than that calculated from bone collagen. The discrepancy in isotopic ratios between enamel and collagen and the nitrogen isotope ratio in collagen shows a negative correlation on individual and population levels, suggesting diets with variable proportions of terrestrial and marine resources. This study highlights the usefulness of coupling tooth enamel and bone collagen in carbon isotopic studies to reconstruct prehistoric human diet. Am J Phys Anthropol, 2015. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Effects of growth and dissolution on the fractionation of silicon isotopes by estuarine diatoms

NASA Astrophysics Data System (ADS)

Sun, Xiaole; Olofsson, Martin; Andersson, Per S.; Fry, Brian; Legrand, Catherine; Humborg, Christoph; Mörth, Carl-Magnus

2014-04-01

Studies of silicon (Si) isotope fractionation during diatom growth in open ocean systems have documented lower Si isotopic values (δ30Si) in the biogenic silica of diatom frustules compared to dissolved silicon. Recent findings also indicate that Si isotope fractionation occurs during dissolution of diatom frustules, producing higher δ30Si values in the remaining biogenic silica. This study focuses on diatoms from high production areas in estuarine and coastal areas that represent approximately 30-50% of the global marine primary production. Two species of diatoms, Thalassiosira baltica and Skeletonema marinoi, were isolated from the brackish Baltic Sea, one of the largest estuarine systems in the world. These species were used for laboratory investigations of Si isotope fractionation during diatom growth and the subsequent dissolution of the diatom frustules. Both species of diatoms give an identical Si isotope fractionation factor during growth of -1.50 ± 0.36‰ (2σ) for 30Si, which falls in the range of -2.09‰ to -0.55‰ of published data. Our results also suggest a dissolution-induced Si isotope fractionation factor of -0.86‰ at early stage of dissolution, but this effect was observed only in DSi and no significant Si isotope change was observed for BSi. The growth and dissolution results are applied to a Baltic Sea sediment core to reconstruct DSi utilization by diatoms, and found to be in agreement with the observed DSi uptake rates in the overlying water column during diatom growth.

Stable isotope labeling by essential nutrients in cell culture for preparation of labeled coenzyme A and its thioesters.

PubMed

Basu, Sankha S; Mesaros, Clementina; Gelhaus, Stacy L; Blair, Ian A

2011-02-15

Stable isotope dilution mass spectrometry (MS) represents the gold standard for quantification of endogenously formed cellular metabolites. Although coenzyme A (CoA) and acyl-CoA thioester derivatives are central players in numerous metabolic pathways, the lack of a commercially available isotopically labeled CoA limits the development of rigorous MS-based methods. In this study, we adapted stable isotope labeling by amino acids in cell culture (SILAC) methodology to biosynthetically generate stable isotope labeled CoA and thioester analogues for use as internal standards in liquid chromatography/multiple reaction monitoring mass spectrometry (LC/MRM-MS) assays. This was accomplished by incubating murine hepatocytes (Hepa 1c1c7) in media in which pantothenate (a precursor of CoA) was replaced with [(13)C(3)(15)N(1)]-pantothenate. Efficient incorporation into various CoA species was optimized to >99% [(13)C(3)(15)N(1)]-pantothenate after three passages of the murine cells in culture. Charcoal-dextran-stripped fetal bovine serum (FBS) was found to be more efficient for serum supplementation than dialyzed or undialyzed FBS, due to lower contaminating unlabeled pantothenate content. Stable isotope labeled CoA species were extracted and utilized as internal standards for CoA thioester analysis in cell culture models. This methodology of stable isotope labeling by essential nutrients in cell culture (SILEC) can serve as a paradigm for using vitamins and other essential nutrients to generate stable isotope standards that cannot be readily synthesized.

Nuclear spectroscopy of r-process nuclei around N = 126 using KISS

NASA Astrophysics Data System (ADS)

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

2017-09-01

The beta-decay properties and atomic mass of nuclei with neutron magic number of N = 126 are considered critical for understanding the production of heavy elements such as gold and platinum at astrophysical sites. We will produce and measure the half-lives and masses of the nuclei with Z = 74-77 around N = 126 by using the multinucleon transfer (MNT) reaction of ^{136} Xe/ ^{238} U beams and ^{198} Pt target system. For this purpose, we have constructed the KEK Isotope Separation System (KISS) at RIKEN RIBF facility. KISS consists of an argon gas cell based laser ion source (atomic number selection) and an isotope separation on-line (ISOL) (mass number selection), to produce pure low-energy beams of neutron-rich isotopes around N = 126 . We performed the on-line tests to study the basic properties of the KISS and, successfully extracted laser-ionized nuclei around N = 126.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

DOE PAGES

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.; ...

2016-06-23

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

NASA Astrophysics Data System (ADS)

Knowles, Justin; Skutnik, Steven; Glasgow, David; Kapsimalis, Roger

2016-10-01

Rapid nondestructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the Oak Ridge National Laboratory High Flux Isotope Reactor Neutron Activation Analysis facility has developed a generalized nondestructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and makes use of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a complete characterization of isotopic identification, mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% recovery bias have been conducted on standards of 235U and 239Pu as low as 12 ng in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 198 ng of fissile mass with less than 7% recovery bias. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. It is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation facilities, and account for increasingly complex sample matrices.

A generalized method for characterization of 235U and 239Pu content using short-lived fission product gamma spectroscopy

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

Knowles, Justin R.; Skutnik, Steven E.; Glasgow, David C.

Rapid non-destructive assay methods for trace fissile material analysis are needed in both nuclear forensics and safeguards communities. To address these needs, research at the High Flux Isotope Reactor Neutron Activation Analysis laboratory has developed a generalized non-destructive assay method to characterize materials containing fissile isotopes. This method relies on gamma-ray emissions from short-lived fission products and capitalizes off of differences in fission product yields to identify fissile compositions of trace material samples. Although prior work has explored the use of short-lived fission product gamma-ray measurements, the proposed method is the first to provide a holistic characterization of isotopic identification,more » mass ratios, and absolute mass determination. Successful single fissile isotope mass recoveries of less than 6% error have been conducted on standards of 235U and 239Pu as low as 12 nanograms in less than 10 minutes. Additionally, mixtures of fissile isotope standards containing 235U and 239Pu have been characterized as low as 229 nanograms of fissile mass with less than 12% error. The generalizability of this method is illustrated by evaluating different fissile isotopes, mixtures of fissile isotopes, and two different irradiation positions in the reactor. Furthermore, it is anticipated that this method will be expanded to characterize additional fissile nuclides, utilize various irradiation sources, and account for increasingly complex sample matrices.« less

Effects of Iron and Nitrogen Limitation on Sulfur Isotope Fractionation during Microbial Sulfate Reduction

PubMed Central

Ono, Shuhei; Bosak, Tanja

2012-01-01

Sulfate-reducing microbes utilize sulfate as an electron acceptor and produce sulfide that is depleted in heavy isotopes of sulfur relative to sulfate. Thus, the distribution of sulfur isotopes in sediments can trace microbial sulfate reduction (MSR), and it also has the potential to reflect the physiology of sulfate-reducing microbes. This study investigates the relationship between the availability of iron and reduced nitrogen and the magnitude of S-isotope fractionation during MSR by a marine sulfate-reducing bacterium, DMSS-1, a Desulfovibrio species, isolated from salt marsh in Cape Cod, MA. Submicromolar levels of iron increase sulfur isotope fractionation by about 50% relative to iron-replete cultures of DMSS-1. Iron-limited cultures also exhibit decreased cytochrome c-to-total protein ratios and cell-specific sulfate reduction rates (csSRR), implying changes in the electron transport chain that couples carbon and sulfur metabolisms. When DMSS-1 fixes nitrogen in ammonium-deficient medium, it also produces larger fractionation, but it occurs at faster csSRRs than in the ammonium-replete control cultures. The energy and reducing power required for nitrogen fixation may be responsible for the reverse trend between S-isotope fractionation and csSRR in this case. Iron deficiency and nitrogen fixation by sulfate-reducing microbes may lead to the large observed S-isotope effects in some euxinic basins and various anoxic sediments. PMID:23001667

Exploring the Potential of Laser Ablation Carbon Isotope Analysis for Examining Ecology during the Ontogeny of Middle Pleistocene Hominins from Sima de los Huesos (Northern Spain)

PubMed Central

Garcia, Nuria; Feranec, Robert S.; Passey, Benjamin H.; Cerling, Thure E.; Arsuaga, Juan Luis

2015-01-01

Laser ablation of tooth enamel was used to analyze stable carbon isotope compositions of teeth of hominins, red deer, and bears from middle Pleistocene sites in the Sierra de Atapuerca in northern Spain, to investigate the possibility that this technique could be used as an additional tool to identify periods of physiological change that are not detectable as changes in tooth morphology. Most of the specimens were found to have minimal intra-tooth variation in carbon isotopes (< 2.3‰), suggesting isotopically uniform diets through time and revealing no obvious periods of physiological change. However, one of the two sampled hominin teeth displayed a temporal carbon isotope shift (3.2‰) that was significantly greater than observed for co-occurring specimens. The δ13C value of this individual averaged about -16‰ early in life, and -13‰ later in life. This isotopic change occurred on the canine crown about 4.2 mm from the root, which corresponds to an approximate age of two to four years old in modern humans. Our dataset is perforce small owing to the precious nature of hominid teeth, but it demonstrates the potential utility of the intra-tooth isotope profile method for extracting ontogenetic histories of human ancestors. PMID:26673156

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.

Geochemical and strontium isotope characterization of produced waters from Marcellus Shale natural gas extraction.

PubMed

Chapman, Elizabeth C; Capo, Rosemary C; Stewart, Brian W; Kirby, Carl S; Hammack, Richard W; Schroeder, Karl T; Edenborn, Harry M

2012-03-20

Extraction of natural gas by hydraulic fracturing of the Middle Devonian Marcellus Shale, a major gas-bearing unit in the Appalachian Basin, results in significant quantities of produced water containing high total dissolved solids (TDS). We carried out a strontium (Sr) isotope investigation to determine the utility of Sr isotopes in identifying and quantifying the interaction of Marcellus Formation produced waters with other waters in the Appalachian Basin in the event of an accidental release, and to provide information about the source of the dissolved solids. Strontium isotopic ratios of Marcellus produced waters collected over a geographic range of ~375 km from southwestern to northeastern Pennsylvania define a relatively narrow set of values (ε(Sr)(SW) = +13.8 to +41.6, where ε(Sr) (SW) is the deviation of the (87)Sr/(86)Sr ratio from that of seawater in parts per 10(4)); this isotopic range falls above that of Middle Devonian seawater, and is distinct from most western Pennsylvania acid mine drainage and Upper Devonian Venango Group oil and gas brines. The uniformity of the isotope ratios suggests a basin-wide source of dissolved solids with a component that is more radiogenic than seawater. Mixing models indicate that Sr isotope ratios can be used to sensitively differentiate between Marcellus Formation produced water and other potential sources of TDS into ground or surface waters.

Heterodyne laser spectroscopy system

DOEpatents

Wyeth, Richard W.; Paisner, Jeffrey A.; Story, Thomas

1989-01-01

A heterodyne laser spectroscopy system utilizes laser heterodyne techniques for purposes of laser isotope separation spectroscopy, vapor diagnostics, processing of precise laser frequency offsets from a reference frequency and the like, and provides spectral analysis of a laser beam.

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, H.D. Jr.

1993-04-20

A process is described for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Molybdenum isotope systematics in subduction zones

NASA Astrophysics Data System (ADS)

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

2016-08-01

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

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

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

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

2014-05-02

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

Fingerprinting two metal contaminants in streams with Cu isotopes near the Dexing Mine, China.

PubMed

Song, Shiming; Mathur, Ryan; Ruiz, Joaquin; Chen, Dandan; Allin, Nicholas; Guo, Kunyi; Kang, Wenkai

2016-02-15

Transition metal isotope signatures are becoming useful for fingerprinting sources in surface waters. This study explored the use of Cu isotope values to trace dissolved metal contaminants in stream water throughout a watershed affected by mining by-products of the Dexing Mine, the largest porphyry Cu operation in Asia. Cu isotope values of stream water were compared to potential mineral sources of Cu in the mining operation, and to proximity to the known Cu sources. The first mineral source, chalcopyrite, CuFeS2 has a 'tight' cluster of Cu isotope values (-0.15‰ to +1.65‰; +0.37 ± 0.6‰, 1σ, n=10), and the second mineral source, pyrite (FeS2), has a much larger range of Cu isotope values (-4‰ to +11.9‰; 2.7 ± 4.3‰, 1σ, n=16). Dissolved Cu isotope values of stream water indicated metal derived from either chalcopyrite or pyrite. Above known Cu mineralization, stream waters are approximately +1.5‰ greater than the average chalcopyrite and are interpreted as derived from weathering of chalcopyrite. In contrast, dissolved Cu isotope values in stream water emanating from tailings piles had Cu isotope values similar to or greater than pyrite (>+6‰, a common mineral in the tailings). These values are interpreted as sourced from the tailings, even in solutions that possess significantly lower concentrations of Cu (<0.05 ppm). Elevated Cu isotope values were also found in two soil and two tailings samples (δ(65)Cu ranging between +2 to +5‰). These data point to the mineral pyrite in tailings as the mineral source for the elevated Cu isotope values. Therefore, Cu isotope values of waters emanating from a clearly contaminated drainage possess different Cu isotope values, permitting the discrimination of Cu derived from chalcopyrite and pyrite in solution. Data demonstrate the utility of Cu isotopic values in waters, minerals, and soils to fingerprint metallic contamination for environmental problems. Copyright © 2015 Elsevier B.V. All rights reserved.

The early bird gets the shrimp: Confronting assumptions of isotopic equilibrium and homogeneity in a wild bird population

USGS Publications Warehouse

Wunder, Michael B.; Jehl, Joseph R.; Stricker, Craig A.

2012-01-01

1. Because stable isotope distributions in organic material vary systematically across energy gradients that exist in ecosystems, community and population structures, and in individual physiological systems, isotope values in animal tissues have helped address a broad range of questions in animal ecology. It follows that every tissue sample provides an isotopic profile that can be used to study dietary or movement histories of individual animals. Interpretations of these profiles depend on the assumption that metabolic pools are isotopically well mixed and in equilibrium with dietary resources prior to tissue synthesis, and they extend to the population level by assuming isotope profiles are identically distributed for animals using the same proximal dietary resource. As these assumptions are never fully met, studying structure in the variance of tissue isotope values from wild populations is informative. 2. We studied variation in δ13C, δ15N, δ2H and δ18O data for feathers from a population of eared grebes (Podiceps nigricollis) that migrate to Great Salt Lake each fall to moult feathers. During this time, they cannot fly and feed almost exclusively on superabundant brine shrimp (Artemia franciscana). The ecological simplicity of this situation minimized the usual spatial and trophic complexities often present in natural studies of feather isotope values. 3. Ranges and variances of isotope values for the feathers were larger than those from previously published studies that report feather isotopic variance, but they were bimodally distributed in all isotope dimensions. Isotope values for proximal dietary resources and local surface water show that some of the feathers we assumed to have been grown locally must have been grown before birds reached isotopic equilibrium with local diet or immediately prior to arrival at Great Salt Lake. 4. Our study provides novel insights about resource use strategies in eared grebes during migration. More generally, it demonstrates the utility of studying variance structures and questioning assumptions implicit in the interpretation of stable isotope data from wild animals.

The Alaska Water Isotope Network (AKWIN): Precipitation, lake, river and stream dynamics

NASA Astrophysics Data System (ADS)

Rogers, M.; Welker, J. M.; Toohey, R.

2011-12-01

The hydrologic cycle is central to the structure and function of northern landscapes. The movement of water creates interactions between terrestrial, aquatic, marine and atmospheric processes. Understanding the processes and the spatial patterns that govern the isotopic (δ18O & δD) characteristics of the hydrologic cycle is especially important today as: a) modern climate/weather-isotope relations allow for more accurate interpretation of climate proxies and the calibration of atmospheric models, b) water isotopes facilitate understanding the role of storm tracks in regulating precipitation isotopic variability, c) water isotopes allow for estimates of glacial melt water inputs into aquatic systems, d) water isotopes allow for quantification of surface and groundwater interactions, e) water isotopes allow for quantification of permafrost meltwater use by plant communities, f) water isotopes aid in migratory bird forensics, g) water isotopes are critical to estimating field metabolic rates, h) water isotopes allow for crop and diet forensics and i) water isotopes can provide insight into evaporation and transpiration processes. As part of a new NSF MRI project at the Environment and Natural Resources Institute (ENRI) at the University of Alaska Anchorage and as an extension of the US Network for Isotopes in Precipitation (USNIP); we are forming AKWIN. The network will utilize long-term weekly sampling at Denali National Park and Caribou Poker Creek Watershed (USNIP sites-1989 to present), regular sampling across Alaska involving land management agencies (USGS, NPS, USFWS, EPA), educators, volunteers and citizen scientists, UA extended campuses, individual research projects, opportunistic sampling and published data to construct isoscapes and time series databases and information packages. We will be using a suite of spatial and temporal analysis methods to characterize water isotopes across Alaska and will provide web portals for data products. Our network is designed to interface with the existing USNIP and will provide a research and data platform that will assist with answering the core questions of NEON addressing climate and land use change in Alaska, in the north and across the US.

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

USGS Publications Warehouse

Morgan, J.L.L.; Gordon, G.W.; Arrua, R.C.; Skulan, J.L.; Anbar, A.D.; Bullen, T.D.

2011-01-01

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios (44Ca/42Ca and 44Ca/43Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10000; Ca/Ti > 10000000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ44/42Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).

Technical developments for an upgrade of the LEBIT Penning trap mass spectrometry facility for rare isotopes

NASA Astrophysics Data System (ADS)

Redshaw, M.; Barquest, B. R.; Bollen, G.; Bustabad, S. E.; Campbell, C. M.; Ferrer, R.; Gehring, A.; Kwiatkowski, A. A.; Lincoln, D. L.; Morrissey, D. J.; Pang, G. K.; Ringle, R.; Schwarz, S.

2011-07-01

The LEBIT (Low Energy Beam and Ion Trap) facility is the only Penning trap mass spectrometry (PTMS) facility to utilize rare isotopes produced via fast-beam fragmentation. This technique allows access to practically all elements lighter than uranium, and in particular enables the production of isotopes that are not available or that are difficult to obtain at isotope separation on-line facilities. The preparation of the high-energy rare-isotope beam produced by projectile fragmentation for low-energy PTMS experiments is achieved by gas stopping to slow down and thermalize the fast-beam ions, along with an rf quadrupole cooler and buncher and rf quadrupole ion guides to deliver the beam to the Penning trap. During its first phase of operation LEBIT has been very successful, and new developments are now underway to access rare isotopes even farther from stability, which requires dealing with extremely short lifetimes and low production rates. These developments aim at increasing delivery efficiency, minimizing delivery and measurement time, and maximizing use of available beam time. They include an upgrade to the gas-stopping station, active magnetic field monitoring and stabilization by employing a miniature Penning trap as a magnetometer, the use of stored waveform inverse Fourier transform (SWIFT) to most effectively remove unwanted ions, and charge breeding.

Locally Grown, Natural Ingredients? The Isotope Ratio Can Reveal a Lot!

PubMed

Rossier, Joël S; Maury, Valérie; Pfammatter, Elmar

2016-01-01

This communication gives an overview of selected isotope analyses applied to food authenticity assessment. Different isotope ratio detection technologies such as isotope ratio mass spectrometry (IRMS) and cavity ring down spectroscopy (CRDS) are briefly described. It will be explained how δ(18)O of water contained in fruits and vegetables can be used to assess their country of production. It will be explained why asparagus grown in Valais, in the centre of the Alps carries much less heavy water than asparagus grown closer to the sea coast. On the other hand, the use of δ(13)C can reveal whether a product is natural or adulterated. Applications including honey or sparkling wine adulteration detection will be briefly presented.

Precision mass measurements of cesium isotopes—new entries in the ISOLTRAP chronicles

NASA Astrophysics Data System (ADS)

Atanasov, D.; Beck, D.; Blaum, K.; Borgmann, Ch; Cakirli, R. B.; Eronen, T.; George, S.; Herfurth, F.; Herlert, A.; Kowalska, M.; Kreim, S.; Litvinov, Yu A.; Lunney, D.; Manea, V.; Neidherr, D.; Rosenbusch, M.; Schweikhard, L.; Wienholtz, F.; Wolf, R. N.; Zuber, K.

2017-04-01

Alkali ion beams are among the most intense produced by the ISOLDE facility. These were the first to be studied by the ISOLTRAP mass spectrometer and ever since, new measurements have been regularly reported. Recently the masses of very neutron-rich and short-lived cesium isotopes were determined at ISOLTRAP. The isotope 148Cs was measured directly for the first time by Penning-trap mass spectrometry. Using the new results, the trend of two-neutron separation energies in the cesium isotopic chain is revealed to be smooth and gradually decreasing, similar to the ones of the barium and xenon isotopic chains. Predictions of selected microscopic models are employed for a discussion of the experimental data in the region.

Gamma ray spectroscopy monitoring method and apparatus

DOEpatents

Stagg, William R; Policke, Timothy A

2017-05-16

The present invention relates generally to the field of gamma ray spectroscopy monitoring and a system for accomplishing same to monitor one or more aspects of various isotope production processes. In one embodiment, the present invention relates to a monitoring system, and method of utilizing same, for monitoring one or more aspects of an isotope production process where the monitoring system comprises: (A) at least one sample cell; (B) at least one measuring port; (C) at least one adjustable collimator device; (D) at least one shutter; and (E) at least one high resolution gamma ray spectrometer.

Synthesis and characterization of surrogate nuclear explosion debris: urban glass matrix

DOE PAGES

Campbell, Keri; Judge, Elizabeth J.; Dirmyer, Matthew R.; ...

2017-07-26

Surrogate nuclear explosive debris was synthesized and characterized for major, minor, and trace elemental composition as well as uranium isotopics. The samples consisted of an urban glass matrix, equal masses soda lime and cement, doped with 500 ppm uranium with varying enrichments. The surface and cross section morphology were measured with SEM, and the major elemental composition was determined by XPS. LA-ICP-MS was used to measure the uranium isotopic abundance comparing different sampling techniques. Furthermore, the results provide an example of the utility of LA-ICP-MS for forensics applications.

Ether Lipids of Planktonic Archaea in the Marine Water Column

PubMed Central

Hoefs, M.; Schouten, S.; De Leeuw, J. W.; King, L. L.; Wakeham, S. G.; Damste, J.

1997-01-01

Acyclic and cyclic biphytanes derived from the membrane ether lipids of archaea were found in water column particulate and sedimentary organic matter from several oxic and anoxic marine environments. Compound-specific isotope analyses of the carbon skeletons suggest that planktonic archaea utilize an isotopically heavy carbon source such as algal carbohydrates and proteins or dissolved bicarbonate. Due to their high preservation potential, these lipids provide a fossil record of planktonic archaea and suggest that they have thrived in marine environments for more than 50 million years. PMID:16535669

Copper and Zinc isotope composition of CR, CB and CH-like meteorites.

NASA Astrophysics Data System (ADS)

Russell, S.; Zhu, X.; Guo, Y.; Mullane, E.; Gounelle, M.; Mason, T.; Coles, B.

2003-04-01

Copper and zinc isotopes have recently been shown to be variable in isotopic composi-tion among terrestrial and extraterrestrial materials [1-3]. For this study, we have se-lected samples (bulk meteorite and chondrule separates) from the CR meteorite clan: Bencubbin (CB), Renazzo (CR2), NWA 801 (CR2), and HaH237 (CH-like). These meteorites were selected because meteorites from this clan have experienced very little alteration since their initial formation [4] and for their extremely high refrac-tory/volatile element ratios. The latter characteristic may allow a test of the correlation observed by [2] between element ratios and Cu isotope composition. Measurements were performed on NHM/IC Micromass Isoprobe and Oxford Nu MC-ICP-MS using techniques described elsewhere [1,5]. Each of the meteorites measured so far for Cu and Zn are isotopically light compared to the terrestrial mantle. This suggests that the terrestrial value may have been altered from the pristine solar system value, or else there were multiple early solar system components. Zinc isotopic com-positions lie on a fractionation line and range from δ66ZnNIST = -1.4±0.1ppm (bulk NWA801) to -1.9±0.1ppm (separated chondrule, NWA 801). Copper isotope compositions vary from δ65CuNIST976 = -1.5±0.1ppm (bulk Renazzo) to -3.1±0.1ppm (separated chondrule, NWA 801). Two chondrules from NWA 801 have differing Cu isotope values (-3.1±0.1 and -2.0±0.1ppm) and both are lighter than the bulk meteorite (-1.9±0.1ppm), suggesting a lack of equilibration with respect to Cu in this meteorite. The light values for the two separated chondrules, compared the bulk meteorite, hints that chondrules may be isotopically lighter than co-existing matrix, metal and sulphides with respect to Cu. The copper isotope compositions are not as isotopically light as expected for the high refractory/volatile element ratio observed in these chondrites. Thus a model to account for the Cu isotopes in chondrites may require greater com-plexity than one involving simple mixing of two primordial components. References: [1] Zhu et al., Chem. Geol. 163,139-149 (2000). [2] Luck et al., GCA 67 143 (2002). [3] Luck et al., MAPS 35 A100 (2000) [4] Krot et al., MAPS 37 1451-1490 (2002) [5] Mason et al. EOS Trans. AGU abstract V21A-0966 82 (2001)

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

PubMed

Marsh, B A

2014-02-01

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

Hydrologic, chemical, and isotopic characterization of two small watersheds on Catoctin Mountain, north-central Maryland, U.S.A.

USGS Publications Warehouse

Rice, Karen C.; Bricker, O.P.

1993-01-01

Two small (100 ha) watersheds located on Catoctin Mountain in north-central Maryland were intensively instrumented in 1990 and have been hydrologically, chemically, and isotopically monitored for 3 years. Dissolved concentrations of major ions (Ca2+, Mg2+, Na+, K+, total AI, CI-, NO3-, SO42- , HCO3-, and SiO2) and stable isotopic (D and 18O) values have been analyzed for most types of water (precipitation, throughfall, two depths of soil water, shallow groundwater, and streamwater) that enter, travel through, and exit each watershed. The major objectives of the study were to characterize the chemical and isotopic signatures of all aqueous components of the watersheds and to interpret the causes of the changes in chemical and isotopic compositions of streamwater during storm runoff. This paper describes selected results of the study.

Isotopically selective two-photon ionization of aniline in supersonic beams

NASA Astrophysics Data System (ADS)

Leutwyler, S.; Even, U.

1981-08-01

Tunable laser two-photon ionization of aniline cooled in supersonic expansions combined with TOF mass spectrometry reveal an isotopic shift of the vibronic origin at 2938 Å (ππ ∗; 1B 2← 1A 1 transition). The shift (+4.6 cm -1) is smaller than the rotational bandwidth and would be unobservable by laser-induced fluorescence.

Caution on the use of Viton® or FETFE® O-rings in carbon dioxide sample containers for δ180 analysis

USGS Publications Warehouse

Revesz, Kinga M.; Coplen, Tyler B.

1991-01-01

Caution needs to be exercised in selecting sample containers for CO2 isotope-ratio samples of < 200 μmol. If stopcocks are used in construction of containers for such samples, the use of all-glass stopcocks with Apiezon N® hydrocarbon-based grease will eliminate the fractionation of oxygen isotopes.

Rapid analytical determination of glutaraldehyde concentrations

NASA Technical Reports Server (NTRS)

Frigerio, N. A.; Shaw, M. H.

1971-01-01

Technique utilizes the iodimetric procedure which adds unknown excess of bisulfite to glutaraldehyde /GA/ then titrates unreacted bisulfite with standard iodine isotope to determine GA concentrations. Technique may interest microscopists, food researchers, biochemical or medical laboratories, and drug manufacturers.

Development and Attestation of Gamma-Ray Measurement Methodologies for use by Rostekhnadzor Inspectors in the Russian Federation

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

Jeff Sanders

2006-09-01

Development and attestation of gamma-ray non-destructive assay measurement methodologies for use by inspectors of the Russian Federal Service for Environmental, Technological, and Nuclear Oversight (Rostekhnadzor, formerly Gosatomnadzor or GAN), as well as for use by Russian nuclear facilities, has been completed. Specifically, a methodology utilizing the gamma-ray multi group analysis (MGA) method for determining plutonium isotopic composition has been developed, while existing methodologies to determining uranium enrichment and isotopic composition have been revised to make them more appropriate to the material types and conditions present in nuclear facilities in the Russian Federation. This paper will discuss the development and revisionmore » of these methodologies, the metrological characteristics of the final methodologies, as well as the limitations and concerns specific to the utilization of these analysis methods in the Russian Federation.« less

Strontium isotope evidence for a highly mobile population on the Pamir Plateau 2500 years ago

NASA Astrophysics Data System (ADS)

Wang, Xueye; Tang, Zihua; Wu, Jing; Wu, Xinhua; Wu, Yiqun; Zhou, Xinying

2016-10-01

Archeological researches have proposed arguments for human mobility and long-distance trading over the Eurasia before the Silk Roads. Here we utilize biologically available strontium isotope analysis to assess the extent of pre-Silk Road population movements and cultural communications across the Asian interior. From an early Iron Age cemetery (ca. 2500 yr B.P.) on the eastern Pamir Plateau, mean 87Sr/86Sr ratios from 34 individuals display considerable isotopic variability, and 10 individuals are distinguished as migrants based on the local strontium isotope range of 0.710296-0.710572 defined by 12 ovicaprine bones. Comparison of the proportion (10/34) with the regional census data completed in 1909 A.D. (3% non-locals) suggests a highly migratory behavior on the plateau 2500 years ago. Furthermore, exotic mortuary objects, such as silk fabrics from eastern China and angular harp originated from the Near East, clearly demonstrate an interaction between different cultures on the plateau before the establishment of the Silk Road.

Comparison of two stable hydrogen isotope-ratio measurement techniques on Antarctic surface-water and ice samples

USGS Publications Warehouse

Hopple, J.A.; Hannon, J.E.; Coplen, T.B.

1998-01-01

A comparison of the new hydrogen isotope-ratio technique of Vaughn et al. ([Vaughn, B.H., White, J.W.C., Delmotte, M., Trolier, M., Cattani, O., Stievenard, M., 1998. An automated system for hydrogen isotope analysis of water. Chem. Geol. (Isot. Geosci. Sect.), 152, 309-319]; the article immediately preceding this article) for the analysis of water samples utilizing automated on-line reduction by elemental uranium showed that 94% of 165 samples of Antarctic snow, ice, and stream water agreed with the ??2H values determined by H2-H2O platinum equilibration, exhibiting a bias of +0.5??? and a 2 - ?? variation of 1.9???. The isotopic results of 10 reduction technique samples, however, gave ??2H values that differed by 3.5??? or more, and were too negative by as much as 5.4??? and too positive by as much as 4.9??? with respect to those determined using the platinum equilibration technique.

Use of an intact core and stable-metal isotopes to examine leaching characteristics of a fluvial tailings deposit

USGS Publications Warehouse

Ranville, James F.; Smith, Kathleen S.; Lamothe, Paul J.; Jackson, Brian P.; Walton-Day, Katherine

2003-01-01

In this paper, we use Cd as an example of the utility of stable-metal isotopes in geochemical studies. In the case of Cd, after the core was partially saturated, the 111Cd spike was released as evidenced by a change in the Cd isotope ratios in the effluent. This release continued during the fully saturated leaching phase, however, the total Cd concentration did not increase. These results suggest that the 111Cd spike was retained inside the core during the unsaturated leaching phase, and only partially released as reducing conditions developed. Results from this core-leaching experiment indicate there is a large reservoir of water-soluble material within the fluvial tailings deposit, which yields elevated metal concentrations and high acidity, and which may degrade adjacent ground- and surface-water quality. Use of stable metal isotopes in this study facilitated the determination of different metal-retention processes, metal-release processes, and metal sources in the fluvial tailings deposit in response to changing geochemical conditions.

Prostate Specific or Enriched Genes as Composite Biomarkers for Prostate Cancer

DTIC Science & Technology

2008-02-01

isotope dilution by comparing to the 13C- or 15N-labeled reference peptides. The MRM method is best practiced utilizing a triple quadrupole mass...specific, androgen- regulated gene. Here, we evaluate its utility as a prostate cancer tissue marker for diagnosis and prognostic evaluation. Experimental...prevalence of adverse prognostic factors such as capsular penetration, seminal vesicle invasion, and positive surgical margins is rather high compared with

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates, nicotianamine, and phytosiderophore, and new Fe isotopic measurements in higher plants

NASA Astrophysics Data System (ADS)

Moynier, Frédéric; Fujii, Toshiyuki; Wang, Kun; Foriel, Julien

2013-05-01

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ˜3‰ (56Fe/54Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ˜1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate2 and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ56Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.

Tooth enamel stable isotopes of Holocene and Pleistocene fossil fauna reveal glacial and interglacial paleoenvironments of hominins in Indonesia

NASA Astrophysics Data System (ADS)

Janssen, Renée; Joordens, Josephine C. A.; Koutamanis, Dafne S.; Puspaningrum, Mika R.; de Vos, John; van der Lubbe, Jeroen H. J. L.; Reijmer, John J. G.; Hampe, Oliver; Vonhof, Hubert B.

2016-07-01

The carbon (δ13C) and oxygen (δ18O) isotope compositions of fossilized animal tissues have become important proxies of paleodiet and paleoenvironment, but such stable isotope studies have not yet been extensively applied to the fossil assemblages of Sundaland (the biogeographical region comprising most of the Indonesian Archipelago). Here, we use the isotope composition of tooth enamel to investigate the diet and habitat of bovids, cervids, and suids from several Holocene and Pleistocene sites on Java and Sumatra. Our carbon isotope results indicate that individual sites are strongly dominated by either C3-browsers or C4-grazers. Herbivores from the Padang Highlands (Sumatra) and Hoekgrot (Java) cave faunas were mainly C3-browsers, while herbivores from Homo erectus-bearing sites Trinil and Sangiran (Java) utilized an almost exclusive C4 diet. The suids from all sites show a wide range of δ13C values, corroborating their omnivorous diet. For the dataset as a whole, oxygen and carbon isotope values are positively correlated. This suggests that isotopic enrichment of rainwater and vegetation δ18O values coincides with an increase of C4-grasslands. We interpret this pattern to mainly reflect the environmental contrast between glacial (drier, more C4) and interglacial (wetter, more C3) conditions. Intermediate herbivore δ13C values indicating mixed C3/C4 feeding is relatively rare, which we believe to reflect the abruptness of the transition between glacial and interglacial precipitation regimes in Sundaland. For seven Homo erectus bone samples we were not able distinguish between diagenetic overprint and original isotope values, underlining the need to apply this isotopic approach to Homo erectus tooth enamel instead of bone. Importantly, our present results on herbivore and omnivore faunas provide the isotopic framework that will allow interpretation of such Homo erectus enamel isotope data.

Stable isotopic comparison between loggerhead sea turtle tissues.

PubMed

Vander Zanden, Hannah B; Tucker, Anton D; Bolten, Alan B; Reich, Kimberly J; Bjorndal, Karen A

2014-10-15

Stable isotope analysis has been used extensively to provide ecological information about diet and foraging location of many species. The difference in isotopic composition between animal tissue and its diet, or the diet-tissue discrimination factor, varies with tissue type. Therefore, direct comparisons between isotopic values of tissues are inaccurate without an appropriate conversion factor. We focus on the loggerhead sea turtle (Caretta caretta), for which a variety of tissues have been used to examine diet, habitat use, and migratory origin through stable isotope analysis. We calculated tissue-to-tissue conversions between two commonly sampled tissues. Epidermis and scute (the keratin covering on the carapace) were sampled from 33 adult loggerheads nesting at two beaches in Florida (Casey Key and Canaveral National Seashore). Carbon and nitrogen stable isotope ratios were measured in the epidermis and the youngest portion of the scute tissue, which reflect the isotopic composition of the diet and habitat over similar time periods of the order of several months. Significant linear relationships were observed between the δ(13)C and δ(15)N values of these two tissues, indicating they can be converted reliably. Whereas both epidermis and scute samples are commonly sampled from nesting sea turtles to study trophic ecology and habitat use, the data from these studies have not been comparable without reliable tissue-to-tissue conversions. The equations provided here allow isotopic datasets using the two tissues to be combined in previously published and subsequent studies of sea turtle foraging ecology and migratory movement. In addition, we recommend that future isotopic comparisons between tissues of any organism utilize linear regressions to calculate tissue-to-tissue conversions. Copyright © 2014 John Wiley & Sons, Ltd.

Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

NASA Technical Reports Server (NTRS)

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

2012-01-01

We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

Graphite for the nuclear industry

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

Burchell, T.D.; Fuller, E.L.; Romanoski, G.R.

Graphite finds applications in both fission and fusion reactors. Fission reactors harness the energy liberated when heavy elements, such as uranium or plutonium, fragment or fission''. Reactors of this type have existed for nearly 50 years. The first nuclear fission reactor, Chicago Pile No. 1, was constructed of graphite under a football stand at Stagg Field, University of Chicago. Fusion energy devices will produce power by utilizing the energy produced when isotopes of the element hydrogen are fused together to form helium, the same reaction that powers our sun. The role of graphite is very different in these two reactormore » systems. Here we summarize the function of the graphite in fission and fusion reactors, detailing the reasons for their selection and discussing some of the challenges associated with their application in nuclear fission and fusion reactors. 10 refs., 15 figs., 1 tab.« less

Designing Radiation Resistance in Materials for Fusion Energy

NASA Astrophysics Data System (ADS)

Zinkle, S. J.; Snead, L. L.

2014-07-01

Proposed fusion and advanced (Generation IV) fission energy systems require high-performance materials capable of satisfactory operation up to neutron damage levels approaching 200 atomic displacements per atom with large amounts of transmutant hydrogen and helium isotopes. After a brief overview of fusion reactor concepts and radiation effects phenomena in structural and functional (nonstructural) materials, three fundamental options for designing radiation resistance are outlined: Utilize matrix phases with inherent radiation tolerance, select materials in which vacancies are immobile at the design operating temperatures, or engineer materials with high sink densities for point defect recombination. Environmental and safety considerations impose several additional restrictions on potential materials systems, but reduced-activation ferritic/martensitic steels (including thermomechanically treated and oxide dispersion-strengthened options) and silicon carbide ceramic composites emerge as robust structural materials options. Materials modeling (including computational thermodynamics) and advanced manufacturing methods are poised to exert a major impact in the next ten years.

Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

DOE PAGES

Xie, Jiahan; Yin, Kehua; Serov, Alexey; ...

2016-12-15

Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O 2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H 2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials formore » alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.« less

Ar39 Detection at the 10-16 Isotopic Abundance Level with Atom Trap Trace Analysis

NASA Astrophysics Data System (ADS)

Jiang, W.; Williams, W.; Bailey, K.; Davis, A. M.; Hu, S.-M.; Lu, Z.-T.; O'Connor, T. P.; Purtschert, R.; Sturchio, N. C.; Sun, Y. R.; Mueller, P.

2011-03-01

Atom trap trace analysis, a laser-based atom counting method, has been applied to analyze atmospheric Ar39 (half-life=269yr), a cosmogenic isotope with an isotopic abundance of 8×10-16. In addition to the superior selectivity demonstrated in this work, the counting rate and efficiency of atom trap trace analysis have been improved by 2 orders of magnitude over prior results. The significant applications of this new analytical capability lie in radioisotope dating of ice and water samples and in the development of dark matter detectors.

Calcium isotope systematics at hydrothermal conditions: Mid-ocean ridge vent fluids and experiments in the CaSO4-NaCl-H2O system

NASA Astrophysics Data System (ADS)

Scheuermann, Peter P.; Syverson, Drew D.; Higgins, John A.; Pester, Nicholas J.; Seyfried, William E.

2018-04-01

Two sets of hydrothermal experiments were performed to explore Ca isotope fractionation and exchange rates at hydrothermal conditions (410-450 °C, 31.0-50.0 MPa). The first set of experiments determined the magnitude of vapor-liquid Ca isotope fractionation and anhydrite solubility in the CaSO4-NaCl-H2O system. The data indicate no statistical difference between the Ca isotopic composition of coexisting vapor and liquid. The second set of experiments utilized an anomalous 43Ca spike to determine the rate of Ca exchange between fluid and anhydrite as a function of total dissolved Ca concentration. Results show that the rate of exchange increases with dissolved Ca concentrations (12-23 mM/kg), but no change in exchange rate is observed when the Ca concentration increases from 23 to 44 mM/kg Ca. 74-142 days are required to achieve 90% anhydrite-fluid Ca isotope exchange at the conditions investigated, while only several hours are necessary for vapor-liquid isotopic equilibrium. The lack of vapor-liquid Ca isotope fractionation in our experiments is consistent with δ44Ca of mid-ocean ridge hydrothermal vent fluids that remain constant, regardless of chlorinity. Moreover, the narrow range of end member fluid δ44Ca, -0.98 to -1.13‰ (SW), is largely indistinguishable from MORB δ44Ca, suggesting that neither phase separation nor fluid-rock interactions at depth significantly fractionate Ca isotopes in modern high-temperature mid-ocean ridge hydrothermal systems.

Lead isotope determinations from sulfide mineral occurrences--Russian Far East

USGS Publications Warehouse

Church, Stan E.; Goryachev, Nikolai A.; Shpikerman, Vladimir I.

2013-01-01

The lead isotope database for sulfide deposits and occurrences in the Russian Far East was funded by the Mineral Resources Program, U.S. Geological Survey (USGS) in conjunction with the collaborative studies of mineral resources by the Russian Academy of Sciences and the U. S. Geological Survey (Nokleberg and others, 1996). Comparisons of these data with similar lead isotope data from Alaska published in Church, Delevaux, and others (1987) and Gaccetta and Church (1989) provide a basis for the following three-fold project objectives: 1. To utilize lead isotope signatures, in conjunction with regional mapping, to assess the relative ages and to categorize the types of mineral deposits studied, 2. To relate the lead isotope and trace-element geochemical signatures of specific deposits and occurrences to ore-forming processes, and 3. To use the lead isotope data to correlate lithotectonic terranes within the northern Cordillera (Alaska, Yukon Territories and British Columbia in Canada, and the western Cordillera of the United States). The report by Church, Gray, and others (1987) shows how this fingerprinting methodology can be applied to trace the offset of lithotectonic (or lithostratigraphic as labeled by some authors) terranes.The lead isotope data presented in table 1 represent the work completed on sulfide mineral deposits located in the Russian Far East from 1993 to 1995, when this study was terminated due to lack of funding. The lead isotope data are reported here for use by investigators who may find them of value in mineral exploration. No attempt is made to summarize the voluminous literature on these mineral deposits.

DISSOLUTION AND ANALYSIS OF YELLOWCAKE COMPONENTS FOR FINGERPRINTING UOC SOURCES

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

Hexel, Cole R; Bostick, Debra A; Kennedy, Angel K

2012-01-01

There are a number of chemical and physical parameters that might be used to help elucidate the ore body from which uranium ore concentrate (UOC) was derived. It is the variation in the concentration and isotopic composition of these components that can provide information as to the identity of the ore body from which the UOC was mined and the type of subsequent processing that has been undertaken. Oak Ridge National Laboratory (ORNL) in collaboration with Lawrence Livermore and Los Alamos National Laboratories is surveying ore characteristics of yellowcake samples from known geologic origin. The data sets are being incorporatedmore » into a national database to help in sourcing interdicted material, as well as aid in safeguards and nonproliferation activities. Geologic age and attributes from chemical processing are site-specific. Isotopic abundances of lead, neodymium, and strontium provide insight into the provenance of geologic location of ore material. Variations in lead isotopes are due to the radioactive decay of uranium in the ore. Likewise, neodymium isotopic abundances are skewed due to the radiogenic decay of samarium. Rubidium decay similarly alters the isotopic signature of strontium isotopic composition in ores. This paper will discuss the chemical processing of yellowcake performed at ORNL. Variations in lead, neodymium, and strontium isotopic abundances are being analyzed in UOC from two geologic sources. Chemical separation and instrumental protocols will be summarized. The data will be correlated with chemical signatures (such as elemental composition, uranium, carbon, and nitrogen isotopic content) to demonstrate the utility of principal component and cluster analyses to aid in the determination of UOC provenance.« less

The utilization of a Pacific salmon Oncorhynchus nerka subsidy by three populations of charr Salvelinus spp.

PubMed

Denton, K P; Rich, H B; Moore, J W; Quinn, T P

2010-09-01

The L(F) -at-age trajectories differentiated two populations of Dolly Varden charr Salvelinus malma and a population of Arctic charr Salvelinus alpinus from the eastern end of Iliamna Lake, Alaska. Salvelinus malma from the Pedro Bay ponds were the smallest for a given age, followed by Salvelinus alpinus from the lake, and S. malma from the Iliamna River were much larger. The utilization of a large sockeye salmon Oncorhynchus nerka subsidy by the three Salvelinus spp. populations was then investigated by comparing diet data and mixing model (MixSIR) outputs based on carbon and nitrogen stable isotopes. Stomach contents indicated that both S. malma populations fed on O. nerka products, especially eggs and larval Diptera that had scavenged O. nerka carcasses, whereas S. alpinus fed on a variety of prey items such as three-spined sticklebacks Gasterosteus aculeatus and snails. Stable-isotope analysis corroborated the diet data; the two S. malma populations incorporated more O. nerka-derived nutrients into their tissues than did S. alpinus from the lake, although all populations showed substantial utilization of O. nerka-derived resources. Salvelinus alpinus also seemed to be much more omnivorous, as shown by stable-isotope mixing models, than the S. malma populations. The dramatic differences in growth rate between the two S. malma populations, despite similar trophic patterns, indicate that other important genetic or environmental factors affect their life history, including proximate temperature controls and ultimate predation pressures. © 2010 The Authors. Journal compilation © 2010 The Fisheries Society of the British Isles.

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.

Advances in stable isotope assisted labeling strategies with information science.

PubMed

Kigawa, Takanori

2017-08-15

Stable-isotope (SI) labeling of proteins is an essential technique to investigate their structures, interactions or dynamics by nuclear magnetic resonance (NMR) spectroscopy. The assignment of the main-chain signals, which is the fundamental first step in these analyses, is usually achieved by a sequential assignment method based on triple resonance experiments. Independently of the triple resonance experiment-based sequential assignment, amino acid-selective SI labeling is beneficial for discriminating the amino acid type of each signal; therefore, it is especially useful for the signal assignment of difficult targets. Various combinatorial selective labeling schemes have been developed as more sophisticated labeling strategies. In these strategies, amino acids are represented by combinations of SI labeled samples, rather than simply assigning one amino acid to one SI labeled sample as in the case of conventional amino acid-selective labeling. These strategies have proven to be useful for NMR analyses of difficult proteins, such as those in large complex systems, in living cells, attached or integrated into membranes, or with poor solubility. In this review, recent advances in stable isotope assisted labeling strategies will be discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars.

PubMed

Shaheen, R; Abramian, A; Horn, J; Dominguez, G; Sullivan, R; Thiemens, Mark H

2010-11-23

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess (17)O (0.4-3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O(3) reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth.

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

PubMed

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

2018-06-01

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

Detection of oxygen isotopic anomaly in terrestrial atmospheric carbonates and its implications to Mars

PubMed Central

Shaheen, R.; Abramian, A.; Horn, J.; Dominguez, G.; Sullivan, R.; Thiemens, Mark H.

2010-01-01

The debate of life on Mars centers around the source of the globular, micrometer-sized mineral carbonates in the ALH84001 meteorite; consequently, the identification of Martian processes that form carbonates is critical. This paper reports a previously undescribed carbonate formation process that occurs on Earth and, likely, on Mars. We identified micrometer-sized carbonates in terrestrial aerosols that possess excess 17O (0.4–3.9‰). The unique O-isotopic composition mechanistically describes the atmospheric heterogeneous chemical reaction on aerosol surfaces. Concomitant laboratory experiments define the transfer of ozone isotopic anomaly to carbonates via hydrogen peroxide formation when O3 reacts with surface adsorbed water. This previously unidentified chemical reaction scenario provides an explanation for production of the isotopically anomalous carbonates found in the SNC (shergottites, nakhlaites, chassignites) Martian meteorites and terrestrial atmospheric carbonates. The anomalous hydrogen peroxide formed on the aerosol surfaces may transfer its O-isotopic signature to the water reservoir, thus producing mass independently fractionated secondary mineral evaporites. The formation of peroxide via heterogeneous chemistry on aerosol surfaces also reveals a previously undescribed oxidative process of utility in understanding ozone and oxygen chemistry, both on Mars and Earth. PMID:21059939

Archean Pb Isotope Evolution: Implications for the Early Earth.

NASA Astrophysics Data System (ADS)

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

2008-12-01

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

Identification of a Compound Spinel and Silicate Presolar Grain in a Chondritic Interplanetary Dust Particle

NASA Technical Reports Server (NTRS)

Nguyen, A. N.; Nakamura-Messenger, K.; Messenger, S.; Keller, L. P.; Kloeck, W.

2014-01-01

Anhydrous chondritic porous interplanetary dust particles (CP IDPs) have undergone minimal parent body alteration and contain an assemblage of highly primitive materials, including molecular cloud material, presolar grains, and material that formed in the early solar nebula [1-3]. The exact parent bodies of individual IDPs are not known, but IDPs that have extremely high abundances of presolar silicates (up to 1.5%) most likely have cometary origins [1, 4]. The presolar grain abundance among these minimally altered CP IDPs varies widely. "Isotopically primitive" IDPs distinguished by anomalous bulk N isotopic compositions, numerous 15N-rich hotspots, and some C isotopic anomalies have higher average abundances of presolar grains (375 ppm) than IDPs with isotopically normal bulk N (<10 ppm) [5]. Some D and N isotopic anomalies have been linked to carbonaceous matter, though this material is only rarely isotopically anomalous in C [1, 5, 6]. Previous studies of the bulk chemistry and, in some samples, the mineralogy of select anhydrous CP IDPs indicate a link between high C abundance and pyroxene-dominated mineralogy [7]. In this study, we conduct coordinated mineralogical and isotopic analyses of samples that were analyzed by [7] to characterize isotopically anomalous materials and to establish possible correlations with C abundance.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Equilibrium cycle pin by pin transport depletion calculations with DeCART

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

Kochunas, B.; Downar, T.; Taiwo, T.

As the Advanced Fuel Cycle Initiative (AFCI) program has matured it has become more important to utilize more advanced simulation methods. The work reported here was performed as part of the AFCI fellowship program to develop and demonstrate the capability of performing high fidelity equilibrium cycle calculations. As part of the work here, a new multi-cycle analysis capability was implemented in the DeCART code which included modifying the depletion modules to perform nuclide decay calculations, implementing an assembly shuffling pattern description, and modifying iteration schemes. During the work, stability issues were uncovered with respect to converging simultaneously the neutron flux,more » isotopics, and fluid density and temperature distributions in 3-D. Relaxation factors were implemented which considerably improved the stability of the convergence. To demonstrate the capability two core designs were utilized, a reference UOX core and a CORAIL core. Full core equilibrium cycle calculations were performed on both cores and the discharge isotopics were compared. From this comparison it was noted that the improved modeling capability was not drastically different in its prediction of the discharge isotopics when compared to 2-D single assembly or 2-D core models. For fissile isotopes such as U-235, Pu-239, and Pu-241 the relative differences were 1.91%, 1.88%, and 0.59%), respectively. While this difference may not seem large it translates to mass differences on the order of tens of grams per assembly, which may be significant for the purposes of accounting of special nuclear material. (authors)« less

Improved sample utilization in thermal ionization mass spectrometry isotope ratio measurements: refined development of porous ion emitters for nuclear forensic applications

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

Baruzzini, Matthew Louis

The precise and accurate determination of isotopic composition in nuclear forensic samples is vital for assessing origin, intended use and process history. Thermal ionization mass spectrometry (TIMS) is widely accepted as the gold standard for high performance isotopic measurements and has long served as the workhorse in the isotopic ratio determination of nuclear materials. Nuclear forensic and safeguard specialists have relied heavily on such methods for both routine and atypical e orts. Despite widespread use, TIMS methods for the assay of actinide systems continue to be hindered by poor ionization e ciency, often less than tenths of a percent; themore » majority of a sample is not measured. This represents a growing challenge in addressing nextgeneration nuclear detection needs by limiting the ability to analyze ultratrace quantities of high priority elements that could potentially provide critical nuclear forensic signatures. Porous ion emitter (PIE) thermal ion sources were developed in response to the growing need for new TIMS ion source strategies for improved ionization e ciency, PIEs have proven to be simple to implement, straightforward approach to boosting ion yield. This work serves to expand the use of PIE techniques for the analysis of trace quantities of plutonium and americium. PIEs exhibited superior plutonium and americium ion yields when compared to direct lament loading and the resin bead technique, one of the most e cient methods for actinide analysis, at similar mass loading levels. Initial attempts at altering PIE composition for the analysis of plutonium proved to enhance sample utilization even further. Preliminary investigations of the instrumental fractionation behavior of plutonium and uranium analyzed via PIE methods were conducted. Data collected during these initial trial indicate that PIEs fractionate in a consistent, reproducible manner; a necessity for high precision isotope ratio measurements. Ultimately, PIEs methods were applied for the age determination of various uranium isotopic standards. PIEs did not exhibit signi cant advantages for the determination of model ages when compared to traditional laments; however, this trial was able to provide valuable insight for guiding future investigations.« less

Signal or noise? Separating grain size-dependent Nd isotope variability from provenance shifts in Indus delta sediments, Pakistan

NASA Astrophysics Data System (ADS)

Jonell, T. N.; Li, Y.; Blusztajn, J.; Giosan, L.; Clift, P. D.

2017-12-01

Rare earth element (REE) radioisotope systems, such as neodymium (Nd), have been traditionally used as powerful tracers of source provenance, chemical weathering intensity, and sedimentary processes over geologic timescales. More recently, the effects of physical fractionation (hydraulic sorting) of sediments during transport have called into question the utility of Nd isotopes as a provenance tool. Is source terrane Nd provenance resolvable if sediment transport strongly induces noise? Can grain-size sorting effects be quantified? This study works to address such questions by utilizing grain size analysis, trace element geochemistry, and Nd isotope geochemistry of bulk and grain-size fractions (<63μm, 63-125 μm, 125-250 μm) from the Indus delta of Pakistan. Here we evaluate how grain size effects drive Nd isotope variability and further resolve the total uncertainties associated with Nd isotope compositions of bulk sediments. Results from the Indus delta indicate bulk sediment ɛNd compositions are most similar to the <63 µm fraction as a result of strong mineralogical control on bulk compositions by silt- to clay-sized monazite and/or allanite. Replicate analyses determine that the best reproducibility (± 0.15 ɛNd points) is observed in the 125-250 µm fraction. The bulk and finest fractions display the worst reproducibility (±0.3 ɛNd points). Standard deviations (2σ) indicate that bulk sediment uncertainties are no more than ±1.0 ɛNd points. This argues that excursions of ≥1.0 ɛNd points in any bulk Indus delta sediments must in part reflect an external shift in provenance irrespective of sample composition, grain size, and grain size distribution. Sample standard deviations (2s) estimate that any terrigenous bulk sediment composition should vary no greater than ±1.1 ɛNd points if provenance remains constant. Findings from this study indicate that although there are grain-size dependent Nd isotope effects, they are minimal in the Indus delta such that resolvable provenance-driven trends can be identified in bulk sediment ɛNd compositions over the last 20 k.y., and that overall provenance trends remain consistent with previous findings.

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.

135Cs/ 137Cs isotopic composition of environmental samples across Europe: Environmental transport and source term emission applications

DOE PAGES

Snow, Mathew S.; Snyder, Darin C.

2015-11-02

135Cs/ 137Cs isotopic analyses represent an important tool for studying the fate and transport of radiocesium in the environment; in this work the 135Cs/ 137Cs isotopic composition in environmental samples taken from across Europe is reported. Surface soil and vegetation samples from western Russia, Ukraine, Austria, and Hungary show consistent aged thermal fission product 135Cs/ 137Cs isotope ratios of 0.58 ± 0.01 (age corrected to 1/1/15), with the exception of one sample of soil-moss from Hungary which shows an elevated 135Cs/ 137Cs ratio of 1.78 ± 0.12. With the exception of the outlier sample from Hungary, surface soil/vegetation data aremore » in quantitative agreement with values previously reported for soils within the Chernobyl exclusion zone, suggesting that radiocesium at these locations is primarily composed of homogenous airborne deposition from Chernobyl. Seawater samples taken from the Irish Sea show 135Cs/ 137Cs isotope ratios of 1.22 ± 0.11 (age corrected to 1/1/15), suggesting aged thermal fission product Cs discharged from Sellafield. Furthermore, the differences in 135Cs/ 137Cs isotope ratios between Sellafield, Chernobyl, and global nuclear weapons testing fallout indicate that 135Cs/ 137Cs isotope ratios can be utilized to discriminate between and track radiocesium transport from different nuclear production source terms, including major emission sources in Europe.« less

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

PubMed

Liao, Wenta; Draper, William M

2013-02-21

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

Estimating the Triple-Point Isotope Effect and the Corresponding Uncertainties for Cryogenic Fixed Points

NASA Astrophysics Data System (ADS)

Tew, W. L.

2008-02-01

The sensitivities of melting temperatures to isotopic variations in monatomic and diatomic atmospheric gases using both theoretical and semi-empirical methods are estimated. The current state of knowledge of the vapor-pressure isotope effects (VPIE) and triple-point isotope effects (TPIE) is briefly summarized for the noble gases (except He), and for selected diatomic molecules including oxygen. An approximate expression is derived to estimate the relative shift in the melting temperature with isotopic substitution. In general, the magnitude of the effects diminishes with increasing molecular mass and increasing temperature. Knowledge of the VPIE, molar volumes, and heat of fusion are sufficient to estimate the temperature shift or isotopic sensitivity coefficient via the derived expression. The usefulness of this approach is demonstrated in the estimation of isotopic sensitivities and uncertainties for triple points of xenon and molecular oxygen for which few documented estimates were previously available. The calculated sensitivities from this study are considerably higher than previous estimates for Xe, and lower than other estimates in the case of oxygen. In both these cases, the predicted sensitivities are small and the resulting variations in triple point temperatures due to mass fractionation effects are less than 20 μK.

Analysis of Coolant Options for Advanced Metal Cooled Nuclear Reactors

DTIC Science & Technology

2006-12-01

24 Table 3.3 Hazards of Sodium Reaction Products, Hydride And Oxide...........................26 Table 3.4 Chemical Reactivity Of Selected...Liquid Metal Fast Breeder Reactor ORIGEN Oak Ridge Isotope Generator ORIGENARP Oak Ridge Isotope Generator Automated Rapid Processing PWR ...nuclear reactors, both because of the possibility of increased reactivity due to boiling and the potential loss of effectiveness of coolant heat transfer

LASER BIOLOGY AND MEDICINE: Laser analysis of the 13C/12C isotope ratio in CO2 in exhaled air

NASA Astrophysics Data System (ADS)

Stepanov, E. V.

2002-11-01

Tunable diode lasers (TDLs) are applied to the diagnostics of gastroenterological diseases using respiratory tests and preparations enriched with the stable 13C isotope. This method of the analysis of the 13C/12C isotope ratio in CO2 in exhaled air is based on the selective measurement of the resonance absorption at the vibrational — rotational structure of 12CO2 and 13CO2. The CO2 transmission spectra in the region of 4.35 μm were measured with a PbEuSe double-heterostructure TDL. The accuracy of carbon isotope ratio measurements in CO2 of exhaled air performed with the TDL was ~0.5%. The data of clinical tests of the developed laser-based analyser are presented.

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

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

Dodds, W. K.; Collins, S. M.; Hamilton, S. K.

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N available in sampled food sources such as decomposing leaves, epilithon, and fine particulate detritus over feeding periods of weeks or more. Thus, common methods of sampling food sources consumed by animals in streams do not sufficiently reflect the pool of N they assimilate. Lastly, Isotope tracer studies, combined with modeling andmore » food separation techniques, can improve estimation of N pools in food sources that are assimilated by consumers.« less

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

DOE PAGES

Dodds, W. K.; Collins, S. M.; Hamilton, S. K.; ...

2014-10-01

Analyses of 21 15N stable isotope tracer experiments, designed to examine food web dynamics in streams around the world, indicated that the isotopic composition of food resources assimilated by primary consumers (mostly invertebrates) poorly reflected the presumed food sources. Modeling indicated that consumers assimilated only 33–50% of the N available in sampled food sources such as decomposing leaves, epilithon, and fine particulate detritus over feeding periods of weeks or more. Thus, common methods of sampling food sources consumed by animals in streams do not sufficiently reflect the pool of N they assimilate. Lastly, Isotope tracer studies, combined with modeling andmore » food separation techniques, can improve estimation of N pools in food sources that are assimilated by consumers.« less

pH-dependent equilibrium isotope fractionation associated with the compound specific nitrogen and carbon isotope analysis of substituted anilines by SPME-GC/IRMS.

PubMed

Skarpeli-Liati, Marita; Turgeon, Aurora; Garr, Ashley N; Arnold, William A; Cramer, Christopher J; Hofstetter, Thomas B

2011-03-01

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.

The δ2H and δ18O of tap water from 349 sites in the United States and selected territories

USGS Publications Warehouse

Coplen, Tyler B.; Landwehr, Jurate M.; Qi, Haiping; Lorenz, Jennifer M.

2013-01-01

Because the stable isotopic compositions of hydrogen (δ2H) and oxygen (δ18O) of animal (including human) tissues, such as hair, nail, and urine, reflect the δ2H and δ18O of water and food ingested by an animal or a human and because the δ2H and δ18O of environmental waters vary geographically, δ2H and δ18O values of tap water samples collected in 2007-2008 from 349 sites in the United States and three selected U.S. territories have been measured in support of forensic science applications, creating one of the largest databases of tap water δ2H and δ18O values to date. The results of replicate isotopic measurements for these tap water samples confirm that the expanded uncertainties (U = 2μc) obtained over a period of years by the Reston Stable Isotope Laboratory from δ2H and δ18O dual-inlet mass spectrometric measurements are conservative, at ±2‰ and ±0.2 ‰, respectively. These uncertainties are important because U.S. Geological Survey data may be needed for forensic science applications, including providing evidence in court cases. Half way through the investigation, an isotope-laser spectrometer was acquired, enabling comparison of dual-inlet isotope-ratio mass spectrometric results with isotope-laser spectrometric results. The uncertainty of the laser-based δ2H measurement results for these tap water samples is comparable to the uncertainty of the mass spectrometric method, with the laser-based method having a slightly lower uncertainty. However, the δ18O uncertainty of the laser-based method is more than a factor of ten higher than that of the dual-inlet isotoperatio mass spectrometric method.

Selecting the best stable isotope mixing model to estimate grizzly bear diets in the Greater Yellowstone Ecosystem

PubMed Central

Hopkins, John B.; Ferguson, Jake M.; Tyers, Daniel B.; Kurle, Carolyn M.

2017-01-01

Past research indicates that whitebark pine seeds are a critical food source for Threatened grizzly bears (Ursus arctos) in the Greater Yellowstone Ecosystem (GYE). In recent decades, whitebark pine forests have declined markedly due to pine beetle infestation, invasive blister rust, and landscape-level fires. To date, no study has reliably estimated the contribution of whitebark pine seeds to the diets of grizzlies through time. We used stable isotope ratios (expressed as δ13C, δ15N, and δ34S values) measured in grizzly bear hair and their major food sources to estimate the diets of grizzlies sampled in Cooke City Basin, Montana. We found that stable isotope mixing models that included different combinations of stable isotope values for bears and their foods generated similar proportional dietary contributions. Estimates generated by our top model suggest that whitebark pine seeds (35±10%) and other plant foods (56±10%) were more important than meat (9±8%) to grizzly bears sampled in the study area. Stable isotope values measured in bear hair collected elsewhere in the GYE and North America support our conclusions about plant-based foraging. We recommend that researchers consider model selection when estimating the diets of animals using stable isotope mixing models. We also urge researchers to use the new statistical framework described here to estimate the dietary responses of grizzlies to declines in whitebark pine seeds and other important food sources through time in the GYE (e.g., cutthroat trout), as such information could be useful in predicting how the population will adapt to future environmental change. PMID:28493929

Selecting the best stable isotope mixing model to estimate grizzly bear diets in the Greater Yellowstone Ecosystem.

PubMed

Hopkins, John B; Ferguson, Jake M; Tyers, Daniel B; Kurle, Carolyn M

2017-01-01

Past research indicates that whitebark pine seeds are a critical food source for Threatened grizzly bears (Ursus arctos) in the Greater Yellowstone Ecosystem (GYE). In recent decades, whitebark pine forests have declined markedly due to pine beetle infestation, invasive blister rust, and landscape-level fires. To date, no study has reliably estimated the contribution of whitebark pine seeds to the diets of grizzlies through time. We used stable isotope ratios (expressed as δ13C, δ15N, and δ34S values) measured in grizzly bear hair and their major food sources to estimate the diets of grizzlies sampled in Cooke City Basin, Montana. We found that stable isotope mixing models that included different combinations of stable isotope values for bears and their foods generated similar proportional dietary contributions. Estimates generated by our top model suggest that whitebark pine seeds (35±10%) and other plant foods (56±10%) were more important than meat (9±8%) to grizzly bears sampled in the study area. Stable isotope values measured in bear hair collected elsewhere in the GYE and North America support our conclusions about plant-based foraging. We recommend that researchers consider model selection when estimating the diets of animals using stable isotope mixing models. We also urge researchers to use the new statistical framework described here to estimate the dietary responses of grizzlies to declines in whitebark pine seeds and other important food sources through time in the GYE (e.g., cutthroat trout), as such information could be useful in predicting how the population will adapt to future environmental change.

Identification of a novel acetate-utilizing bacterium belonging to Synergistes group 4 in anaerobic digester sludge.

PubMed

Ito, Tsukasa; Yoshiguchi, Kazumi; Ariesyady, Herto Dwi; Okabe, Satoshi

2011-12-01

Major acetate-utilizing bacterial and archaeal populations in methanogenic anaerobic digester sludge were identified and quantified by radioisotope- and stable-isotope-based functional analyses, microautoradiography-fluorescence in situ hybridization (MAR-FISH) and stable-isotope probing of 16S rRNA (RNA-SIP) that can directly link 16S rRNA phylogeny with in situ metabolic function. First, MAR-FISH with (14)C-acetate indicated the significant utilization of acetate by only two major groups, unidentified bacterial cells and Methanosaeta-like filamentous archaeal cells, in the digester sludge. To identify the acetate-utilizing unidentified bacteria, RNA-SIP was conducted with (13)C(6)-glucose and (13)C(3)-propionate as sole carbon source, which were followed by phylogenetic analysis of 16S rRNA. We found that bacteria belonging to Synergistes group 4 were commonly detected in both 16S rRNA clone libraries derived from the sludge incubated with (13)C-glucose and (13)C-propionate. To confirm that this bacterial group can utilize acetate, specific FISH probe targeting for Synergistes group 4 was newly designed and applied to the sludge incubated with (14)C-acetate for MAR-FISH. The MAR-FISH result showed that bacteria belonging to Synergistes group 4 significantly took up acetate and their active population size was comparable to that of Methanosaeta in this sludge. In addition, as bacteria belonging to Synergistes group 4 had high K(m) for acetate and maximum utilization rate, they are more competitive for acetate over Methanosaeta at high acetate concentrations (2.5-10  mM). To our knowledge, it is the first time to report the acetate-utilizing activity of uncultured bacteria belonging to Synergistes group 4 and its competitive significance to acetoclastic methanogen, Methanosaeta.

Identification of a novel acetate-utilizing bacterium belonging to Synergistes group 4 in anaerobic digester sludge

PubMed Central

Ito, Tsukasa; Yoshiguchi, Kazumi; Ariesyady, Herto Dwi; Okabe, Satoshi

2011-01-01

Major acetate-utilizing bacterial and archaeal populations in methanogenic anaerobic digester sludge were identified and quantified by radioisotope- and stable-isotope-based functional analyses, microautoradiography-fluorescence in situ hybridization (MAR-FISH) and stable-isotope probing of 16S rRNA (RNA-SIP) that can directly link 16S rRNA phylogeny with in situ metabolic function. First, MAR-FISH with 14C-acetate indicated the significant utilization of acetate by only two major groups, unidentified bacterial cells and Methanosaeta-like filamentous archaeal cells, in the digester sludge. To identify the acetate-utilizing unidentified bacteria, RNA-SIP was conducted with 13C6-glucose and 13C3-propionate as sole carbon source, which were followed by phylogenetic analysis of 16S rRNA. We found that bacteria belonging to Synergistes group 4 were commonly detected in both 16S rRNA clone libraries derived from the sludge incubated with 13C-glucose and 13C-propionate. To confirm that this bacterial group can utilize acetate, specific FISH probe targeting for Synergistes group 4 was newly designed and applied to the sludge incubated with 14C-acetate for MAR-FISH. The MAR-FISH result showed that bacteria belonging to Synergistes group 4 significantly took up acetate and their active population size was comparable to that of Methanosaeta in this sludge. In addition, as bacteria belonging to Synergistes group 4 had high Km for acetate and maximum utilization rate, they are more competitive for acetate over Methanosaeta at high acetate concentrations (2.5–10 m). To our knowledge, it is the first time to report the acetate-utilizing activity of uncultured bacteria belonging to Synergistes group 4 and its competitive significance to acetoclastic methanogen, Methanosaeta. PMID:21562600

Isotope separation apparatus and method

DOEpatents

Cotter, Theodore P.

1982-12-28

The invention relates to a method and apparatus for laser isotope separation by photodeflection. A molecular beam comprising at least two isotopes to be separated intersects, preferable substantially perpendicular to one broad side of the molecular beam, with a laser beam traveling in a first direction. The laser beam is reflected back through the molecular beam, preferably in a second direction essentially opposite to the first direction. The laser beam comprises .pi.-pulses of a selected wavelength which excite unexcited molecules, or cause stimulated emission of excited molecules of one of the isotopes. Excitation caused by first direction .pi.-pulses moves molecules of the isotope excited thereby in the first direction. Stimulated emission of excited molecules of the isotope is brought about by returning .pi.-pulses traveling in the second direction. Stimulated emission moves emitting molecules in a direction opposite to the photon emitted. Because emitted photons travel in the second direction, emitting molecules move in the first direction. Substantial molecular movement is accomplished by a large number of .pi.-pulse-molecule interactions. A beam corer collects the molecules in the resulting enriched divergent portions of the beam.

The production of ultra-high purity single isotopes or tailored isotope mixtures by ICP-MS

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

Liezers, Martin; Farmer, Orville T.; Dion, Michael P.

2015-01-01

We report the development and testing of a simple collector arrangement for a commercial quadrupole ICP-MS that for the first time has been used to produce small quantities of highly enriched (>99.99%) single isotopes, with deposition rates >10 ng/hour. The collector assembly replaces the standard instrument detector allowing for implantation with simultaneous monitoring of the incident ion current. Even under zero bias implant conditions, low energy (<10 eV), ion collection efficiency was observed to be very high ~99%. 151Eu ion currents of 0.1-0.5 nA were collected on a simple, planar foil without resorting to any type of cup configuration. Recoverymore » of the enriched isotope from such foils is much simpler than from a more complex cup configuration. High rejection of adjacent mass isotopes was demonstrated by selectively implanting 167Er without any discernible co-implantation of 166Er and 168Er. The important analytical possibilities of the new approach to isotope ratio measurement, tracer purification and radiation measurements are discussed.« less

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.

Impact investigation of reactor fuel operating parameters on reactivity for use in burnup credit applications

NASA Astrophysics Data System (ADS)

Sloma, Tanya Noel

When representing the behavior of commercial spent nuclear fuel (SNF), credit is sought for the reduced reactivity associated with the net depletion of fissile isotopes and the creation of neutron-absorbing isotopes, a process that begins when a commercial nuclear reactor is first operated at power. Burnup credit accounts for the reduced reactivity potential of a fuel assembly and varies with the fuel burnup, cooling time, and the initial enrichment of fissile material in the fuel. With regard to long-term SNF disposal and transportation, tremendous benefits, such as increased capacity, flexibility of design and system operations, and reduced overall costs, provide an incentive to seek burnup credit for criticality safety evaluations. The Nuclear Regulatory Commission issued Interim Staff Guidance 8, Revision 2 in 2002, endorsing burnup credit of actinide composition changes only; credit due to actinides encompasses approximately 30% of exiting pressurized water reactor SNF inventory and could potentially be increased to 90% if fission product credit were accepted. However, one significant issue for utilizing full burnup credit, compensating for actinide and fission product composition changes, is establishing a set of depletion parameters that produce an adequately conservative representation of the fuel's isotopic inventory. Depletion parameters can have a significant effect on the isotopic inventory of the fuel, and thus the residual reactivity. This research seeks to quantify the reactivity impact on a system from dominant depletion parameters (i.e., fuel temperature, moderator density, burnable poison rod, burnable poison rod history, and soluble boron concentration). Bounding depletion parameters were developed by statistical evaluation of a database containing reactor operating histories. The database was generated from summary reports of commercial reactor criticality data. Through depletion calculations, utilizing the SCALE 6 code package, several light water reactor assembly designs and in-core locations are analyzed in establishing a combination of depletion parameters that conservatively represent the fuel's isotopic inventory as an initiative to take credit for fuel burnup in criticality safety evaluations for transportation and storage of SNF.

Neocytolysis contributes to the anemia of renal disease

NASA Technical Reports Server (NTRS)

Rice, L.; Alfrey, C. P.; Driscoll, T.; Whitley, C. E.; Hachey, D. L.; Suki, W.

1999-01-01

Neocytolysis is a recently described physiological process affecting the selective hemolysis of young red blood cells in circumstances of plethora. Erythropoietin (EPO) depression appears to initiate the process, providing the rationale to investigate its contributions to the anemia of renal disease. When EPO therapy was withheld, four of five stable hemodialysis patients showed chromium 51 (51Cr)-red cell survival patterns indicative of neocytolysis; red cell survival was short in the first 9 days, then normalized. Two of these four patients received oral 13C-glycine and 15N-glycine, and there was a suggestion of pathological isotope enrichment of stool porphyrins when EPO therapy was held, again supporting selective hemolysis of newly released red cells that take up the isotope (one patient had chronic hemolysis indicated by isotope studies of blood and stool). Thus, neocytolysis can contribute to the anemia of renal disease and explain some unresolved issues about such anemia. One implication is the prediction that intravenous bolus EPO therapy is metabolically and economically inefficient compared with lower doses administered more frequently subcutaneously.

Site-selective nitrogen isotopic ratio measurement of nitrous oxide using a TE-cooled CW-RT-QCL based spectrometer.

PubMed

Li, Jingsong; Zhang, Lizhu; Yu, Benli

2014-12-10

The feasibility of laser spectroscopic isotopic composition measurements of atmospheric N2O was demonstrated, although making them useful will require further improvements. The system relies on a thermoelectrically (TE) cooled continuous-wave (CW) room temperature (RT) quantum cascade laser source emitting wavelength of around 4.6μm, where strong fundamental absorption bands occur for the considered specie and its isotopomers. The analysis technique is based on wavelength modulation spectroscopy with second-harmonic detection and the combination of long-path absorption cell. Primary laboratory tests have been performed to estimate the achievable detection limits and the signal reproducibility levels in view of possible measurements of (15)N/(14)N and (18)O/(16)O isotope ratios. The experiment results showed that the site-selective (15)N/(14)N ratio can be measured with a precision of 3‰ with 90s averaging time using natural-abundance N2O sample of 12.7ppm. Copyright © 2014 Elsevier B.V. All rights reserved.

Stable isotope fractionation of tungsten during adsorption on Fe and Mn (oxyhydr)oxides

NASA Astrophysics Data System (ADS)

Kashiwabara, Teruhiko; Kubo, Sayuri; Tanaka, Masato; Senda, Ryoko; Iizuka, Tsuyoshi; Tanimizu, Masaharu; Takahashi, Yoshio

2017-05-01

The similar, but not identical chemical properties of W compared with Mo suggest that the stable isotope system of W could be a novel proxy to explore the modern and ancient ocean as is the case in the well-established utility of Mo isotopes. We experimentally investigated the isotopic fractionation of W during adsorption on Fe and Mn (oxyhydr)oxides (ferrihydrite and δ-MnO2), a key process in the global ocean budget of this element. Our adsorption experiments confirmed that W isotopes fractionate substantially on both ferrihydrite and δ-MnO2: lighter W isotopes are preferentially adsorbed on both oxides as a result of equilibrium isotopic exchange between dissolved and adsorbed species, and the obtained values of Δ186/183Wliquid-solid (= δ186Wdissolved - δ186Wadsorbed) are 0.76 ± 0.09‰ for ferrihydrite and 0.88 ± 0.21‰ for δ-MnO2 (2σ, n = 6). Compared with the case of Mo isotopes, fractionation of W isotopes is (i) of comparable magnitude between ferrihydrite and δ-MnO2, and (ii) much smaller than that of Mo on δ-MnO2. Our previous XAFS observations and newly-performed DFT calculations both indicate that the observed W isotopic fractionations are caused by the symmetry change from Td (tetrahedral) WO42- to distorted Oh (octahedral) monomeric W species via formation of inner-sphere complexes on both ferrihydrite and δ-MnO2. The similar isotopic fractionations between the two oxides relate to the strong tendency for W to form inner-sphere complexes, which causes the symmetry change, in contrast to the outer-sphere complex of Mo on ferrihydrite. The smaller isotopic fractionation of W compared with Mo on δ-MnO2 despite their similar molecular symmetry seems to be due to their different degrees of distortion of Oh species. Our findings imply that the isotopic composition of W in modern oxic seawater is likely to become heavier relative to the input by removal of lighter W isotopes via adsorption on ferromanganese oxides in analogy with the Mo isotope budget. In contrast, the isotopic composition of W in ancient seawater should have evolved in response to the extent of deposition of both Fe and Mn oxides; this is likely to be different compared with that of the Mo isotopes, which is strongly associated with the occurrence of Mn oxides relative to Fe oxides.

Dual-Carbon sources fuel the OCS deep-reef Community, a stable isotope investigation

USGS Publications Warehouse

Sulak, Kenneth J.; Berg, J.; Randall, Michael T.; Dennis, George D.; Brooks, R.A.

2008-01-01

The hypothesis that phytoplankton is the sole carbon source for the OCS deep-reef community (>60 m) was tested. Trophic structure for NE Gulf of Mexico deep reefs was analyzed via carbon and nitrogen stable isotopes. Carbon signatures for 114 entities (carbon sources, sediment, fishes, and invertebrates) supported surface phytoplankton as the primary fuel for the deep reef. However, a second carbon source, the macroalga Sargassum, with its epiphytic macroalgal associate, Cladophora liniformis, was also identified. Macroalgal carbon signatures were detected among 23 consumer entities. Most notably, macroalgae contributed 45 % of total carbon to the 13C isotopic spectrum of the particulate-feeding reef-crest gorgonian Nicella. The discontinuous spatial distribution of some sessile deep-reef invertebrates utilizing pelagic macroalgal carbon may be trophically tied to the contagious distribution of Sargassum biomass along major ocean surface features.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

USGS Publications Warehouse

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

2018-01-01

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

Carbon isotope fractionation by sulfate-reducing bacteria using different pathways for the oxidation of acetate.

PubMed

Goevert, Dennis; Conrad, Ralf

2008-11-01

Acetate is a key intermediate in the anaerobic degradation of organic matter. In anoxic environments, available acetate is a competitive substrate for sulfate-reducing bacteria (SRB) and methane-producing archaea. Little is known about the fractionation of carbon isotopes by sulfate reducers. Therefore, we determined carbon isotope compositions in cultures of three acetate-utilizing SRB, Desulfobacter postgatei, Desulfobacter hydrogenophilus, and Desulfobacca acetoxidans. We found that these species showed strong differences in their isotope enrichment factors (epsilon) of acetate. During the consumption of acetate and sulfate, acetate was enriched in 13C by 19.3% per hundred in Desulfobacca acetoxidans. By contrast, both D. postgatei and D. hydrogenophilus showed a slight depletion of 13C resulting in epsilon(ac)-values of 1.8 and 1.5% per hundred, respectively. We suggest that the different isotope fractionation is due to the different metabolic pathways for acetate oxidation. The strongly fractionating Desulfobacca acetoxidans uses the acetyl-CoA/carbon monoxide dehydrogenase pathway, which is also used by acetoclastic methanogens that show a similar fractionation of acetate (epsilon(ac) = -21 to -27% per hundred). In contrast, Desulfobacter spp. oxidize acetate to CO2 via the tricarboxylic acid (TCA) cycle and apparently did not discriminate against 13C. Our results suggestthat carbon isotope fractionation in environments with sulfate reduction will strongly depend on the composition of the sulfate-reducing bacterial community oxidizing acetate.

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.

The uranium-isotopic composition of Saharan dust collected over the central Atlantic Ocean

NASA Astrophysics Data System (ADS)

Aciego, Sarah M.; Aarons, Sarah M.; Sims, Kenneth W. W.

2015-06-01

Uranium isotopic compositions, (234U/238U)activity , are utilized by earth surface disciplines as chronometers and source tracers, including in soil science where aeolian dust is a significant source to the total nutrient pool. However, the (234U/238U)activity composition of dust is under characterized due to material and analytical constraints. Here we present new uranium isotope data measured by high precision MC-ICP-MS on ten airborne dust samples collected on the M55 trans-Atlantic cruise in 2002. Two pairs of samples are presented with different size fractions, coarse (1-30 μm) and fine (<1 μm), and all samples were processed to separate the water soluble component in order to assess the controls on the (234U/238U)activity of mineral aerosols transported from the Sahara across the Atlantic. Our results indicate (234U/238U)activity above one for both the water soluble (1.13-1.17) and the residual solid (1.06-1.18) fractions of the dust; no significant correlation is found between isotopic composition and travel distance. Residual solids indicate a slight dependance of (234U/238U)activity on particle size. Future modeling work that incorporates dust isotopic compositions into mixing or isotopic fractionation models will need to account for the wide variability in dust (234U/238U)activity .

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.

Isotopic disproportionation during hydrogen isotopic analysis of nitrogen-bearing organic compounds

USGS Publications Warehouse

Nair, Sreejesh; Geilmann, Heike; Coplen, Tyler B.; Qi, Haiping; Gehre, Matthias; Schimmelmann, Arndt; Brand, Willi A.

2015-01-01

Rationale High-precision hydrogen isotope ratio analysis of nitrogen-bearing organic materials using high-temperature conversion (HTC) techniques has proven troublesome in the past. Formation of reaction products other than molecular hydrogen (H2) has been suspected as a possible cause of incomplete H2 yield and hydrogen isotopic fractionation. Methods The classical HTC reactor setup and a modified version including elemental chromium, both operated at temperatures in excess of 1400 °C, have been compared using a selection of nitrogen-bearing organic compounds, including caffeine. A focus of the experiments was to avoid or suppress hydrogen cyanide (HCN) formation and to reach quantitative H2 yields. The technique also was optimized to provide acceptable sample throughput. Results The classical HTC reaction of a number of selected compounds exhibited H2 yields from 60 to 90 %. Yields close to 100 % were measured for the experiments with the chromium-enhanced reactor. The δ2H values also were substantially different between the two types of experiments. For the majority of the compounds studied, a highly significant relationship was observed between the amount of missing H2and the number of nitrogen atoms in the molecules, suggesting the pyrolytic formation of HCN as a byproduct. A similar linear relationship was found between the amount of missing H2 and the observed hydrogen isotopic result, reflecting isotopic fractionation. Conclusions The classical HTC technique to produce H2 from organic materials using high temperatures in the presence of glassy carbon is not suitable for nitrogen-bearing compounds. Adding chromium to the reaction zone improves the yield to 100 % in most cases. The initial formation of HCN is accompanied by a strong hydrogen isotope effect, with the observed hydrogen isotope results on H2 being substantially shifted to more negative δ2H values. The reaction can be understood as an initial disproportionation leading to H2 and HCN with the HCN-hydrogen systematically enriched in 2H by more than 50 ‰. In the reaction of HCN with chromium, H2 and chromium-containing solid residues are formed quantitatively.

Estimation of Plutonium-240 Mass in Waste Tanks Using Ultra-Sensitive Detection of Radioactive Xenon Isotopes from Spontaneous Fission

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

Bowyer, Theodore W.; Gesh, Christopher J.; Haas, Daniel A.

This report details efforts to develop a technique which is able to detect and quantify the mass of 240Pu in waste storage tanks and other enclosed spaces. If the isotopic ratios of the plutonium contained in the enclosed space is also known, then this technique is capable of estimating the total mass of the plutonium without physical sample retrieval and radiochemical analysis of hazardous material. Results utilizing this technique are reported for a Hanford Site waste tank (TX-118) and a well-characterized plutonium sample in a laboratory environment.

Evolutionary differences in Δ13C detected between spore and seed bearing plants following exposure to a range of atmospheric O2:CO2 ratios; implications for paleoatmosphere reconstruction

NASA Astrophysics Data System (ADS)

Porter, Amanda S.; Yiotis, Charilaos; Montañez, Isabel P.; McElwain, Jennifer C.

2017-09-01

The stable carbon isotopes of fossil plants are a reflection of the atmosphere and environment in which they grew. Fossil plant remains have thus stored information about the isotopic composition and concentration of atmospheric carbon dioxide (pCO2) and possibly pO2 through time. Studies to date, utilizing extant plants, have linked changes in plant stable carbon isotopes (δ13Cp) or carbon isotope discrimination (Δ13C) to changes in pCO2 and/or pO2. These studies have relied heavily on angiosperm representatives, a phylogenetic group only present in the fossil record post-Early Cretaceous (∼140 million years ago (mya)), whereas gymnosperms, monilophytes and lycophytes dominated terrestrial ecosystems prior to this time. The aim of this study was to expand our understanding of carbon isotope discrimination in all vascular plant groups of C3 plants including lycophytes, monilophytes, gymnosperms and angiosperms, under elevated CO2 and sub-ambient O2 to explore their utility as paleo-atmospheric proxies. To achieve this goal, plants were grown in controlled environment chambers under a range of O2:CO2 ratio treatments. Results reveal a strong phylogenetic dependency on Δ13C, where spore-bearing (lycophytes and monilophytes) have significantly higher 13C discrimination than seed plants (gymnosperms and angiosperms) by ∼5‰. We attribute this strong phylogenetic signal to differences in Ci/Ca likely mediated by fundamental differences in how spore and seed bearing plants control stomatal aperture. Decreasing O2:CO2 ratio in general resulted in increased carbon isotope discrimination in all plant groups. Notably, while all plant groups respond unidirectionally to elevated atmospheric CO2 (1900 ppm and ambient O2), they do not respond equally to sub-ambient O2 (16%). We conclude that (1) Δ13C has a strong phylogenetic or 'reproductive grade' bias, whereby Δ13C of spore reproducing plants is significantly different to seed reproducing taxa. (2) Δ13C increases with decreasing O2:CO2 ratios (where significant) but is more likely a result of mechanistically uncoupled responses to elevated pCO2 and sub-ambient O2; and (3) due to this response we find δ13Ca cannot be calculated from δ13Cp unless environmental influences such as O2:CO2 ratio can be independently constrained. Therefore, interpretations of trends in fossil plant δ13Cp to reconstruct paleoatmospheric CO2 concentration should include cross calibration based on a nearest living relative, appropriate nearest living equivalent, or utilizing the phylogenetic corrections produced from this study.

Differential resource utilization by extant great apes and australopithecines: towards solving the C4 conundrum.

PubMed

Sponheimer, Matt; Lee-Thorp, Julia A

2003-09-01

Morphological and biogeochemical evidence suggest that australopithecines had diets markedly different from those of extant great apes. Stable carbon isotope analysis, for example, has shown that significant amounts of the carbon consumed by australopithecines were derived from C(4) photosynthesis in plants. This means that australopithecines were eating large quantities of C(4) plants such as tropical grasses and sedges, or were eating animals that were themselves eating C(4) plants. In contrast, there is no evidence that modern apes consume appreciable amounts of any of these foods, even in the most arid extents of their ranges where these foods are most prevalent. Environmental reconstructions of early australopithecine environments overlap with modern chimpanzee habitats. This, in conjunction with the stable isotope evidence, suggests that australopithecines and great apes, even in similar environments, would utilize available resources differently. Thus, the desire or capacity to use C(4) foods may be a basal character of our lineage. We do not know, however, which of the nutritionally disparate C(4) foods were utilized by hominids. Here we discuss which C(4) resources were most likely consumed by australopithecines, as well as the potential nutritional, physiological, and social consequences of eating these foods.

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

USGS Publications Warehouse

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

2004-01-01

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

Separation of uranium isotopes by chemical exchange

DOEpatents

Ogle, P.R. Jr.

1974-02-26

A chemical exchange method is provided for separating /sup 235/U from / sup 238/U comprising contacting a first phase containing UF/sub 6/ with a second phase containing a compound selected from the group consisting of NOUF/sub 6/, NOUF/sub 7/, and NO/sub 2/UF/sub 7/ until the U Fsub 6/ in the first phase becomes enriched in the /sup 235/U isotope. (Official Gazette)

Highly efficient preparation of selectively isotope cluster-labeled long chain fatty acids via two consecutive C(sp3)-C(sp3) cross-coupling reactions.

PubMed

Lethu, Sébastien; Matsuoka, Shigeru; Murata, Michio

2014-02-07

An efficient synthesis involving two copper-catalyzed alkyl-alkyl coupling reactions has been designed to easily access doubly isotope-labeled fatty acids. Such NMR- and IR-active compounds were obtained in excellent overall yields and will be further used for determining the conformation of an alkyl chain of lipidic biomolecules upon interaction with proteins.

Radioisotope Concentration in Lake Sediments of Maracaibo, Venezuela

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

Salas, A. Rangel; Viloria, T.; Sajo-Bohus, L.

2007-10-26

Maracaibo Lake is one of the most important water basing and oil producing regions in Venezuela. Changes in the local environment have been monitored for chemical pollution in the past. For this study we selected a set of sediment samples collected in the shore and analyzed for its radioisotope content. Results show the gamma emitting isotopes distribution. Isotopes concentrations have been determined within the natural K, Th and U families.

Isotope ratio mass spectrometry in nutrition research

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

Luke, A.H.

Many of the biochemical pathways and processes that form the foundation of modern nutrition research was elucidated using stable isotopes as physiological tracers. Since the discovery of stable isotopes, improvements and innovations in mass spectrometry and chromatography have led to greatly expanded applications. This research project was designed to evaluate gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) as a tool for isotopic tracer studies and to delineate the operational parameters for the analysis of {sup 13}C-labeled cholesterol, leucine and {alpha}-ketoisocaproate. The same isotope ratio mass spectrometer was then used as the base instrument for the ratio mass spectrometer was then usedmore » as the base instrument for the development of two additional inlet systems: a continuous-flow inlet for the analyses of {sup 13}C and {sup 18}O as CO{sub 2} and a filament inlet for on-line combustion and isotopic analysis of non-volatile organic compounds. Each of these three inlets was evaluated and their utility in nutrition research illustrated. GC/C/IRMS was used to analyze cholesterol, leucine and {alpha}-ketoisocaproate with good accuracy, precision and little isotopic memory. For all three compounds the detection limits achieved well surpassed currently used technologies. For compounds that can be well separated by GC, GC/C/IRMS is a valuable analytical tool. The continuous-flow inlet provided good accuracy and precision for measurements of {sup 13}CO{sub 2} from breath tests and {sup 18}O as CO{sub 2} from total energy expenditure tests. Most importantly, the continuous-flow inlet increased sample throughput by at least a factor of three over conventional analytical techniques. The filament inlet provided accurate and precise {sup 13}C ratio measurements of both natural abundance and enriched standards of non-volatile organic compounds of physiological interest.« less

Hydrogen stable isotopic constraints on methane emissions from oil and gas extraction in the Colorado Front Range, USA

NASA Astrophysics Data System (ADS)

Townsend-Small, A.; Botner, E. C.; Jimenez, K.; Blake, N. J.; Schroeder, J.; Meinardi, S.; Barletta, B.; Simpson, I. J.; Blake, D. R.; Flocke, F. M.; Pfister, G.; Bon, D.; Crawford, J. H.

2015-12-01

The climatic implications of a shift from oil and coal to natural gas depend on the magnitude of fugitive emissions of methane from the natural gas supply chain. Attempts to constrain methane emissions from natural gas production regions can be confounded by other sources of methane. Here we demonstrate the utility of stable isotopes, particularly hydrogen isotopes, for source apportionment of methane emissions. The Denver, Colorado area is home to a large oil and gas field with both conventional oil and gas wells and newer hydraulic fracturing wells. The region also has a large metropolitan area with several landfills and a sizable cattle population. As part of the DISCOVER-AQ and FRAPPE field campaigns in summer 2014, we collected three types of canister samples for analysis of stable isotopic composition of methane: 1), samples from methane sources; 2), samples from two stationary ground sites, one in the Denver foothills, and one in an oil and gas field; and 3), from the NCAR C-130 aircraft in samples upwind and downwind of the region. Our results indicate that hydrogen isotope ratios are excellent tracers of sources of methane in the region, as we have shown previously in California and Texas. Use of carbon isotope ratios is complicated by the similarity of natural gas isotope ratios to that of background methane. Our results indicate that, despite the large amount of natural gas production in the region, biological sources such as cattle feedlots and landfills account for at least 50% of total methane emissions in the Front Range. Future work includes comparison of isotopes and alkane ratios as tracers of methane sources, and calculation of total methane fluxes in the region using continuous measurements of methane concentrations during aircraft flights.

Utility of multiple chemical techniques in archaeological residential mobility studies: case studies from Tiwanaku- and Chiribaya-affiliated sites in the Andes.

PubMed

Knudson, Kelly J; Price, T Douglas

2007-01-01

In the south central Andes, archaeologists have long debated the extent of Tiwanaku colonization during the Middle Horizon (AD 500-1000). We tested the hypotheses regarding the nature of Tiwanaku influence using strontium isotope, trace element concentration, and oxygen isotope data from archaeological human tooth enamel and bone from Tiwanaku- and Chiribaya-affiliated sites in the south central Andes. Strontium isotope analysis of 25 individuals buried at the Tiwanaku-affiliated Moquegua Valley site of Chen Chen demonstrates that it was likely a Tiwanaku colony. In contrast, no immigrants from the Lake Titicaca Basin were present in 27 individuals analyzed from the San Pedro de Atacama cemeteries of Coyo Oriental, Coyo-3, and Solcor-3; it is likely that these sites represent economic and religious alliances, but not colonies. However, strontium isotope analysis alone cannot distinguish movement between the Tiwanaku- and Chiribaya-affiliated sites in the Moquegua and Ilo Valleys of southern Peru. Analyzing oxygen isotope and trace element concentration data and comparing it with strontium isotope data from the same individuals provides a more detailed picture of residential mobility in the Tiwanaku and Chiribaya polities. In addition to monitoring diagenetic contamination, trace element concentration data identified movement during adulthood for certain individuals. However, these data could not distinguish movement between the Moquegua and Ilo Valleys. While oxygen isotope data could clearly distinguish the high-altitude sites from others, more data is needed to characterize the local oxygen isotope ratios of these regions. These data demonstrate the potential for archaeological reconstruction of residential mobility through multiple lines of evidence. (c) 2006 Wiley-Liss, Inc

Differential soil water sourcing of managed Loblolly Pine and Sweet Gum revealed by stable isotopes in the Upper Coastal Plain, USA

NASA Astrophysics Data System (ADS)

Brockman, L. E.; Younger, S. E.; Jackson, C. R.; McDonnell, J.; Janzen, K. F.

2017-12-01

Stable isotope signatures of stem water can illuminate where in the soil profile different types of trees are accessing soil water and thereby contribute to our understanding of water movement through the soil plant atmosphere continuum. The objective of this study was to use 2H and 18O isotopes to characterize water sources of fourteen-year-old intensively managed Loblolly Pine and Sweet Gum stands in replicated (n=3) paired plots. In order to differentiate the isotopic signatures of tree and soil water, both species and five soil depths were sampled monthly for one year. Tree sap and soil water were extracted cryogenically and their isotopic signatures were determined. Although plant water uptake is generally considered a non-fractionating process, our dataset suggests a source of fractionation in 2H signatures in both species and during most of the thirteen sampling events. As a result, only the 18O isotopic data were used to determine the vertical distribution of soil water contributions to stem water. Statistically, we grouped the five soil sampling depths into three isotopic horizons. Shallow, intermediate and deep soil represent sampling depths of 0-10cm, 30-70cm and 100-125cm, respectively. These isotopic horizons were used in a direct inference approach and Bayesian mixing model analysis to determine the origin of stem water. In this study, Loblolly Pine used more water from intermediate and deep soil while Sweet Gum used more water from shallow and intermediate soil. In the winter months, January through March, Loblolly Pine transpired primarily deep soil where as Sweet Gum mainly utilized shallow soil for transpiration. These results indicate that both species have opportunistic water use patterns with seasonal variation.

A Portable, Field-Deployable Analyzer for Isotopic Water Measurements

NASA Astrophysics Data System (ADS)

Berman, E. S.; Gupta, M.; Huang, Y. W.; Lacelle, D.; McKay, C. P.; Fortson, S.

2015-12-01

Water stable isotopes have for many years been used to study the hydrological cycle, catchment hydrology, and polar climate among other applications. Typically, discrete water samples are collected and transported to a laboratory for isotope analysis. Due to the expense and labor associated with such sampling, isotope studies have generally been limited in scope and time-resolution. Field sampling of water isotopes has been shown in recent years to provide dense data sets with the increased time resolution illuminating substantially greater short term variability than is generally observed during discrete sampling. A truly portable instrument also opens the possibility to utilize the instrument as a tool for identifying which water samples would be particularly interesting for further laboratory investigation. To make possible such field measurements of liquid water isotopes, Los Gatos Research has developed a miniaturized, field-deployable liquid water isotope analyzer. The prototype miniature liquid water isotope analyzer (mini-LWIA) uses LGR's patented Off-Axis ICOS (Integrated Cavity Output Spectroscopy) technology in a rugged, Pelican case housing for easy transport and field operations. The analyzer simultaneously measures both δ2H and δ18O from liquid water, with both manual and automatic water introduction options. The laboratory precision for δ2H is 0.6 ‰, and for δ18O is 0.3 ‰. The mini-LWIA was deployed in the high Arctic during the summer of 2015 at Inuvik in the Canadian Northwest Territories. Samples were collected from Sachs Harbor, on the southwest coast of Banks Island, including buried basal ice from the Lurentide Ice Sheet, some ice wedges, and other types of ground ice. Methodology and water analysis results from this extreme field deployment will be presented.

Constraints on Martian Differentiation Processes from Rb-Sr and Sm-Nd Isotopic Analyses of the Basaltic Shergottite QUE 94201

NASA Technical Reports Server (NTRS)

Borg, Lars E.; Nyquist, Larry E.; Taylor, Larry A.; Wiesmann, Henry; Shih, Chi-Y.

1997-01-01

Isotopic analyses of mineral, leachate, and whole rock fractions from the Martian shergottite meteorite QUE 94201 yield Rb-Sr and Sm-Nd crystallization ages of 327 +/- 12 and 327 +/- 19 Ma, respectively. These ages are concordant, although the isochrons are defined by different fractions within the meteorite. Comparison of isotope dilution Sm and Nd data for the various QUE 94201 fractions with in situ ion microprobe data for QUE 94201 minerals from the literature demonstrate the presence of a leachable crustal component in the meteorite. This component is likely to have been added to QUE 94201 by secondary alteration processes on Mars, and can affect the isochrons by selectively altering the isotopic systematics of the leachates and some of the mineral fractions. The absence of crustal recycling processes on Mars may preserve the geochemical evidence for early differentiation and the decoupling of the Rb-Sr and Sm-Nd isotopic systems, underscoring one of the fundamental differences between geologic processes on Mars and the Earth.

The plasma separation process as a pre-cursor for large scale radioisotope production

NASA Astrophysics Data System (ADS)

Stevenson, Nigel R.

2001-07-01

Radioisotope production generally employs either accelerators or reactors to convert stable (usually enriched) isotopes into the desired product species. Radioisotopes have applications in industry, environmental sciences, and most significantly in medicine. The production of many potentially useful radioisotopes is significantly hindered by the lack of availability or by the high cost of key enriched stable isotopes. To try and meet this demand, certain niche enrichment processes have been developed and commercialized. Calutrons, centrifuges, and laser separation processes are some of the devices and techniques being employed to produce large quantities of selective enriched stable isotopes. Nevertheless, the list of enriched stable isotopes in sufficient quantities remains rather limited and this continues to restrict the availability of many radioisotopes that otherwise could have a significant impact on society. The Plasma Separation Process is a newly available commercial technique for producing large quantities of a wide range of enriched isotopes and thereby holds promise of being able to open the door to producing new and exciting applications of radioisotopes in the future.

Intracellular metabolite levels shape sulfur isotope fractionation during microbial sulfate respiration

PubMed Central

Wing, Boswell A.; Halevy, Itay

2014-01-01

We present a quantitative model for sulfur isotope fractionation accompanying bacterial and archaeal dissimilatory sulfate respiration. By incorporating independently available biochemical data, the model can reproduce a large number of recent experimental fractionation measurements with only three free parameters: (i) the sulfur isotope selectivity of sulfate uptake into the cytoplasm, (ii) the ratio of reduced to oxidized electron carriers supporting the respiration pathway, and (iii) the ratio of in vitro to in vivo levels of respiratory enzyme activity. Fractionation is influenced by all steps in the dissimilatory pathway, which means that environmental sulfate and sulfide levels control sulfur isotope fractionation through the proximate influence of intracellular metabolites. Although sulfur isotope fractionation is a phenotypic trait that appears to be strain specific, we show that it converges on near-thermodynamic behavior, even at micromolar sulfate levels, as long as intracellular sulfate reduction rates are low enough (<<1 fmol H2S⋅cell−1⋅d−1). PMID:25362045

Systematic study on the isotopic behavior of fusion barrier using the density-dependent nucleon-nucleon interactions

NASA Astrophysics Data System (ADS)

Ghodsi, O. N.; Khalaj, M.

By changing the neutron and nuclear matter incompressibility constant K, we investigate the isotopic behavior of the fusion barriers for the collision of large number of different isotopes with condition of 0.7 ≤ N/Z ≤ 1.36. Here, the double folding (DF) model which is accompanied by density-dependent (DD) versions of M3Y interactions is adopted as a basic heavy ion-ion potential. We show that the selected DD potentials predict a linear behavior for the calculated fusion barrier heights as a function of (N/Z - 1) for both proton- and neutron-rich systems. Moreover, the results indicate that the isotopic behavior of these values depend linearly on the change in the K constant. The isotopic studies conducted on the fusion cross-section also shows that the properties of the nuclear matter in the range of energy which is below the fusion barrier will quite affect the fusion process.

Sudbury project (University of Muenster-Ontario Geological Survey): Petrology, chemistry, and origin of breccia formations

NASA Technical Reports Server (NTRS)

Stoeffler, D.; Deutsch, A.; Avermann, M.; Brockmeyer, P.; Lakomy, R.; Mueller-Mohr, V.

1992-01-01

Within the Sudbury Project of the University of Muenster and the Ontario Geological Survey special emphasis was put on the breccia formations exposed at the Sudbury structure (SS) because of their crucial role for the impact hypothesis. They were mapped and sampled in selected areas of the north, east, and south ranges of the SS. The relative stratigraphic positions of these units are summarized. Selected samples were analyzed by optical microscopy, SEM, microprobe, XRF and INAA, Rb-Sr and SM-Nd-isotope geochemistry, and carbon isotope analysis. The results of petrographic and chemical analysis for those stratigraphic units that were considered the main structural elements of a large impact basin are summarized.

Response of local vascular volumes to lower body negative pressure stress

NASA Technical Reports Server (NTRS)

Wolthuis, R. A.; Leblanc, A.; Carpentier, W. A.; Bergman, S. A., Jr.

1975-01-01

The present study involved an intravenous injection of radioactive iodinated serum albumin, equilibration of this isotope within the vascular space, and the continuous measurement of isotope activity over selected anatomical areas before, during and following multiple human LBNP tests. Both rate and magnitude of vascular pooling were distinctly different within each of five selected lower body anatomical areas. In the upper body, all areas except the abdomen showed depletions from their resting vascular volumes during LBNP. The presence of uniquely different pooling patterns in the lower body, the apparent stability of abdominal vascular volumes, and a possible decrease in cerebral blood volume during LBNP represent the major findings of this study.

Stable isotopes in juvenile marine fishes and their invertebrate prey from the Thames Estuary, UK, and adjacent coastal regions

NASA Astrophysics Data System (ADS)

Leakey, Chris D. B.; Attrill, Martin J.; Jennings, Simon; Fitzsimons, Mark F.

2008-04-01

Estuaries are regarded as valuable nursery habitats for many commercially important marine fishes, potentially providing a thermal resource, refuge from predators and a source of abundant prey. Stable isotope analysis may be used to assess relative resource use from isotopically distinct sources. This study comprised two major components: (1) development of a spatial map and discriminant function model of stable isotope variation in selected invertebrate groups inhabiting the Thames Estuary and adjacent coastal regions; and (2) analysis of stable isotope signatures of juvenile bass ( Dicentrarchus labrax), sole ( Solea solea) and whiting ( Merlangius merlangus) for assessment of resource use and feeding strategies. The data were also used to consider anthropogenic enrichment of the estuary and potential energetic benefits of feeding in estuarine nursery habitat. Analysis of carbon (δ 13C), nitrogen (δ 15N) and sulphur (δ 34S) isotope data identified significant differences in the 'baseline' isotopic signatures between estuarine and coastal invertebrates, and discriminant function analysis allowed samples to be re-classified to estuarine and coastal regions with 98.8% accuracy. Using invertebrate signatures as source indicators, stable isotope data classified juvenile fishes to the region in which they fed. Feeding signals appear to reflect physiological (freshwater tolerance) and functional (mobility) differences between species. Juvenile sole were found to exist as two isotopically-discrete sub-populations, with no evidence of mixing between the two. An apparent energetic benefit of estuarine feeding was only found for sole.

Isolation and Puification of Uranium Isotopes for Measurement by Mass-Spectrometry (233, 234, 235, 236, 238U) and Alpha Spectrometry (232U)

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

Marinelli, R; Hamilton, T; Brown, T

2006-05-30

This report describes a standardized methodology used by researchers from the Center for Accelerator Mass Spectrometry (CAMS) (Energy and Environment Directorate) and the Environmental Radiochemistry Group (Chemistry and Materials Science Directorate) at the Lawrence Livermore National Laboratory (LLNL) for the full isotopic analysis of uranium from solution. The methodology has largely been developed for use in characterizing the uranium composition of selected nuclear materials but may also be applicable to environmental studies and assessments of public, military or occupational exposures to uranium using in-vitro bioassay monitoring techniques. Uranium isotope concentrations and isotopic ratios are measured using a combination of Multimore » Collector Inductively Coupled Plasma Mass Spectrometry (MC ICP-MS), Accelerator Mass Spectrometry (AMS) and Alpha Spectrometry.« less

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

PubMed Central

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

2011-01-01

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

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

DOE PAGES

Smith, Suzanne V.; Mccutchan, Elizabeth; Gurdal, Gulhan; ...

2017-09-13

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

Optimizing sample pretreatment for compound-specific stable carbon isotopic analysis of amino sugars in marine sediment

NASA Astrophysics Data System (ADS)

Zhu, R.; Lin, Y.-S.; Lipp, J. S.; Meador, T. B.; Hinrichs, K.-U.

2014-01-01

Amino sugars are quantitatively significant constituents of soil and marine sediment, but their sources and turnover in environmental samples remain poorly understood. The stable carbon isotopic composition of amino sugars can provide information on the lifestyles of their source organisms and can be monitored during incubations with labeled substrates to estimate the turnover rates of microbial populations. However, until now, such investigation has been carried out only with soil samples, partly because of the much lower abundance of amino sugars in marine environments. We therefore optimized a procedure for compound-specific isotopic analysis of amino sugars in marine sediment employing gas chromatography-isotope ratio mass spectrometry. The whole procedure consisted of hydrolysis, neutralization, enrichment, and derivatization of amino sugars. Except for the derivatization step, the protocol introduced negligible isotopic fractionation, and the minimum requirement of amino sugar for isotopic analysis was 20 ng, i.e. equivalent to ~ 8 ng of amino sugar carbon. Our results obtained from δ13C analysis of amino sugars in selected marine sediment samples showed that muramic acid had isotopic imprints from indigenous bacterial activities, whereas glucosamine and galactosamine were mainly derived from organic detritus. The analysis of stable carbon isotopic compositions of amino sugars opens a promising window for the investigation of microbial metabolisms in marine sediments and the deep marine biosphere.

Tree-ring δ18O in African mahogany (Entandrophragma utile) records regional precipitation and can be used for climate reconstructions

NASA Astrophysics Data System (ADS)

van der Sleen, Peter; Groenendijk, Peter; Zuidema, Pieter A.

2015-04-01

The availability of instrumental climate data in West and Central Africa is very restricted, both in space and time. This limits the understanding of the regional climate system and the monitoring of climate change and causes a need for proxies that allow the reconstruction of paleoclimatic variability. Here we show that oxygen isotope values (δ18O) in tree rings of Entandrophragma utile from North-western Cameroon correlate to precipitation on a regional to sub-continental scale (1930-2009). All found correlations were negative, following the proposed recording of the 'amount effect' by trees in the tropics. The capacity of E. utile to record the variability of regional precipitation is also confirmed by the significant correlation of tree-ring δ18O with river discharge data (1944-1983), outgoing longwave radiation (a proxy for cloud cover; 1974-2011) and sea surface salinity in the Gulf of Guinea (1950-2011). Furthermore, the high values in the δ18O chronology from 1970 onwards coincide with the Sahel drought period. Given that E. utile presents clear annual growth rings, has a wide-spread distribution in tropical Africa and is long lived (> 250 years), we argue that the analysis of oxygen isotopes in growth rings of this species is a promising tool for the study of paleoclimatic variability during the last centuries in West and Central Africa.

Detection of the actinides and cesium from environmental samples

NASA Astrophysics Data System (ADS)

Snow, Mathew Spencer

Detection of the actinides and cesium in the environment is important for a variety of applications ranging from environmental remediation to safeguards and nuclear forensics. The utilization of multiple different elemental concentrations and isotopic ratios together can significantly improve the ability to attribute contamination to a unique source term and/or generation process; however, the utilization of multiple elemental "signatures" together from environmental samples requires knowledge of the impact of chemical fractionation for various elements under a variety of environmental conditions (including predominantly aqueous versus arid conditions). The research reported in this dissertation focuses on three major areas: 1. Improving the understanding of actinide-mineral interactions at ultra-low concentrations. Chapter 2 reports a batch sorption and modeling study of Np(V) sorption to the mineral goethite from attomolar to micromolar concentrations. 2. Improving the detection capabilities for Thermal Ionization Mass Spectrometry (TIMS) analyses of ultra-trace cesium from environmental samples. Chapter 4 reports a new method which significantly improves the chemical yields, purification, sample processing time, and ultimately, the detection limits for TIMS analyses of femtogram quantities of cesium from a variety of environmental sample matrices. 3. Demonstrating how actinide and cesium concentrations and isotopic ratios from environmental samples can be utilized together to determine a wealth of information including environmental transport mechanisms (e.g. aqueous versus arid transport) and information on the processes which generated the original material. Chapters1, 3 and 5 demonstrate these principles using Pu, Am, Np, and Cs concentrations and isotopic ratios from contaminated soils taken near the Subsurface Disposal Area (SDA) of Idaho National Laboratory (INL) (a low level radioactive waste disposal site in southeastern Idaho).

Ontogenetic shifts in the diet of plains hog-nosed snakes (Heterodon nasicus) revealed by stable isotope analysis.

PubMed

Durso, Andrew M; Mullin, Stephen J

2017-02-01

Wild snake diets are difficult to study using traditional methods, but stable isotopes offer several advantages, including integrating dietary information over time, providing data from individuals that have not fed recently, and avoiding bias towards slowly-digesting prey items. We used stable isotope signatures of carbon and nitrogen from scale tissue, red blood cells, and blood plasma to assess the diet of wild plains hog-nosed snakes (Heterodon nasicus) in Illinois. We developed Bayesian mixing models which, taken together, predicted that H. nasicus shifted from a juvenile diet predominantly (31-63%) composed of six-lined racerunners (Aspidoscelis sexlineatus) and their eggs to an adult diet predominantly (44-56%) composed of eggs of the aquatic turtles Chrysemys picta and Chelydra serpentina, with a contribution from toads (Anaxyrus sp.; 6-27%) during their adolescent years. These results agreed with sparse data from gut contents. Combining traditional and isotopic techniques for studying the diets of wild snakes can increase the utility of both types of data. Copyright © 2016 Elsevier GmbH. All rights reserved.

Mid-IR enhanced laser ablation molecular isotopic spectrometry

NASA Astrophysics Data System (ADS)

Brown, Staci; Ford, Alan; Akpovo, Codjo A.; Johnson, Lewis

2016-08-01

A double-pulsed laser-induced breakdown spectroscopy (DP-LIBS) technique utilizing wavelengths in the mid-infrared (MIR) for the second pulse, referred to as double-pulse LAMIS (DP-LAMIS), was examined for its effect on detection limits compared to single-pulse laser ablation molecular isotopic spectrometry (LAMIS). A MIR carbon dioxide (CO2) laser pulse at 10.6 μm was employed to enhance spectral emissions from nanosecond-laser-induced plasma via mid-IR reheating and in turn, improve the determination of the relative abundance of isotopes in a sample. This technique was demonstrated on a collection of 10BO and 11BO molecular spectra created from enriched boric acid (H3BO3) isotopologues in varying concentrations. Effects on the overall ability of both LAMIS and DP-LAMIS to detect the relative abundance of boron isotopes in a starting sample were considered. Least-squares fitting to theoretical models was used to deduce plasma parameters and understand reproducibility of results. Furthermore, some optimization for conditions of the enhanced emission was achieved, along with a comparison of the overall emission intensity, plasma density, and plasma temperature generated by the two techniques.

In situ dating on Mars: A new approach to the K-Ar method utilizing cosmogenic argon

NASA Astrophysics Data System (ADS)

Cassata, William S.

2014-01-01

Cosmogenic argon isotopes are produced in feldspars via nuclear reactions between cosmic rays and Ca and K atoms within the lattice. These cosmogenic isotopes can be used as proxies for K and Ca, much like nuclear reactor-derived 39Ar and 37Ar are used as proxies for K and Ca, respectively, in 40Ar/39Ar geochronology. If Ca and K are uniformly distributed, then the ratio of radiogenic 40Ar (40Ar*) to cosmogenic 38Ar or 36Ar (38Arcos or 36Arcos) is proportional to the difference between the radioisotopic and exposure ages, as well as the K/Ca ratio of the degassing phase. Thus cosmogenic, radiogenic, and trapped Ar isotopes, all of which can be measured remotely and are stable over geologic time, are sufficient to generate an isochron-like diagram from which the isotopic composition of the trapped component may be inferred. Such data also provide a means to assess the extent to which the system has remained closed with respect to 40Ar*, thereby mitigating otherwise unquantifiable uncertainties that complicate the conventional K-Ar dating method.

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.

Determination of 13C isotopic enrichment of valine and threonine by GC-C-IRMS after formation of the N(O,S)-ethoxycarbonyl ethyl ester derivatives of the amino acids.

PubMed

Godin, Jean-Philippe; Faure, Magali; Breuille, Denis; Hopfgartner, Gérard; Fay, Laurent-Bernard

2007-06-01

We describe a new method of assessing, in a single run, (13)C isotopic enrichment of both Val and Thr by gas chromatography-combustion-isotope-ratio mass spectrometry (GC-C-IRMS). This method characterised by a rapid one-step derivatisation procedure performed at room temperature to form the N(O,S)-ethoxycarbonyl ethyl ester derivatives, and a polar column for GC. The suitability of this method for Val and Thr in in-vivo samples (mucosal hydrolysate) was demonstrated by studying protein metabolism with two tracers ((13)C-valine or (13)C-threonine). The intra-day and inter-day repeatability were both assessed either with standards or with in-vivo samples at natural abundance and at low (13)C isotopic enrichment. For inter-day repeatability CVs were between 0.8 and 1.5% at natural abundance and lower than 5.5% at 0.112 and 0.190 atom% enrichment for Val and Thr, respectively. Overall isotopic precision was studied for eleven standard amino acid derivatives (those of Val, Ala, Leu, Iso, Gly, Pro, Asp, Thr, Ser, Met, and Phe) and was assessed at 0.32 per thousand. The (13)C isotopic measurement was then extended to the other amino acids (Ala, Val, Leu, Iso, Gly, Pro, Thr, and Phe) at natural abundance for in-vivo samples. The isotopic precision was better than 0.002 atom% per amino acid (for n = 4 rats). This analytical method was finally applied to an animal study to measure Thr utilization in protein synthesis.

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

USGS Publications Warehouse

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

2010-01-01

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

Enhanced understanding of ectoparasite: host trophic linkages on coral reefs through stable isotope analysis

USGS Publications Warehouse

Demopoulos, Amanda W. J.; Sikkel, Paul C.

2015-01-01

Parasitism, although the most common type of ecological interaction, is usually ignored in food web models and studies of trophic connectivity. Stable isotope analysis is widely used in assessing the flow of energy in ecological communities and thus is a potentially valuable tool in understanding the cryptic trophic relationships mediated by parasites. In an effort to assess the utility of stable isotope analysis in understanding the role of parasites in complex coral-reef trophic systems, we performed stable isotope analysis on three common Caribbean reef fish hosts and two kinds of ectoparasitic isopods: temporarily parasitic gnathiids (Gnathia marleyi) and permanently parasitic cymothoids (Anilocra). To further track the transfer of fish-derived carbon (energy) from parasites to parasite consumers, gnathiids from host fish were also fed to captive Pederson shrimp (Ancylomenes pedersoni) for at least 1 month. Parasitic isopods had δ13C and δ15N values similar to their host, comparable with results from the small number of other host–parasite studies that have employed stable isotopes. Adult gnathiids were enriched in 15N and depleted in13C relative to juvenile gnathiids, providing insights into the potential isotopic fractionation associated with blood-meal assimilation and subsequent metamorphosis. Gnathiid-fed Pedersen shrimp also had δ13C values consistent with their food source and enriched in 15N as predicted due to trophic fractionation. These results further indicate that stable isotopes can be an effective tool in deciphering cryptic feeding relationships involving parasites and their consumers, and the role of parasites and cleaners in carbon transfer in coral-reef ecosystems specifically.

Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

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

Isselhardt, Brett H.

2011-09-01

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of 235U/ 238U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser inmore » a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.« less

DN/DG Screening of Environmental Swipe Samples: FY2016 Report

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

Glasgow, David C.; Croft, Stephen; Venkataraman, Ramkumar

The Delayed Neutron Delayed Gamma (DNDG) technique provides a new analytical capability to the International Atomic Energy Agency (IAEA) for detecting undeclared nuclear activities. IAEA’s Long Term R&D (LTRD) plan has a stated high urgency need to develop elemental and isotopic signatures of nuclear fuel cycle activities and processes (LTRD 2.2). The new DNDG capability is used to co-detect both uranium and plutonium as an extension of a DN only method that is already being utilized by the IAEA for the analysis of swipes to inform on undeclared nuclear activities. Analytical method involving irradiation of swipe samples potentially containing tracemore » quantities of fissile material in a thermal neutron field, followed by the counting of delayed neutrons, is a well-known technique in the field of safeguards and nonproliferation. It is used for detecting the presence of microscopic amounts of fissile material, (typically a linear combination of 233U, 235U, 239Pu, and 241Pu)and quantifying it in terms of the equivalent mass of 235U. The delayed neutron (DN) technique is very sensitive and is been routinely employed at the High Flux Isotope Reactor (HFIR) facility at Oak Ridge National Laboratory (ORNL). Both uranium and plutonium are of high safeguards value. However, the DN technique is not well suited for distinguishing between U and Pu isotopes since the decay curves overlap closely. The delayed gamma (DG) technique will help detect the presence of 239Pu in a mixture of U and Pu. Thus the DNDG approach combines the best of both worlds; the sensitivity of DN counting and the isotopic specificity of DG counting. The present work seeks to build on the delayed neutron and delayed gamma methods that have been developed at ORNL. It is recognized that the distribution profile of heavy fission products remains fairly invariant for the fissile nuclides whereas the distribution of light fission products varies from one isotope to another. That is, the ratio of the yield of a light fission fragment to a heavy fission fragments is isotope specific. Measurement of the ratio of the net full energy peak (FEP) from low/high mass fission products is an elegant way to characterize the fraction of fissile materials present in a mixture. By empirically calibrating the ratio of the net FEP as a function of known concentration of the binary mixture, one can determine the fraction of fissile isotopes in an unknown sample. In the work done in fiscal year (FY) 2016, samples of single fissile material isotopes as well as binary mixtures were irradiated in a well thermalized irradiation field in the HFIR. Delayed neutron counting was performed using the neutron counter at the HFIR Neutron Activation Analysis (NAA) laboratory. Delayed gamma counting was performed using a shielded high purity germanium (HPGe) detector. Delayed neutron decay curve results highlighted the difficulty of distinguishing between U and Pu isotopes, and the need for including the delayed gamma component. Based on delayed gamma spectrometry, twelve ratios of low mass/high fission product gamma ray FEP have been identified as valid candidates. Linearity of the ratios, as a function of 239Pu fraction in 235U+ 239Pu mixtures, was confirmed for the low mass/high mass candidates that were selected. The DNDG method we are spearheading allows not only the presence of total fissile content to be detected, but whether the material is predominantly U or predominantly Pu, or a mixture. This provides additional SG relevant information.« less

Bringing organic carbon isotopes and phytoliths to the table as additional constraints on paleoelevation

NASA Astrophysics Data System (ADS)

Sheldon, N. D.; Cotton, J. M.; Hren, M. T.; Hyland, E. G.; Smith, S. Y.; Strömberg, C. A. E.

2015-12-01

A commonly used tool in paleotectonic and paleoaltimetry studies is the oxygen isotopic composition of authigenic carbonates formed that formed in lakes or soils, with both spatial (e.g., shoreline to mountain top) or temporally resolved records potentially providing constraints. However, in many cases there is a substantial spread in the oxygen isotope data for a given time period, often to the point of allowing for essentially any interpretation of the data depending upon how they have been used by the investigator. One potential way of distinguishing between different potential paleotectonic or paleoaltimetric interpretations is to use carbon isotope and plant microfossil (phytolith) analyses from the same paleosols to screen the oxygen isotope data by looking for evidence of evaporative enrichment. For example, if both inorganic (carbonate) and organic carbon isotopes are measured from the same paleosol, then in it possible to determine if the two isotope record equilibrium conditions or if they record disequilibrium driven by kinetic effects. In the former case, the oxygen isotope results can be considered reliable whereas in the latter case, the oxygen isotope results can be considered unreliable and could be culled from the interpretation. Similarly, because the distribution of C4 plants varies as a function of temperature and elevation, the presence/absence or abundance of C4 plant phytoliths, or of carbon isotope compositions that require a component of C4 vegetation can also be used to constrain paleoelevation by providing a maximum elevation constraint. Worked examples will include the late Miocene-Pliocene of Catamarca, Argentina, where phytoliths and organic carbon isotopes provide a maximum elevation constraint and can be used to demonstrate that oxygen isotopes do not provide a locally useful constraint on paleoelevation, and Eocene-Miocene of southwestern Montana where organic matter and phytoliths can be used to select between different potential uplift histories as indicated by pedogenic carbonate oxygen isotope data.

An overview of methods using (13)C for improved compound identification in metabolomics and natural products.

PubMed

Clendinen, Chaevien S; Stupp, Gregory S; Ajredini, Ramadan; Lee-McMullen, Brittany; Beecher, Chris; Edison, Arthur S

2015-01-01

Compound identification is a major bottleneck in metabolomics studies. In nuclear magnetic resonance (NMR) investigations, resonance overlap often hinders unambiguous database matching or de novo compound identification. In liquid chromatography-mass spectrometry (LC-MS), discriminating between biological signals and background artifacts and reliable determination of molecular formulae are not always straightforward. We have designed and implemented several NMR and LC-MS approaches that utilize (13)C, either enriched or at natural abundance, in metabolomics applications. For LC-MS applications, we describe a technique called isotopic ratio outlier analysis (IROA), which utilizes samples that are isotopically labeled with 5% (test) and 95% (control) (13)C. This labeling strategy leads to characteristic isotopic patterns that allow the differentiation of biological signals from artifacts and yield the exact number of carbons, significantly reducing possible molecular formulae. The relative abundance between the test and control samples for every IROA feature can be determined simply by integrating the peaks that arise from the 5 and 95% channels. For NMR applications, we describe two (13)C-based approaches. For samples at natural abundance, we have developed a workflow to obtain (13)C-(13)C and (13)C-(1)H statistical correlations using 1D (13)C and (1)H NMR spectra. For samples that can be isotopically labeled, we describe another NMR approach to obtain direct (13)C-(13)C spectroscopic correlations. These methods both provide extensive information about the carbon framework of compounds in the mixture for either database matching or de novo compound identification. We also discuss strategies in which (13)C NMR can be used to identify unknown compounds from IROA experiments. By combining technologies with the same samples, we can identify important biomarkers and corresponding metabolites of interest.

Equilibrium stable-isotope fractionation of thallium and mercury

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2005-12-01

In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed range of isotopic fractionations, however, which could point to a major role for kinetic-fractionation or Rayleigh-like distillation processes. Refs.: [1] Rehämper et al. (2002) EPSL 197:65. [2] Xie et al. (2005) J. Anal. Atomic Spectrom. 20:515. [3] Bigeleisen and Mayer (1947) J. Chem. Phys. 15:261.

Probing Aluminum Reactions in Combustion and Explosion Via the Kinetic Isotope Effect

NASA Astrophysics Data System (ADS)

Tappan, Bryce

2015-06-01

The mechanism that controls the reaction speed of aluminum in explosion and combustion is poorly understood, and experimentally difficult to measure. Recently, work in our laboratory has demonstrated that during the combustion of nanoparticulate aluminum with H2O or D2O, different reaction rates due to the kinetic isotope effect are observed. This result is the first-ever observed kinetic isotope effect in a metal combustion reaction and verifies that chemical reaction kinetics play a major role in determining the global burning rate. During or shortly after a detonation, however, the reaction rates are dramatically faster and the physical mechanism controlling Al reaction is likely different than during combustion events. To utilize the kinetic isotope effect to probe Al reactions in detonation, formulations were produced that contain powdered Al in deuterated high explosives and high-fidelity detonation velocity were determined along with PDV measurements to observe early wall velocity expansion measurements. The JWL equation of state was solved to determine temperature, pressure and energies at specific time periods, in addition of Gurney energies, which enables the elucidation of Al reaction extent. By comparison of the Al oxidation with LiF, data indicate that Al oxidation occurs on an extremely fast time scale and isotope effects in both the HE detonation and post-detonation Al reactions are discussed.

Evaluation of Direct Vapour Equilibration for Stable Isotope Analysis of Plant Water.

NASA Astrophysics Data System (ADS)

Millar, C. B.; McDonnell, J.; Pratt, D.

2017-12-01

The stable isotopes of water (2H and 18O), extracted from plants, have been utilized in a variety of ecohydrological, biogeochemical and climatological studies. The array of methods used to extract water from plants are as varied as the studies themselves. Here we perform a comprehensive inter-method comparison of six plant water extraction techniques: direct vapour equilibration, microwave extraction, two unique versions of cryogenic extraction, centrifugation, and high pressure mechanical squeezing. We applied these methods to four isotopically unique plant portions (heads, stems, leaves and root crown) of spring wheat (Triticum aestivum L.). The spring wheat was grown under controlled conditions with irrigation inputs of a known isotopic composition. Our results show that the methods of extraction return significantly different plant water isotopic signals. Centrifugation, microwave extraction, direct vapour equilibration, and squeezing returned more enriched results. Both cryogenic systems and squeezing returned more depleted results, depending upon the plant portion extracted. While cryogenic extraction is currently the most widely used method in the literature, our results suggest that direct vapor equilibration method outperforms it in terms of accuracy, sample throughput and replicability. More research is now needed with other plant species (especially woody plants) to see how far the findings from this study could be extended.

Absolute Calibration of Si iRMs used for Si Paleo-nutrient proxies

NASA Astrophysics Data System (ADS)

Vocke, Robert; Rabb, Savelas

2016-04-01

The Avogadro Project is an ongoing international effort, coordinated by the International Bureau of Weights and Measures (BIPM) and the International Avogadro Coordination (IAC) to redefine the SI unit mole in terms of the Avogadro constant and the SI unit kg in terms of the Planck constant. One of the outgrowths of this effort has been the development of a novel, precise and highly accurate method to measure calibrated (absolute) isotopic ratios that are traceable to the SI (Vocke et al., 2014 Metrologia 51, 361, Azuma et al., 2015 Metrologia 52 360). This approach has also been able to produce absolute Si isotope ratio data with lower levels of uncertainty when compared to the traditional "Atomic Weights" method of absolute isotope ratio measurement. Silicon isotope variations (reported as delta(Si30)and delta(Si29)) in silicic acid dissolved in ocean waters, in biogenic silica and in diatoms are extremely informative paleo-nutrient proxies. The utility and comparability of such measurements however depends on calibration with artifact isotopic Reference Materials (iRMs). We will be reporting new measurements on the iRMs NBS-28 (RM 8546 - Silica Sand), Diatomite, Big Batch and SRM 990 using the Avogadro measurement approach, comparing them with prior assessments of these iRMs.

LU-HF Age and Isotope Systematics of ALH84001

NASA Technical Reports Server (NTRS)

Righter, M.; Lapen, T. J.; Brandon, A. D.; Beard, B. L.; Shafer, J. T.; Peslier, A. H.

2009-01-01

Allan Hills (ALH) 84001 is an orthopyroxenite that is unique among the Martian meteorites in having the oldest inferred crystallization age (approx..4.5 to 4.0 Gyr) [e.g., 1-6 and references therein 7]. Its ancient origin makes this stone a critical constraint on early history of Mars, in particular the evolution of different planetary crust and mantle reservoirs. However, because there is significant variability in reported crystallization ages, determination of initial isotope compositions is imprecise making assessment of planetary reservoirs difficult. Here we report a new Lu-Hf mineral isochron age, initial Hf-176/Hf-177 isotope composition, and inferred Martian mantle source compositions for ALH84001 that place constraints on longlived source reservoirs for the enriched shergottite suite of Martian meteorites including Shergotty, Zagami, NWA4468, NWA856, RBT04262, LAR06319, and Los Angeles. Sm-Nd isotope analyses are under way for the same mineral aliquots analyzed for Lu-Hf. The Lu-Hf system was utilized because Lu and Hf are both lithophile and refractory and are not easily redistributed during short-lived thermal pulses associated with shock metamorphism. Moreover, chromite has relatively modest Hf concentrations with very low Lu/Hf ratios [9] yielding tight constraints on initial Hf-176/Hf-177 isotope compositions

Nitrogen isotopes from terrestrial organic matter as a new paleoclimatic proxy for pre-quaternary time

NASA Astrophysics Data System (ADS)

Tramoy, romain; Schnyder, johann; thuy Nguyen Tu, thanh; Yans, johan; Storme, jean yves; Sebilo, mathieu; Derenne, sylvie; Jacob, jérémy; Baudin, françois

2014-05-01

Marine and lacustrine sedimentary organic matter is often dominated by algal-bacterial production. Its nitrogen isotopic composition (δ15Norg) is frequently used to reconstruct biogeochemical processes involved in the nitrogen cycle, such as N utilization by organisms (e.g. Altabet et al., 1995), denitrification and diagenesis processes (e.g. Altabet et al., 1995; Sebilo et al., 2003; Gälman et al., 2009) or to evidence N sources variability (e.g. Hodell and Schelske, 1998; Vreca and Muri, 2006) . However, all these parameters and processes make N isotopic signals in marine and lacustrine environments often very complex to interpret. After pioneer studies, Mariotti et al. (1981), Austin and Vitousek (1998), Amundson et al. (2003), Swap et al. (2004), and Liu and Wang (2008) have shown that the δ15Norg of modern or quaternary terrestrial plants seem to be positively correlated with temperature and negatively correlated with precipitations. Therefore, δ15Norg of terrestrial OM might be a better record for paleoclimatic studies than δ15Norg of sedimentary OM dominated by algal-bacterial production. Recently, promising organic nitrogen isotopic data (δ15Norg) have been published on lignites from the Dieppe-Hampshire Basin (Paleocene-Eocene transition, Normandy (Storme et al., 2012). Authors suggest that the δ15Norg recorded local paleoclimatic and paleoenvironmental conditions. Following these results, the aim of this work is to test the use of stable nitrogen isotopes in terrestrial OM as a new paleoclimatic marker for pre-quaternary geological series. Does δ15Norg constitute a valuable tool to reconstruct past climates? What are the limits in the use of this proxy and possible methodological bias related to organic sources or diagenetic processes? To address these questions, δ15Norg must be measured in samples from periods associated with large and well documented climate change. We therefore selected a Liassic continental sedimentary succession from Taskomirsay, Kazakhstan. This succession is rich in dispersed OM and wood fragments allowing accurate N isotopes measurements. Preliminary results on δ13Corg and palynology suggest that the Pliensbachian/Toarcian transition is recorded at the top of the sedimentary succession. This transition has been studied for a long time since it is characterized by one of the most important global environmental and climatic change of the Phanerozoic time ( Jenkyns, 1988; Hermoso et al., 2012). We are therefore testing the paleoclimatic "proxy" potential of δ15Norg for this time interval by comparing the δ15Norg signal with other indicators more classically used for paleoclimate studies. We have also investigated the influence of differences in organic sources and of early diagenesis on the δ15Norg variations.

Corticosteroids increase glutamine utilization in human splanchnic bed

USDA-ARS?s Scientific Manuscript database

Glutamine is the most abundant amino acid in the body and is extensively taken up in gut and liver in healthy humans. To determine whether glucocorticosteroids alter splanchnic glutamine metabolism, the effect of prednisone was assessed in healthy volunteers using isotope tracer methods. Two groups ...

A Californium-252 Neutron Source for Student Use

ERIC Educational Resources Information Center

Bowen, H. J.

1975-01-01

Describes an undergraduate chemistry experiment which utilizes small samples of Californium 252 as a neutron source for the activation of 12 other elements. The students prepare decay curves of the radioactive isotopes and perform nondestructive activation analyses for gram amounts of some elements. (MLH)

Reply to MB Krawinkel

USDA-ARS?s Scientific Manuscript database

We appreciate the opportunity to respond to the letter from Dr. Krawinkel regarding our recent publication on the vitamin A equivalency of Golden Rice. In this study we utilized stable isotope methodologies and a single serving (per subject) of Golden Rice (a transgenic rice that produces beta-caro...

Determination of Multiple φ-Torsion Angles in Proteins by Selective and Extensive 13C Labeling and Two-Dimensional Solid-State NMR

NASA Astrophysics Data System (ADS)

Hong, Mei

1999-08-01

We describe an approach to efficiently determine the backbone conformation of solid proteins that utilizes selective and extensive 13C labeling in conjunction with two-dimensional magic-angle-spinning NMR. The selective 13C labeling approach aims to reduce line broadening and other multispin complications encountered in solid-state NMR of uniformly labeled proteins while still enhancing the sensitivity of NMR spectra. It is achieved by using specifically labeled glucose or glycerol as the sole carbon source in the protein expression medium. For amino acids synthesized in the linear part of the biosynthetic pathways, [1-13C]glucose preferentially labels the ends of the side chains, while [2-13C]glycerol labels the Cα of these residues. Amino acids produced from the citric-acid cycle are labeled in a more complex manner. Information on the secondary structure of such a labeled protein was obtained by measuring multiple backbone torsion angles φ simultaneously, using an isotropic-anisotropic 2D correlation technique, the HNCH experiment. Initial experiments for resonance assignment of a selectively 13C labeled protein were performed using 15N-13C 2D correlation spectroscopy. From the time dependence of the 15N-13C dipolar coherence transfer, both intraresidue and interresidue connectivities can be observed, thus yielding partial sequential assignment. We demonstrate the selective 13C labeling and these 2D NMR experiments on a 8.5-kDa model protein, ubiquitin. This isotope-edited NMR approach is expected to facilitate the structure determination of proteins in the solid state.

On the Utility (or Futility) of Using Stable Water Isotopes to Constrain the Bulk Properties of Tropical Convection

NASA Astrophysics Data System (ADS)

Duan, Suqin Q.; Wright, Jonathon S.; Romps, David M.

2018-02-01

Atmospheric water-vapor isotopes have been proposed as a potentially powerful constraint on convection, which plays a critical role in Earth's present and future climate. It is shown here, however, that the mean tropical profile of HDO in the free troposphere does not usefully constrain the mean convective entrainment rate or precipitation efficiency. This is demonstrated using a single-column analytical model of atmospheric water isotopes. The model has three parameters: the entrainment rate, the precipitation efficiency, and the distance that evaporating condensates fall. At a given relative humidity, the possible range of HDO is small: its range is comparable to both the measurement uncertainty in the mean tropical profile and the structural uncertainty of a single-column model. Therefore, the mean tropical HDO profile is unlikely to add information about convective processes in a bulk-plume framework that cannot already be learned from relative humidity alone.

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

Wahid, Ahmad Nazrul Abd, E-mail: a-nazrul@nuclearmalaysia.gov.my; Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor; Rahim, Sahibin Abd, E-mail: haiyan@ukm.edu.my

This study was carried out to evaluate the efficiency use of the nitrogen fertilizer on aerobic rice varieties MR219-4 and MR219-9 which were grown aerobically under field capacity water potential at the controlled environment area or shield house. Direct {sup 15}N isotope tracer method was used in this study, whereby the {sup 15}N isotope was utilized as a tracer for nitrogen nutrient uptake. {sup 15}N isotope presence in the samples is determined by using emission spectrometer analysis and percentage of total nitrogen is determined by using Kjeldahl method. {sup 15}N atom access value contained in the sample will be usedmore » in determining the effectiveness of the use of nitrogen in fertilizers through the specific calculation formulas. In this work, the data several data of nitrogen derived from fertilizer (Ndff), total nitrogen, nitrogen uptake and nitrogen use efficiency was obtained.« less

Reverse isotope dilution method for determining benzene and metabolites in tissues

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

Bechtold, W.E.; Sabourin, P.J.; Henderson, R.F.

1988-07-01

A method utilizing reverse isotope dilution for the analysis of benzene and its organic soluble metabolites in tissues of rats and mice is presented. Tissues from rats and mice that had been exposed to radiolabeled benzene were extracted with ethyl acetate containing known, excess quantities of unlabeled benzene and metabolites. Butylated hydroxytoluene was added as an antioxidant. The ethyl acetate extracts were analyzed with semipreparative reversed-phase HPLC. Isolated peaks were collected and analyzed for radioactivity (by liquid scintillation spectrometry) and for mass (by UV absorption). The total amount of each compound present was calculated from the mass dilution of themore » radiolabeled isotope. This method has the advantages of high sensitivity, because of the high specific activity of benzene, and relative stability of the analyses, because of the addition of large amounts of unlabeled carrier analogue.« less

Stable isotopic fingerprint of a hyporheic-hypolentic boundary in a reservoir

NASA Astrophysics Data System (ADS)

Aseltyne, Todd A.; Rowe, Harold D.; Fryar, Alan E.

2006-12-01

Stable isotopes of H2O are used to define the hyporheic-hypolentic boundary in Ledbetter Creek as it discharges to Kentucky Lake, a constructed reservoir in western Kentucky, USA. High-resolution (centimeter-scale) sample collection and analysis were utilized to determine one-dimensional variations in δ2H and δ18O of H2O and chloride (Cl-) across the boundary. During reservoir low stand in winter, the hyporheic-hypolentic zone contains water from Ledbetter Creek and groundwater separated by an interface at ~10 cm below the channel bottom. Following reservoir-stage increase in spring and summer, water from Kentucky Lake infiltrates into the hyporheic-hypolentic zone to a depth of at least 18 cm below the channel bottom. Reservoir-stage decline in autumn causes source-water mixing, largely obscuring the hyporheic-hypolentic boundary. Stable isotopes provide an effective complement to conventional tracers for delineation of water masses within the hyporheic-hypolentic zone.

Integration of stable isotope and trace contaminant concentration for enhanced forensic acetone discrimination.

PubMed

Moran, James J; Ehrhardt, Christopher J; Wahl, Jon H; Kreuzer, Helen W; Wahl, Karen L

2013-11-15

We analyzed 21 neat acetone samples from 15 different suppliers to demonstrate the utility of a coupled stable isotope and trace contaminant strategy for distinguishing forensically-relevant samples. By combining these two pieces of orthogonal data we could discriminate all of the acetones that were produced by the 15 different suppliers. Using stable isotope ratios alone, we were able to distinguish 8 acetone samples, while the remaining 13 fell into four clusters with highly similar signatures. Adding trace chemical contaminant information enhanced discrimination to 13 individual acetones with three residual clusters. The acetones within each cluster shared a common manufacturer and might, therefore, not be expected to be resolved. The data presented here demonstrates the power of combining orthogonal data sets to enhance sample fingerprinting and highlights the role disparate data could play in future forensic investigations. © 2013 The Authors. Published by Elsevier B.V. All rights reserved.

Analysis of hydrogen isotope mixtures

DOEpatents

Villa-Aleman, Eliel

1994-01-01

An apparatus and method for determining the concentrations of hydrogen isotopes in a sample. Hydrogen in the sample is separated from other elements using a filter selectively permeable to hydrogen. Then the hydrogen is condensed onto a cold finger or cryopump. The cold finger is rotated as pulsed laser energy vaporizes a portion of the condensed hydrogen, forming a packet of molecular hydrogen. The desorbed hydrogen is ionized and admitted into a mass spectrometer for analysis.

Determination of copper by isotopic dilution.

PubMed

Faquim, E S; Munita, C S

1994-01-01

A rapid and selective method was used for the determination of copper by isotopic dilution employing substoichiometric extraction with dithizone in carbon tetrachloride. The appropriate pH range for the substoichiometric extraction was 2-7. In the analysis, even a large excess of elements forming extractable complexes with dithizone does not interfere. The accuracy and precision of the method were evaluated. The method has been applied to analysis of reference materials, wheat flour, wine, and beer.

Autotrophy of green non-sulphur bacteria in hot spring microbial mats: biological explanations for isotopically heavy organic carbon in the geological record

NASA Technical Reports Server (NTRS)

van der Meer, M. T.; Schouten, S.; de Leeuw, J. W.; Ward, D. M.

2000-01-01

Inferences about the evidence of life recorded in organic compounds within the Earth's ancient rocks have depended on 13C contents low enough to be characteristic of biological debris produced by the well-known CO2 fixation pathway, the Calvin cycle. 'Atypically' high values have been attributed to isotopic alteration of sedimentary organic carbon by thermal metamorphism. We examined the possibility that organic carbon characterized by a relatively high 13C content could have arisen biologically from recently discovered autotrophic pathways. We focused on the green non-sulphur bacterium Chloroflexus aurantiacus that uses the 3-hydroxypropionate pathway for inorganic carbon fixation and is geologically significant as it forms modern mat communities analogous to stromatolites. Organic matter in mats constructed by Chloroflexus spp. alone had relatively high 13C contents (-14.9%) and lipids diagnostic of Chloroflexus that were also isotopically heavy (-8.9% to -18.5%). Organic matter in mats constructed by Chloroflexus in conjunction with cyanobacteria had a more typical Calvin cycle signature (-23.5%). However, lipids diagnostic of Chloroflexus were isotopically enriched (-15.1% to -24.1%) relative to lipids typical of cyanobacteria (-33.9% to -36.3%). This suggests that, in mats formed by both cyanobacteria and Chloroflexus, autotrophy must have a greater effect on Chloroflexus carbon metabolism than the photoheterotrophic consumption of cyanobacterial photosynthate. Chloroflexus cell components were also selectively preserved. Hence, Chloroflexus autotrophy and selective preservation of its products constitute one purely biological mechanism by which isotopically heavy organic carbon could have been introduced into important Precambrian geological features.

Selective Hydrogen Isotope Separation via Breathing Transition in MIL-53(Al).

PubMed

Kim, Jin Yeong; Zhang, Linda; Balderas-Xicohténcatl, Rafael; Park, Jaewoo; Hirscher, Michael; Moon, Hoi Ri; Oh, Hyunchul

2017-12-13

Breathing of MIL-53(Al), a flexible metal-organic framework (MOF), leads to dynamic changes as narrow pore (np) transitions to large pore (lp). During the flexible and reversible transition, the pore apertures are continuously adjusted, thus providing the tremendous opportunity to separate mixtures of similar-sized and similar-shaped molecules that require precise pore tuning. Herein, for the first time, we report a strategy for effectively separating hydrogen isotopes through the dynamic pore change during the breathing of MIL-53(Al), a representative of flexible MOFs. The experiment shows that the selectivity for D 2 over H 2 is strongly related to the state of the pore structure of MIL-53(Al). The highest selectivity (S D 2 /H 2 = 13.6 at 40 K) was obtained by optimizing the exposure temperature, pressure, and time to systematically tune the pore state of MIL-53(Al).

Isotope effects in the evaporation of water: a status report of the Craig-Gordon model.

PubMed

Horita, Juske; Rozanski, Kazimierz; Cohen, Shabtai

2008-03-01

The Craig-Gordon model (C-G model) [H. Craig, L.I. Gordon. Deuterium and oxygen 18 variations in the ocean and the marine atmosphere. In Stable Isotopes in Oceanographic Studies and Paleotemperatures, E. Tongiorgi (Ed.), pp. 9-130, Laboratorio di Geologia Nucleare, Pisa (1965).] has been synonymous with the isotope effects associated with the evaporation of water from surface waters, soils, and vegetations, which in turn constitutes a critical component of the global water cycle. On the occasion of the four decades of its successful applications to isotope geochemistry and hydrology, an attempt is made to: (a) examine its physical background within the framework of modern evaporation models, (b) evaluate our current knowledge of the environmental parameters of the C-G model, and (c) comment on a general strategy for the use of these parameters in field applications. Despite its simplistic representation of evaporation processes at the water-air interface, the C-G model appears to be adequate to provide the isotopic composition of the evaporation flux. This is largely due to its nature for representing isotopic compositions (a ratio of two fluxes of different isotopic water molecules) under the same environmental conditions. Among many environmental parameters that are included in the C-G model, accurate description and calculations are still problematic of the kinetic isotope effects that occur in a diffusion-dominated thin layer of air next to the water-air interface. In field applications, it is of importance to accurately evaluate several environmental parameters, particularly the relative humidity and isotopic compositions of the 'free-atmosphere', for a system under investigation over a given time-scale of interest (e.g., hourly to daily to seasonally). With a growing interest in the studies of water cycles of different spatial and temporal scales, including paleoclimate and water resource studies, the importance and utility of the C-G model is also likely to grow in the future.

A Screen for Novel Phosphoinositide 3-kinase Effector Proteins*

PubMed Central

Dixon, Miles J.; Gray, Alexander; Boisvert, François-Michel; Agacan, Mark; Morrice, Nicholas A.; Gourlay, Robert; Leslie, Nicholas R.; Downes, C. Peter; Batty, Ian H.

2011-01-01

Class I phosphoinositide 3-kinases exert important cellular effects through their two primary lipid products, phosphatidylinositol 3,4,5-trisphosphate and phosphatidylinositol 3,4-bisphosphate (PtdIns(3,4)P2). As few molecular targets for PtdIns(3,4)P2 have yet been identified, a screen for PI 3-kinase-responsive proteins that is selective for these is described. This features a tertiary approach incorporating a unique, primary recruitment of target proteins in intact cells to membranes selectively enriched in PtdIns(3,4)P2. A secondary purification of these proteins, optimized using tandem pleckstrin homology domain containing protein-1 (TAPP-1), an established PtdIns(3,4)P2 selective ligand, yields a fraction enriched in proteins of potentially similar lipid binding character that are identified by liquid chromatography-tandem MS. Thirdly, this approach is coupled to stable isotope labeling with amino acids in cell culture using differential isotope labeling of cells stimulated in the absence and presence of the PI 3-kinase inhibitor wortmannin. This provides a ratio-metric readout that distinguishes authentically responsive components from copurifying background proteins. Enriched fractions thus obtained from astrocytoma cells revealed a subset of proteins that exhibited ratios indicative of their initial, cellular responsiveness to PI 3-kinase activation. The inclusion among these of tandem pleckstrin homology domain containing protein-1, three isoforms of Akt, switch associated protein-70, early endosome antigen-1 and of additional proteins expressing recognized lipid binding domains demonstrates the utility of this strategy and lends credibility to the novel candidate proteins identified. The latter encompass a broad set of proteins that include the gene product of TBC1D2A, a putative Rab guanine nucleotide triphosphatase activating protein (GAP) and IQ motif containing GAP1, a potential tumor promoter. A sequence comparison of the former protein indicates the presence of a pleckstrin homology domain whose lipid binding character remains to be established. IQ motif containing GAP1 lacks known lipid interacting components and a preliminary analysis here indicates that this may exemplify a novel class of atypical phosphoinositide (aPI) binding domain. PMID:21263009

Preparing for Harvesting Radioisotopes from FRIB

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

Peaslee, Graham F.; Lapi, Suzanne E.

2015-02-02

The Facility for Rare Isotope Beams (FRIB) is the next generation accelerator facility under construction at Michigan State University. FRIB will produce a wide variety of rare isotopes by a process called projectile fragmentation for a broad range of new experiments when it comes online in 2020. The accelerated rare isotope beams produced in this facility will be more intense than any current facility in the world - in many cases by more than 1000-fold. These beams will be available to the primary users of FRIB in order to do exciting new fundamental research with accelerated heavy ions. In themore » standard mode of operation, this will mean one radioisotope will be selected at a time for the user. However, the projectile fragmentation process also yields hundreds of other radioisotopes at these bombarding energies, and many of these rare isotopes are long-lived and could have practical applications in medicine, national security or the environment. This project developed new methods to collect these long-lived rare isotopes that are by-products of the standard FRIB operation. These isotopes are important to many areas of research, thus this project will have a broad impact in several scientific areas including medicine, environment and homeland security.« less

Compound Specific Isotope Analysis of Fatty Acids in Southern African Aerosols

NASA Astrophysics Data System (ADS)

Billmark, K. A.; Macko, S. A.; Swap, R. J.

2003-12-01

This study, conducted as a part of the Southern African Regional Science Initiative (SAFARI 2000), applied compound specific isotope analysis to describe aerosols at source regions and rural locations. Stable carbon isotopic compositions of individual fatty acids were determined for aerosol samples collected at four sites throughout southern Africa. Mongu, Zambia and Skukuza, South Africa were chosen for their location within intense seasonal Miombo woodland savanna and bushveld savanna biomass burning source regions, respectively. Urban aerosols were collected at Johannesburg, South Africa and rural samples were collected at Sua Pan, Botswana. Fatty acid isotopic compositions varied temporally. Urban aerosols showed significant isotopic enrichment of selected short chain fatty acids (C < 20) compared to aerosols produced during biomass combustion. Sua Pan short chain fatty acid signatures were significantly different from the other non-urban sites, which suggests that sources other than biomass combustion products, such as organic eolian material, impact the Sua Pan aerosol profile. However, a high degree of correlation between Sua Pan and Skukuza long chain fatty acid δ 13C values confirm atmospheric linkages between the two areas and that isotopic signatures of combusted fatty acids are unaltered during atmospheric transport highlighting their potential for use as a conservative tracer.

Isotopic and Chemical Evidence for Primitive Aqueous Alteration in the Tagish Lake Meteorite

NASA Astrophysics Data System (ADS)

Sakuma, Keisuke; Hidaka, Hiroshi; Yoneda, Shigekazu

2018-01-01

Aqueous alteration is one of the primitive activities that occurred on meteorite parent bodies in the early solar system. The Tagish Lake meteorite is known to show an intense parent body aqueous alteration signature. In this study, quantitative analyses of the alkaline elements and isotopic analyses of Sr and Ba from acid leachates of TL (C2-ungrouped) were performed to investigate effects of aqueous alteration. The main purpose of this study is to search for isotopic evidence of extinct 135Cs from the Ba isotopic analyses in the chemical separates from the Tagish Lake meteorite. Barium isotopic data from the leachates show variable 135Ba isotopic anomalies (ε = ‑2.6 ∼ +3.6) which correlatewith 137Ba and 138Ba suggesting a heterogeneous distribution of s- and r-rich nucleosynthetic components in the early solar system. The 87Rb–87Sr and 135Cs–135Ba decay systems on TL in this study do not provide any chronological information. The disturbance of the TL chronometers is likely a reflection of the selective dissolution of Cs and Rb given the relatively higher mobility of Cs and Rb compared to Ba and Sr, respectively, during fluid mineral interactions.

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

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

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

2010-08-11

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

Millennial-scale changes in atmospheric CO2 levels linked to the Southern Ocean carbon isotope gradient and dust flux

NASA Astrophysics Data System (ADS)

Ziegler, Martin; Diz, Paula; Hall, Ian R.; Zahn, Rainer

2013-06-01

The rise in atmospheric CO2 concentrations observed at the end of glacial periods has, at least in part, been attributed to the upwelling of carbon-rich deep water in the Southern Ocean. The magnitude of outgassing of dissolved CO2, however, is influenced by the biological fixation of upwelled inorganic carbon and its transfer back to the deep sea as organic carbon. The efficiency of this biological pump is controlled by the extent of nutrient utilization, which can be stimulated by the delivery of iron by atmospheric dust particles. Changes in nutrient utilization should be reflected in the δ13C gradient between intermediate and deep waters. Here we use the δ13C values of intermediate- and bottom-dwelling foraminifera to reconstruct the carbon isotope gradient between thermocline and abyssal water in the subantarctic zone of the South Atlantic Ocean over the past 360,000 years. We find millennial-scale oscillations of the carbon isotope gradient that correspond to changes in dust flux and atmospheric CO2 concentrations as reported from Antarctic ice cores. We interpret this correlation as a relationship between the efficiency of the biological pump and fertilization by dust-borne iron. As the correlation is exponential, we suggest that the sensitivity of the biological pump to dust-borne iron fertilization may be increased when the background dust flux is low.

Self-powered microthermionic converter

DOEpatents

Marshall, Albert C.; King, Donald B.; Zavadil, Kevin R.; Kravitz, Stanley H.; Tigges, Chris P.; Vawter, Gregory A.

2004-08-10

A self-powered microthermionic converter having an internal thermal power source integrated into the microthermionic converter. These converters can have high energy-conversion efficiencies over a range of operating temperatures. Microengineering techniques are used to manufacture the converter. The utilization of an internal thermal power source increases potential for mobility and incorporation into small devices. High energy efficiency is obtained by utilization of micron-scale interelectrode gap spacing. Alpha-particle emitting radioisotopes can be used for the internal thermal power source, such as curium and polonium isotopes.

Medical Isotope Production Analyses In KIPT Neutron Source Facility

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

Talamo, Alberto; Gohar, Yousry

Medical isotope production analyses in Kharkov Institute of Physics and Technology (KIPT) neutron source facility were performed to include the details of the irradiation cassette and the self-shielding effect. An updated detailed model of the facility was used for the analyses. The facility consists of an accelerator-driven system (ADS), which has a subcritical assembly using low-enriched uranium fuel elements with a beryllium-graphite reflector. The beryllium assemblies of the reflector have the same outer geometry as the fuel elements, which permits loading the subcritical assembly with different number of fuel elements without impacting the reflector performance. The subcritical assembly is drivenmore » by an external neutron source generated from the interaction of 100-kW electron beam with a tungsten target. The facility construction was completed at the end of 2015, and it is planned to start the operation during the year of 2016. It is the first ADS in the world, which has a coolant system for removing the generated fission power. Argonne National Laboratory has developed the design concept and performed extensive design analyses for the facility including its utilization for the production of different radioactive medical isotopes. 99Mo is the parent isotope of 99mTc, which is the most commonly used medical radioactive isotope. Detailed analyses were performed to define the optimal sample irradiation location and the generated activity, for several radioactive medical isotopes, as a function of the irradiation time.« less

A novel technique to determine cobalt exchangeability in soils using isotope dilution.

PubMed

Wendling, Laura A; Kirby, Jason K; McLaughlin, Michael J

2008-01-01

The environmental risk posed by Co contamination is largely a function of its oxidation state. Our objective was to assess the potential biological availability of Co and the reactions and fate of soluble Co(II) after addition to soils with varying physical and chemical characteristics. A potential risk in quantifying exchangeable Co in soils using isotope dilution techniques is the possible presence of two species of Co in soil solution and adsorbed on soil solid phases [Co(II) and Co(III)], coupled with the possibility that when an isotope of Co is added it may undergo a change in oxidation state during the measurement phase. In this study, we have utilized an isotope dilution technique with cation exchange and high-performance liquid chromatography-inductively coupled plasma-mass spectrometry to determine the isotopically exchangeable Co fraction in several soils with varying characteristics such as differing Al, Fe, and Mn oxide content; pH; and organic carbon content. The application of the cation exchange procedure adjusts measurements of isotopically exchangeable Co to correct for the presence of non-exchangeable 57Co not in equilibrium with the solution phase. Results indicated that oxidation of added 57Co(II) to 57Co(III) or precipitation of 57Co(II) may occur on the surfaces of some soils, particularly those with a high pH or substantial quantities of Mn oxide minerals. No detectable Co(III)(aq) was found in the aqueous extracts of the soils examined.

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

Gebauer, R.L.E.; Ehleringer, J.R.

Variation in the ability to utilize pulses of both water and nitrogen (N) is one possible mechanism allowing the coexistence of species in the cold desert community on the Colorado Plateau. The authors simulated 25-mm precipitation events and used stable isotope tracers ({sup 2}H and {sup 15}N) to follow water and N uptake patterns in six dominant perennials (Artemisia filifolia, Coleogyne ramosissima, Cryptantha flava, Ephedra viridis, Quercus havardii, and Vanclevea stylosa) at different times of the growing season. Water pulse utilization varied on a seasonal basis and was to some extent different among species during the summer. Carbon isotope discriminationmore » was negatively related to both plant use of moisture in upper soil layers and foliar N concentration. Species that were similar in water pulse utilization patterns differed in the natural abundance of {sup 15}N, suggesting partitioning in N sources. All species were able to utilize N pulses after rain events, but there were temporal differences in the response among species. The authors also found that water and N uptake in shallow roots do not necessarily occur simultaneously. Artemisia, Cryptantha, and Quercus showed significant uptake of both water and N from the upper soil layers. In contrast, Coleogyne and Ephedra showed the capacity to utilize the water pulse, but not the N pulse. Vanclevea only took up N. The results indicate that different parts of the root system may be responsible for the acquisition of water and N. Their results also suggest that N and water partitioning could contribute to the coexistence of species in highly variable environments such as the Colorado Plateau desert system.« less

Targeted Alpha Therapy: The US DOE Tri-Lab (ORNL, BNL, LANL) Research Effort to Provide Accelerator-Produced 225Ac for Radiotherapy

NASA Astrophysics Data System (ADS)

John, Kevin

2017-01-01

Targeted radiotherapy is an emerging discipline of cancer therapy that exploits the biochemical differences between normal cells and cancer cells to selectively deliver a lethal dose of radiation to cancer cells, while leaving healthy cells relatively unperturbed. A broad overview of targeted alpha therapy including isotope production methods, and associated isotope production facility needs, will be provided. A more general overview of the US Department of Energy Isotope Program's Tri-Lab (ORNL, BNL, LANL) Research Effort to Provide Accelerator-Produced 225Ac for Radiotherapy will also be presented focusing on the accelerator-production of 225Ac and final product isolation methodologies for medical applications.

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

NASA Astrophysics Data System (ADS)

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

2011-03-01

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

Steroid isotopic standards for gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS).

PubMed

Zhang, Ying; Tobias, Herbert J; Brenna, J Thomas

2009-03-01

Carbon isotope ratio (CIR) analysis of urinary steroids using gas chromatography-combustion isotope ratio mass spectrometry (GCC-IRMS) is a recognized test to detect illicit doping with synthetic testosterone. There are currently no universally used steroid isotopic standards (SIS). We adapted a protocol to prepare isotopically uniform steroids for use as a calibrant in GCC-IRMS that can be analyzed under the same conditions as used for steroids extracted from urine. Two separate SIS containing a mixture of steroids were created and coded CU/USADA 33-1 and CU/USADA 34-1, containing acetates and native steroids, respectively. CU/USADA 33-1 contains 5alpha-androstan-3beta-ol acetate (5alpha-A-AC), 5alpha-androstan-3alpha-ol-17-one acetate (androsterone acetate, A-AC), 5beta-androstan-3alpha-ol-11, 17-dione acetate (11-ketoetiocholanolone acetate, 11k-AC) and 5alpha-cholestane (Cne). CU/USADA 34-1 contains 5beta-androstan-3alpha-ol-17-one (etiocholanolone, E), 5alpha-androstan-3alpha-ol-17-one (androsterone, A), and 5beta-pregnane-3alpha, 20alpha-diol (5betaP). Each mixture was prepared and dispensed into a set of about 100 ampoules using a protocol carefully designed to minimize isotopic fractionation and contamination. A natural gas reference material, NIST RM 8559, traceable to the international standard Vienna PeeDee Belemnite (VPDB) was used to calibrate the SIS. Absolute delta(13)C(VPDB) and Deltadelta(13)C(VPDB) values from randomly selected ampoules from both SIS indicate uniformity of steroid isotopic composition within measurement reproducibility, SD(delta(13)C)<0.2 per thousand. This procedure for creation of isotopic steroid mixtures results in consistent standards with isotope ratios traceable to the relevant international reference material.

Individual-specific transgenerational marking of fish populations based on a barium dual-isotope procedure.

PubMed

Huelga-Suarez, Gonzalo; Moldovan, Mariella; Garcia-Valiente, America; Garcia-Vazquez, Eva; Alonso, J Ignacio Garcia

2012-01-03

The present study focuses on the development and evaluation of an individual-specific transgenerational marking procedure using two enriched barium isotopes, (135)Ba and (137)Ba, mixed at a given and selectable molar ratio. The method is based on the deconvolution of the isotope patterns found in the sample into four molar contribution factors: natural xenon (Xe nat), natural barium (Ba nat), Ba135, and Ba137. The ratio of molar contributions between Ba137 and Ba135 is constant and independent of the contribution of natural barium in the sample. This procedure was tested in brown trout ( Salmo trutta ) kept in captivity. Trout were injected with three different Ba137/Ba135 isotopic signatures ca. 7 months and 7 days before spawning to compare the efficiency of the marking procedure at long and short term, respectively. The barium isotopic profiles were measured in the offspring by means of inductively coupled plasma mass spectrometry. Each of the three different isotopic signatures was unequivocally identified in the offspring in both whole eggs and larvae. For 9 month old offspring, the characteristic barium isotope signatures could also be detected in the otoliths even in the presence of a high and variable amount of barium of natural isotope abundance. In conclusion, it can be stated that the proposed dual-isotope marking is inheritable and can be detected after both long-term and short-term marking. Furthermore, the dual-isotope marking can be made individual-specific, so that it allows identification of offspring from a single individual or a group of individuals within a given fish group. © 2011 American Chemical Society

Pb-, Sr- and Nd-Isotopic systematics and chemical characteristics of cenozoic basalts, Eastern China

USGS Publications Warehouse

Peng, Z.C.; Zartman, R.E.; Futa, K.; Chen, D.G.

1986-01-01

Forty-eight Paleogene, Neogene and Quaternary basaltic rocks from northeastern and east-central China have been analyzed for major-element composition, selected trace-element contents, and Pb, Sr and Nd isotopic systematics. The study area lies entirely within the marginal Pacific tectonic domain. Proceeding east to west from the continental margin to the interior, the basalts reveal an isotopic transition in mantle source material and/or degree of crustal interaction. In the east, many of the rocks are found to merge both chemically and isotopically with those previously reported from the Japanese and Taiwan island-arc terrains. In the west, clear evidence exists for component(s) of Late Archean continental lithosphere to be present in some samples. A major crustal structure, the Tan-Lu fault, marks the approximate boundary between continental margin and interior isotopic behaviors. Although the isotopic signature of the western basalts has characteristics of lower-crustal contamination, a subcrustal lithosphere, i.e. an attached mantle keel, is probably more likely to be the major contributor of their continental "flavor". The transition from continental margin to interior is very pronounced for Pb isotopes, although Sr and Nd isotopes also combine to yield correlated patterns that deviate strikingly from the mid-ocean ridge basalt (MORB) and oceanic-island trends. The most distinctive chemical attribute of this continental lithosphere component is its diminished U Pb as reflected in the Pb isotopic composition when compared to sources of MORB, oceanic-island and island-arc volcanic rocks. Somewhat diminished Sm Nd and elevated Rb Sr, especially in comparison to the depleted asthenospheric mantle, are also apparent from the Nd- and Sr-isotopic ratios. ?? 1986.

MIR hollow waveguide (HWG) isotope ratio analyzer for environmental applications

NASA Astrophysics Data System (ADS)

Wang, Zhenyou; Zhuang, Yan; Deev, Andrei; Wu, Sheng

2017-05-01

An advanced commercial Mid-InfraRed Isotope Ratio (IR2) analyzer was developed in Arrow Grand Technologies based on hollow waveguide (HWG) as the sample tube. The stable carbon isotope ratio, i.e. δ13C, was obtained by measuring the selected CO2 absorption peaks in the MIR. Combined with a GC and a combustor, it has been successfully employed to measure compound specific δ13C isotope ratios in the field. By using both the 1- pass HWG and 5-path HWG, we are able to measure δ13C isotope ratio at a broad CO2 concentration of 300 ppm-37,500 ppm. Here, we demonstrate its applications in environmental studies. The δ13C isotope ratio and concentration of CO2 exhaled by soil samples was measured in real time with the isotope analyzer. The concentration was found to change with the time. We also convert the Dissolved Inorganic Carbon (DIC) into CO2, and then measure the δ13C isotope ratio with an accuracy of better than 0.3 ‰ (1 σ) with a 6 min test time and 1 ml sample usage. Tap water, NaHCO3 solvent, coca, and even beer were tested. Lastly, the 13C isotope ratio of CO2 exhaled by human beings was obtained <10 seconds after simply blowing the exhaled CO2 into a tube with an accuracy of 0.5‰ (1 σ) without sample preconditioning. In summary, a commercial HWG isotope analyzer was demonstrated to be able to perform environmental and health studies with a high accuracy ( 0.3 ‰/Hz1/2 1 σ), fast sampling rate (up to 10 Hz), low sample consumption ( 1 ml), and broad CO2 concentration range (300 ppm-37,500 ppm).

Volatile element depletion and K-39/K-41 fractionation in lunar soils

NASA Technical Reports Server (NTRS)

Church, S. E.; Tilton, G. R.; Wright, J. E.; Lee-Hu, C.-N.

1976-01-01

Evidence for selective loss and isotopic fractionation (in the case of K) of volatile elements during formation of agglutinates by micrometeoritic bombardment of lunar soils is presented. Concentrations and isotopic compositions of volatile elements (K, Rb, Pb) and nonvolatile elements (U, Th, Ba, Sr, rare earths) in separates taken from soils 14163, 14259, 15041, 68501, and 71500 are examined. Rayleigh fractionation calculations applied to K-39/K-41 isotopic data indicate ten-fold recycling of bulk soil, to account for observed isotopic anomalies. The lunar soil fines fraction seems to be a site of deposition for volatile or labile Pb produced during agglutination. Local fines (below 75 microns) are viewed as representative of the parent material for agglutinates formed in situ by micrometeoritic impact. Magnetic separation of agglutinates from soil 68501 revealed a bimodal population, with one class comprising welded blocky magnetic glasses.

Composition analysis by scanning femtosecond laser ultraprobing (CASFLU).

DOEpatents

Ishikawa, Muriel Y.; Wood, Lowell L.; Campbell, E. Michael; Stuart, Brent C.; Perry, Michael D.

2002-01-01

The composition analysis by scanning femtosecond ultraprobing (CASFLU) technology scans a focused train of extremely short-duration, very intense laser pulses across a sample. The partially-ionized plasma ablated by each pulse is spectrometrically analyzed in real time, determining the ablated material's composition. The steering of the scanned beam thus is computer directed to either continue ablative material-removal at the same site or to successively remove nearby material for the same type of composition analysis. This invention has utility in high-speed chemical-elemental, molecular-fragment and isotopic analyses of the microstructure composition of complex objects, e.g., the oxygen isotopic compositions of large populations of single osteons in bone.

Sensitivity and Uncertainty Analysis of the GFR MOX Fuel Subassembly

NASA Astrophysics Data System (ADS)

Lüley, J.; Vrban, B.; Čerba, Š.; Haščík, J.; Nečas, V.; Pelloni, S.

2014-04-01

We performed sensitivity and uncertainty analysis as well as benchmark similarity assessment of the MOX fuel subassembly designed for the Gas-Cooled Fast Reactor (GFR) as a representative material of the core. Material composition was defined for each assembly ring separately allowing us to decompose the sensitivities not only for isotopes and reactions but also for spatial regions. This approach was confirmed by direct perturbation calculations for chosen materials and isotopes. Similarity assessment identified only ten partly comparable benchmark experiments that can be utilized in the field of GFR development. Based on the determined uncertainties, we also identified main contributors to the calculation bias.

The behavior of iron and zinc stable isotopes accompanying the subduction of mafic oceanic crust: A case study from Western Alpine ophiolites

NASA Astrophysics Data System (ADS)

Inglis, Edward C.; Debret, Baptiste; Burton, Kevin W.; Millet, Marc-Alban; Pons, Marie-Laure; Dale, Christopher W.; Bouilhol, Pierre; Cooper, Matthew; Nowell, Geoff M.; McCoy-West, Alex J.; Williams, Helen M.

2017-07-01

Arc lavas display elevated Fe3+/ΣFe ratios relative to MORB. One mechanism to explain this is the mobilization and transfer of oxidized or oxidizing components from the subducting slab to the mantle wedge. Here we use iron and zinc isotopes, which are fractionated upon complexation by sulfide, chloride, and carbonate ligands, to remark on the chemistry and oxidation state of fluids released during prograde metamorphism of subducted oceanic crust. We present data for metagabbros and metabasalts from the Chenaillet massif, Queyras complex, and the Zermatt-Saas ophiolite (Western European Alps), which have been metamorphosed at typical subduction zone P-T conditions and preserve their prograde metamorphic history. There is no systematic, detectable fractionation of either Fe or Zn isotopes across metamorphic facies, rather the isotope composition of the eclogites overlaps with published data for MORB. The lack of resolvable Fe isotope fractionation with increasing prograde metamorphism likely reflects the mass balance of the system, and in this scenario Fe mobility is not traceable with Fe isotopes. Given that Zn isotopes are fractionated by S-bearing and C-bearing fluids, this suggests that relatively small amounts of Zn are mobilized from the mafic lithologies in within these types of dehydration fluids. Conversely, metagabbros from the Queyras that are in proximity to metasediments display a significant Fe isotope fractionation. The covariation of δ56Fe of these samples with selected fluid mobile elements suggests the infiltration of sediment derived fluids with an isotopically light signature during subduction.

Method for sequential injection of liquid samples for radioisotope separations

DOEpatents

Egorov, Oleg B.; Grate, Jay W.; Bray, Lane A.

2000-01-01

The present invention is a method of separating a short-lived daughter isotope from a longer lived parent isotope, with recovery of the parent isotope for further use. Using a system with a bi-directional pump and one or more valves, a solution of the parent isotope is processed to generate two separate solutions, one of which contains the daughter isotope, from which the parent has been removed with a high decontamination factor, and the other solution contains the recovered parent isotope. The process can be repeated on this solution of the parent isotope. The system with the fluid drive and one or more valves is controlled by a program on a microprocessor executing a series of steps to accomplish the operation. In one approach, the cow solution is passed through a separation medium that selectively retains the desired daughter isotope, while the parent isotope and the matrix pass through the medium. After washing this medium, the daughter is released from the separation medium using another solution. With the automated generator of the present invention, all solution handling steps necessary to perform a daughter/parent radionuclide separation, e.g. Bi-213 from Ac-225 "cow" solution, are performed in a consistent, enclosed, and remotely operated format. Operator exposure and spread of contamination are greatly minimized compared to the manual generator procedure described in U.S. patent application Ser. No. 08/789,973, now U.S. Pat. No. 5,749,042, herein incorporated by reference. Using 16 mCi of Ac-225 there was no detectable external contamination of the instrument components.

Metabolic flux analysis using 13C peptide label measurements

USDA-ARS?s Scientific Manuscript database

13C metabolic flux analysis (MFA) has become the experimental method of choice to investigate cellular metabolism. MFA has established flux maps of central metabolism for dozens of microbes, cell cultures, and plant seeds. Steady-state MFA utilizes isotopic labeling measurements of amino acids obtai...

Nucleic acid probes as a diagnostic method for tick-borne hemoparasites of veterinary importance.

PubMed

Figueroa, J V; Buening, G M

1995-03-01

An increased number of articles on the use of nucleic acid-based hybridization techniques for diagnostic purposes have been recently published. This article reviews nucleic acid-based hybridization as an assay to detect hemoparasite infections of economic relevance in veterinary medicine. By using recombinant DNA techniques, selected clones containing inserts of Anaplasma, Babesia, Cowdria or Theileria genomic DNA sequences have been obtained, and they are now available to be utilized as specific, highly sensitive DNA or RNA probes to detect the presence of the hemoparasite DNA in an infected animal. Either in an isotopic or non-isotopic detection system, probes have allowed scientists to test for--originally in samples collected from experimentally infected animals and later in samples collected in the field--the presence of hemoparasites during the prepatent, patent, convalescent, and chronic periods of the infection in the host. Nucleic acid probes have given researchers the opportunity to carry out genomic analysis of parasite DNA to differentiate hemoparasite species and to identify genetically distinct populations among and within isolates, strains and clonal populations. Prevalence of parasite infection in the tick vector can now be accomplished more specifically with the nucleic acid probes. Lately, with the advent of the polymerase chain reaction technique, small numbers of hemoparasites can be positively identified in the vertebrate host and tick vector. These techniques can be used to assess the veterinary epidemiological situation in a particular geographical region for the planning of control measures.

Water-use patterns of woody species in pineland and hammock communities of South Florida

USGS Publications Warehouse

Ewe, S.M.L.; da Silveira Lobo Sternberg, Leonel; Sternberg, L.; Busch, D.E.

1999-01-01

Rockland pine forests of south Florida dominated by Pinus elliottii var. densa characteristically have poor soil development in relation to neighboring hardwood hammocks. This has led to the hypothesis that Everglades hammock trees are more reliant on soil moisture derived from local precipitation whereas pineland plants must depend more on groundwater linked to broader regional hydrologic patterns. Because soil moisture sources are likely to vary more than groundwater sources, we hypothesized that hammock plants would exhibit correspondingly higher levels of dry season water stress. This was examined by measuring predawn water potentials, and by analyzing water uptake in representative hammock and pineland woody species using stable isotopes of plant water and that of potential sources during wet and dry seasons. Two species typical of each of the two communities were selected; a fifth species which was found in both communities, Lysiloma latisiliqua Benth., was also analyzed. Water content of soils in both communities decreased from wet to dry season. Consistent with our hypothesis, the change in predawn water potentials between the wet and dry season was less in pineland species than that of hammock species. Water potential changes in L. latisiliqua in both communities resembled that of hammock species more than pineland plants. Isotopic data showed that pineland species rely proportionately more on groundwater than hammock species. Nevertheless, unlike hammock species in the Florida Keys, mainland hammock species utilized a substantial amount of groundwater during the dry season.

Isotope-selective sensor for medical diagnostics based on PAS

NASA Astrophysics Data System (ADS)

Wolff, M.; Groninga, H. G.; Harde, H.

2005-06-01

Development of new optical sensor technologies has a major impact on the progression of diagnostic methods. Of the permanently increasing number of non-invasive 13C-breath tests, the Urea Breath Test for detection of Helicobacter pylori is the most prominent. However, many recent developments go beyond gastroenterological applications. We present a new detection scheme for breath analysis that employs an especially compact and simple set-up based on Photoacoustic Spectroscopy. Using a wavelength-modulated DFB-diode laser and taking advantage of acoustical resonances of the sample cell, we performed very sensitive isotope-selective measurements on CO2. Detection limits for 13CO2 of a few ppm and for the variation of the 13CO2 concentration of approximately 1% were achieved.

Promise and Pitfalls of Lu/Hf-Sm/Nd Garnet Geochronology

NASA Astrophysics Data System (ADS)

King, R. L.; Vervoort, J. D.; Kohn, M. J.; Zirakparvar, N. A.; Hart, G. L.; Corrie, S. L.; Cheng, H.

2007-12-01

Our ability to routinely measure Lu-Hf and Sm-Nd isotopes in garnet allows broad new applications in geochronology, petrology, and tectonics. However, applications of these data can be limited by challenges in interpreting the petrologic record and preparing garnets for analysis. Here, we examine petrologic and chemical pitfalls encountered in garnet geochronology. Petrologic factors influencing trace element compositions in garnet include reactions that modify REE availability and partitioning (1,2), kinetically limited transfer of REEs to garnet (3), and bulk compositional heterogeneities (4). Interpreting the effects of these processes on Sm/Nd and Lu/Hf ages requires characterizing REE zonation prior to isotope analysis and age interpretation. Because garnet fractions are traditionally picked from crushed samples without regard to intracrystalline origins or chemistries, isochrons will represent mixtures derived to varying degrees from all periods of garnet growth. While measured zoning might generally indicate what garnet portion dominates the Lu/Hf or Sm/Nd budget, traditional mineral separation will rarely realize the chronologic potential afforded by high precision Hf and Nd isotope measurements. The potential use of alternative techniques, such as microsampling, necessitates selective digestion and/or leaching to eliminate inclusions within garnet. For Sm/Nd geochronology, H2SO4 leaching removes LREE-rich phosphates (e.g. apatite), but not silicates (e.g. epidote), precluding Sm-Nd dating of some rocks. For Lu/Hf geochronology, ubiquitous zircon microinclusions (c. 1 μm) can significantly disrupt age determinations. Microinclusions cannot be detected optically or separated physically, requiring selective chemical digestion. If complete digestion methods, such as bomb digestion, are used for garnet fractions, then "common Hf" from zircon will be contained in final solutions. These mixed analyses are of dubious utility and will fall into one of two categories based upon inclusion reaction history (5). In "best case" scenarios, zircon will be quasi-co-genetic with garnet formation and all phases will reflect the same Hf pool available during metamorphism. In this case, these "garnet" fractions may retain age information, but will yield underestimated Lu/Hf ratios that severely degrade isochron precision. However, "worst case" scenarios for these mixed-phase analyses will occur when zircon is inherited from prior events, such that garnet analyses represent two, unequilibrated Hf pools. Here, Lu/Hf isotopic analyses do not yield accurate age information on garnet growth as individual isotopic analyses reflect several, unrelated petrologic events. To avoid systematic introduction of errors of this type due to improper digestion procedures, garnet dissolutions should occur via low-pressure, hot-plate style digestion in Teflon beakers. Here, chemical conditions are unlikely to incorporate significant zircon-derived Hf within final solutions, ensuring that Lu/Hf ratios primarily reflect garnet compositions. 1. King et al., 2004, Geochem. Geophys. Geosys. 10.1029/ 2004GC000746; 2.Corrie and Kohn, 2008, J. Metam. Geol. in press; 3.Skora et al., 2006, Contr. Min. Pet. 152, 703-720; 4.Carlson, 2002, Amer.Mineral. 87, 185-204; 3. 5.Scherer et al., 2000, Geochim. Cosmochim. Acta 64, 3413-3432.

Measurement of stable isotopic enrichment and concentration of long-chain fatty acyl-carnitines in tissue by HPLC-MS.

PubMed

Sun, Dayong; Cree, Melanie G; Zhang, Xiao-Jun; Bøersheim, Elisabet; Wolfe, Robert R

2006-02-01

We have developed a new method for the simultaneous measurements of stable isotopic tracer enrichments and concentrations of individual long-chain fatty acyl-carnitines in muscle tissue using ion-pairing high-performance liquid chromatography-electrospray ionization quadrupole mass spectrometry in the selected ion monitoring (SIM) mode. Long-chain fatty acyl-carnitines were extracted from frozen muscle tissue samples by acetonitrile/methanol. Baseline separation was achieved by reverse-phase HPLC in the presence of the volatile ion-pairing reagent heptafluorobutyric acid. The SIM capability of a single quadrupole mass analyzer allows further separation of the ions of interest from the sample matrixes, providing very clean total and selected ion chromatograms that can be used to calculate the stable isotopic tracer enrichment and concentration of long-chain fatty acyl-carnitines in a single analysis. The combination of these two separation techniques greatly simplifies the sample preparation procedure and increases the detection sensitivity. Applying this protocol to biological muscle samples proves it to be a very sensitive, accurate, and precise analytical tool.

Method and apparatus for manufacturing gas tags

DOEpatents

Gross, K.C.; Laug, M.T.

1996-12-17

For use in the manufacture of gas tags employed in a gas tagging failure detection system for a nuclear reactor, a plurality of commercial feed gases each having a respective noble gas isotopic composition are blended under computer control to provide various tag gas mixtures having selected isotopic ratios which are optimized for specified defined conditions such as cost. Using a new approach employing a discrete variable structure rather than the known continuous-variable optimization problem, the computer controlled gas tag manufacturing process employs an analytical formalism from condensed matter physics known as stochastic relaxation, which is a special case of simulated annealing, for input feed gas selection. For a tag blending process involving M tag isotopes with N distinct feed gas mixtures commercially available from an enriched gas supplier, the manufacturing process calculates the cost difference between multiple combinations and specifies gas mixtures which approach the optimum defined conditions. The manufacturing process is then used to control tag blending apparatus incorporating tag gas canisters connected by stainless-steel tubing with computer controlled valves, with the canisters automatically filled with metered quantities of the required feed gases. 4 figs.

Method and apparatus for manufacturing gas tags

DOEpatents

Gross, Kenny C.; Laug, Matthew T.

1996-01-01

For use in the manufacture of gas tags employed in a gas tagging failure detection system for a nuclear reactor, a plurality of commercial feed gases each having a respective noble gas isotopic composition are blended under computer control to provide various tag gas mixtures having selected isotopic ratios which are optimized for specified defined conditions such as cost. Using a new approach employing a discrete variable structure rather than the known continuous-variable optimization problem, the computer controlled gas tag manufacturing process employs an analytical formalism from condensed matter physics known as stochastic relaxation, which is a special case of simulated annealing, for input feed gas selection. For a tag blending process involving M tag isotopes with N distinct feed gas mixtures commercially available from an enriched gas supplier, the manufacturing process calculates the cost difference between multiple combinations and specifies gas mixtures which approach the optimum defined conditions. The manufacturing process is then used to control tag blending apparatus incorporating tag gas canisters connected by stainless-steel tubing with computer controlled valves, with the canisters automatically filled with metered quantities of the required feed gases.

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

Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.

Abstract The continued development of the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma as an ion source for diverse, elemental/isotopic analysis applications continues. To this end, characterization of the capabilities in performing precise and accurate isotope ratio (IR) determinations is essential. Based on past experience with the Thermo Exactive Orbitrap mass analyzer, the LS-APGD was interfaced with this instrument for these tests. While the Orbitrap platform has demonstrated excellent mass resolution and accuracy in “organic” mass spectrometry (MS) applications, work using an Orbitrap for IR analysis is very sparse. These efforts build off previous work in this coupling, where themore » importance of a few of the LS-APGD discharge parameters and Orbitrap data acquisition methods on IR precision and accuracy were probed. Presented here are the results of a study that evaluated the analytical precision for natural uranium sample (assumed 235U/238U = 0.0072) determinations. The instrumental parameters evaluated include the number of microscans and scans making up a data acquisition set, uranium concentration/signal level, sample make-up, and Fourier transform digitization window. Ultimately, a precision of 0.41% relative standard deviation (RSD) can be achieved for a single determination, with a reproducibility of 1.63 %RSD over 10 separate analytical measurements. A preliminary study of matrix effects on IR measurements of U is presented, highlighting the importance of pre-mass selection before injection into the Orbitrap. The analytical system sensitivity is suggested with the ability to produce a calibration function having an R2 value of >0.99 over a range of 4 orders of magnitude of concentration (~1 – 1000 ng mL-1). These efforts demonstrate the very promising pairing of the LS-APGD ionization source and the Orbitrap, pointing as well to definitive paths forward to better utilize both components in high quality isotope ratio mass spectrometry (IRMS).« less

Low-energy Coulomb excitation of neutron-rich zinc isotopes

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

Walle, J. van de; ISOLDE, CERN, Geneva; Aksouh, F.

2009-01-15

At the radioactive ion beam facility REX-ISOLDE, neutron-rich zinc isotopes were investigated using low-energy Coulomb excitation. These experiments have resulted in B(E2,2{sub 1}{sup +}{yields}0{sub 1}{sup +}) values in {sup 74-80}Zn, B(E2,4{sub 1}{sup +}{yields}2{sub 1}{sup +}) values in {sup 74,76}Zn and the determination of the energy of the first excited 2{sub 1}{sup +} states in {sup 78,80}Zn. The zinc isotopes were produced by high-energy proton- (A=74,76,80) and neutron- (A=78) induced fission of {sup 238}U, combined with selective laser ionization and mass separation. The isobaric beam was postaccelerated by the REX linear accelerator and Coulomb excitation was induced on a thin secondarymore » target, which was surrounded by the MINIBALL germanium detector array. In this work, it is shown how the selective laser ionization can be used to deal with the considerable isobaric beam contamination and how a reliable normalization of the experiment can be achieved. The results for zinc isotopes and the N=50 isotones are compared to collective model predictions and state-of-the-art large-scale shell-model calculations, including a recent empirical residual interaction constructed to describe the present experimental data up to 2004 in this region of the nuclear chart.« less

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Bird migration and avian influenza: a comparison of hydrogen stable isotopes and satellite tracking methods

USGS Publications Warehouse

Bridge, Eli S.; Kelly, Jeffrey F.; Xiao, Xiangming; Takekawa, John Y.; Hill, Nichola J.; Yamage, Mat; Haque, Enam Ul; Islam, Mohammad Anwarul; Mundkur, Taej; Yavuz, Kiraz Erciyas; Leader, Paul; Leung, Connie Y.H.; Smith, Bena; Spragens, Kyle A.; Vandegrift, Kurt J.; Hosseini, Parviez R.; Saif, Samia; Mohsanin, Samiul; Mikolon, Andrea; Islam, Ausrafal; George, Acty; Sivananinthaperumal, Balachandran; Daszak, Peter; Newman, Scott H.

2014-01-01

Satellite-based tracking of migratory waterfowl is an important tool for understanding the potential role of wild birds in the long-distance transmission of highly pathogenic avian influenza. However, employing this technique on a continental scale is prohibitively expensive. This study explores the utility of stable isotope ratios in feathers in examining both the distances traveled by migratory birds and variation in migration behavior. We compared the satellite-derived movement data of 22 ducks from 8 species captured at wintering areas in Bangladesh, Turkey, and Hong Kong with deuterium ratios (δD) in the feathers of these and other individuals captured at the same locations. We derived likely molting locations from the satellite tracking data and generated expected isotope ratios based on an interpolated map of δD in rainwater. Although δD was correlated with the distance between wintering and molting locations, surprisingly, measured δD values were not correlated with either expected values or latitudes of molting sites. However, population-level parameters derived from the satellite-tracking data, such as mean distance between wintering and molting locations and variation in migration distance, were reflected by means and variation of the stable isotope values. Our findings call into question the relevance of the rainfall isotope map for Asia for linking feather isotopes to molting locations, and underscore the need for extensive ground truthing in the form of feather-based isoscapes. Nevertheless, stable isotopes from feathers could inform disease models by characterizing the degree to which regional breeding populations interact at common wintering locations. Feather isotopes also could aid in surveying wintering locations to determine where high-resolution tracking techniques (e.g. satellite tracking) could most effectively be employed. Moreover, intrinsic markers such as stable isotopes offer the only means of inferring movement information from birds that have died as a result of infection. In the absence of feather based-isoscapes, we recommend a combination of isotope analysis and satellite-tracking as the best means of generating aggregate movement data for informing disease models.

Surface area dependence of calcium isotopic reequilibration in carbonates: Implications for isotopic signatures in the weathering zone

NASA Astrophysics Data System (ADS)

Fernandez, N. M.; Druhan, J. L.; Potrel, A.; Jacobson, A. D.

2016-12-01

The concept of dynamic equilibrium carries the implicit assumption of continued isotopic exchange between a mineral and the surrounding fluid. While this effect has received much attention in the marine paleoproxy literature, it has been relatively overlooked in application to the terrestrial environment. In weathering systems, a potential consequence is that rapid reequilibration may alter or erase isotopic signatures generated during secondary mineral formation. The extent and timescale over which isotopic signatures are reset in these hydrologic systems is unknown. Using reactive transport modeling, we show isotopic reequilibration under conditions reflecting terrestrial hydrologic settings to be significant and dependent on the reactive surface area of the solid. In particular, we suggest that the non-traditional stable isotopes commonly used in application to carbonates (e.g., Ca, Mg, Sr) are sensitive to these effects due to their rapid reaction rates. We aim to characterize the dependence of Ca isotopic reequilibration on surface area during calcite precipitation via batch experiments conducted at ambient temperature over 48-hour time periods. Calcite precipitation was performed in a closed batch reactor utilizing a controlled free-drift method. The batch reactors contained mixed supersaturated solutions of CaCl2 and NaHCO3 at an initial pH of 8.54. Precipitation was initiated by seed inoculation of calcite crystals with two distinct, pre-constrained surface areas. All experiments achieved the same final state of chemical equilibrium, but as expected, the fastest approach to equilibrium occurred for experiments employing calcite seeds with the highest surface area. This implies that differences in equilibrated Ca isotope ratios (δ44/40Ca) should reflect differences in surface area. This prediction is upheld by models of the experiments, indicating a measureable difference in δ44Ca during calcite precipitation where the higher surface area corresponds to lower δ44Ca values and a faster approach to isotopic equilibrium. The dependence of δ44Ca resetting on calcite surface areas has broad ramifications for tracing carbonate weathering in the Critical Zone.

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

NASA Technical Reports Server (NTRS)

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

2010-01-01

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Compound-specific carbon, nitrogen, and hydrogen isotopic ratios for amino acids in CM and CR chondrites and their use in evaluating potential formation pathways

NASA Astrophysics Data System (ADS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-09-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (δD, δ13C, and δ15N) of organic compounds can reveal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1/2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CR2 Graves Nunataks (GRA) 95229, CR2 Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing δ13C and increasing δD with increasing carbon number in the α-H, α-NH2 amino acids that correspond to predictions made for formation via Strecker-cyanohydrin synthesis. We also observe light δ13C signatures for β-alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ω-amino acids). Higher deuterium enrichments are observed in α-methyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than in CM chondrites, reflecting different parent-body chemistry.

Compound-Specific Carbon, Nitrogen, and Hydrogen Isotopic Ratios for Amino Acids in CM and CR Chondrites and their use in Evaluating Potential Formation Pathways

NASA Technical Reports Server (NTRS)

Elsila, Jamie E.; Charnley, Steven B.; Burton, Aaron S.; Glavin, Daniel P.; Dworkin, Jason P.

2012-01-01

Stable hydrogen, carbon, and nitrogen isotopic ratios (oD, 013C, and olSN) of organic compounds can revcal information about their origin and formation pathways. Several formation mechanisms and environments have been postulated for the amino acids detected in carbonaceous chondrites. As each proposed mechanism utilizes different precursor molecules, the isotopic signatures of the resulting amino acids may indicate the most likely of these pathways. We have applied gas chromatography with mass spectrometry and combustion isotope ratio mass spectrometry to measure the compound-specific C, N, and H stable isotopic ratios of amino acids from seven CM and CR carbonaceous chondrites: CM1I2 Allan Hills (ALH) 83100, CM2 Murchison, CM2 Lewis Cliff (LEW) 90500, CM2 Lonewolf Nunataks (LON) 94101, CRZ Graves Nunataks (GRA) 95229, CRZ Elephant Moraine (EET) 92042, and CR3 Queen Alexandra Range (QUE) 99177. We compare the isotopic compositions of amino acids in these meteorites with predictions of expected isotopic enrichments from potential formation pathways. We observe trends of decreasing ODC and increasing oD with increasing carbon number in the aH, (l-NH2 amino acids that correspond to predictions made for formation via Streckercyanohydrin synthesis. We also observe light ODC signatures for -alanine, which may indicate either formation via Michael addition or via a pathway that forms primarily small, straight-chain, amine-terminal amino acids (n-ro-amino acids). Higher deuterium enrichments are observed in amethyl amino acids, indicating formation of these amino acids or their precursors in cold interstellar or nebular environments. Finally, individual amino acids are more enriched in deuterium in CR chondrites than CM chondrites, reflecting different parent-body chemistry.

Mercury contamination and stable isotopes reveal variability in foraging ecology of generalist California gulls

USGS Publications Warehouse

Peterson, Sarah; Ackerman, Joshua T.; Eagles-Smith, Collin A.

2017-01-01

Environmental contaminants are a concern for animal health, but contaminant exposure can also be used as a tracer of foraging ecology. In particular, mercury (Hg) concentrations are highly variable among aquatic and terrestrial food webs as a result of habitat- and site-specific biogeochemical processes that produce the bioaccumulative form, methylmercury (MeHg). We used stable isotopes and total Hg (THg) concentrations of a generalist consumer, the California gull (Larus californicus), to examine foraging ecology and illustrate the utility of using Hg contamination as an ecological tracer under certain conditions. We identified four main foraging clusters of gulls during pre-breeding and breeding, using a traditional approach based on light stable isotopes. The foraging cluster with the highest δ15N and δ34S values in gulls (cluster 4) had mean blood THg concentrations 614% (pre-breeding) and 250% (breeding) higher than gulls with the lowest isotope values (cluster 1). Using a traditional approach of stable-isotope mixing models, we showed that breeding birds with a higher proportion of garbage in their diet (cluster 2: 63–82% garbage) corresponded to lower THg concentrations and lower δ15N and δ34S values. In contrast, gull clusters with higher THg concentrations, which were more enriched in 15N and 34S isotopes, consumed a higher proportion of more natural, estuarine prey. δ34S values, which change markedly across the terrestrial to marine habitat gradient, were positively correlated with blood THg concentrations in gulls. The linkage we observed between stable isotopes and THg concentrations suggests that Hg contamination can be used as an additional tool for understanding animal foraging across coastal habitat gradients.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Study on strontium isotope abundance-ratio measurements by using a 13-MeV proton beam

NASA Astrophysics Data System (ADS)

Jeong, Cheol-Ki; Jang, Han; Lee, Goung-Jin

2016-09-01

The Rb-Sr dating method is used in dating Paleozoic and Precambrian rocks. This method measures the 87Rb and the 87Sr concentrations by using thermal ionization mass spectrometry (TIMS) [J. Hefne et al., Inter. J. Phys. Sci. 3(1), 28 (2008)]. In addition, it calculates the initial 87Sr/86Sr ratio to increase the reliability of Rb-Sr dating. In this study, the 87Sr/86Sr ratio was measured by using a 13-MeV proton accelerator. Proton kinetic energies are in the range of tens of megaelectronvolts, and protons have large absorption cross-sections for ( p, n) reactions with most substances. After absorbing a proton with such a high kinetic energy, an element is converted into a nuclide with its atomic number increased by one via nuclear transmutation. These nuclides usually have short half-lives and return to the original state through radioactive decay. When a strontium sample is irradiated with protons, nuclear transmutation occurs; thus, the strontium isotope present in the sample changes to a yttrium isotope, which is an activated radioisotope. Based on this, the 87Sr/86Sr ratio was calculated by analyzing the gamma-rays emitted by each yttrium isotope. The KIRAMS-13 cyclotron at the Cyclotron Center of Chosun University, where 13-MeV protons can be extracted, was utilized in our experiment. The 87Sr/86Sr isotope ratio was computed for samples irradiated with these protons, and the result was similar to the isotope ratio for the Standard Reference Material, i.e., 98.2 ± 3.4%. As part of the analysis, proton activation analyses were performed using 13-MeV protons, and the experimental results of this research suggest a possible approach for measuring the strontium-isotope abundance ratio of samples.

Isotopic Measurements in CAIs with the Nanosims: Implications to the understanding of the Formation process of Ca, Al-Rich Inclusions

NASA Technical Reports Server (NTRS)

Ito, M.; Messenger, S.; Walker, Robert M.

2007-01-01

Ca, Al-rich Inclusions (CAIs) preserve evidence of thermal events that they experienced during their formation in the early solar system. Most CAIs from CV and CO chondrites are characterized by large variations in O-isotopic compositions of primary minerals, with spinel, hibonite, and pyroxene being more O-16-rich than melilite and anorthite, with delta 17, O-18 = approx. -40%o (DELTA O-17 = delta O-17 - 0.52 x delta O-18 = approx. - 20%o ). These anomalous compositions cannot be accounted for by standard mass dependent fractionation and diffusive process of those minerals. It requires the presence of an anomalous oxygen reservoir of nucleosynthetic origin or mass independent fractionations before the formation of CAIs in the early solar system. The CAMECA NanoSIMS is a new generation ion microprobe that offers high sensitivity isotopic measurements with sub 100 nm spatial resolution. The NanoSIMS has significantly improved abilities in the study of presolar grains in various kind of meteorites and the decay products of extinct nuclides in ancient solar system matter. This instrument promises significant improvements over other conventional ion probes in the precision isotopic characterization of sub-micron scales. We report the results of our first O isotopic measurements of various CAI minerals from EK1-6-3 and 7R19-1(a) utilizing the JSC NanoSIMS 50L ion microprobe. We evaluate the measurement conditions, the instrumental mass fractionation factor (IMF) for O isotopic measurement and the accuracy of the isotopic ratio through the analysis of a San Carlos olivine standard and CAI sample of 7R19-1(a).

The Carbon Isotope Ratio in Local Molecular Clouds

NASA Astrophysics Data System (ADS)

Goto, Miwa; Usuda, Tomonori; Takato, Naruhisa; Masahiko, Hayashi; Sakamoto, Seiichi; Mitchell, George

We report the carbon isotope ratio in nearby molecular clouds LkHα 101, AFGL 490, and Mon R2 IRS 3. The vibrational transition bands of 12CO ν = 2 ← 0 and 13CO ν = 1 ← 0 were observed with high resolution near-infrared spectroscopy (R = 23,000) to measure the relative abundance of 13CO to 12CO. The isotopic ratios are 12CO/13CO = 1379 (LkHα 101), 8649 (AFGL 490), and 158 (Mon R2 IRS 3), which is twice higher than in the solar neighborhood. The molecular clouds are with high visible extinction (AV = 10 70 mag), well shielded from destructive FUV field. It is questionable that the selective photo-destruction of 13CO plays a major role in biasing isotope ratio. Uncertainty in the Doppler parameters of the unresolved absorption lines, and possible emission filling of fundamental transitions are suspected to account for the high 12CO/13CO ratio. Higher resolution spectroscopy (R ~ 100,000) is the key to go for the accurate measurement of isotope ratio.

Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

NASA Astrophysics Data System (ADS)

Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.

2017-09-01

Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude less than each of the modern ocean outputs and imparts no isotopic fractionation. Thallium removal into pyrite appears to be associated with a small negative fractionation between -1 and -3 ε205Tl, which renders Tl-depleted waters below the chemocline enriched in isotopically-heavy Tl. Due to the quantitative removal of Tl from euxinic seawater, Tl isotope analyses of the authigenic fraction of underlying euxinic sediments from both the Black Sea and Cariaco Basin capture the Tl isotope value of the oxic portion of their respective water column with no net isotope fractionation. Since the Tl isotope composition of seawater is largely dictated by the relative fraction of Mn-oxide burial versus oceanic crust alteration, we contend that the Tl isotope composition of authigenic Tl in black shales, deposited under euxinic conditions but well-connected to the open ocean, can be utilized to reconstruct the Tl isotope composition of seawater, and thus to reconstruct the global history of Mn-oxide burial.

Compound-specific isotopes of fatty acids as indicators of trophic interactions in the East China Sea ecosystem

NASA Astrophysics Data System (ADS)

Wu, Ying; Wang, Na; Zhang, Jing; Wan, Ruijing; Dai, Fangqun; Jin, Xianshi

2016-09-01

The composition and compound-specific isotopes of fatty acids were studied within food webs in the East China Sea. Lipid-normalized stable carbon isotopes of total organic carbon had a good correlation with trophic level. Variations in fatty acid compositions among diff erent species were observed but were unclear. Diff erent dietary structures could be traced from molecular isotopes of selected fatty acids in the Shiba shrimp ( Matapenaeus joyneri), the coastal mud shrimp ( Solenocera crassicornis) and the northern Maoxia shrimp ( Acetes chinensis). Both M. joyneri and S. crassicornis are mainly benthos feeders, while A. chinensis is a pelagic species, although they have a similar fatty acid composition. There was a good correlation for isotopes of arachidonic acid (C20:4n6; ARA) and docosahexaenoic acid (C22:6n3; DHA) among pelagic species from higher trophic levels. The isotopic compositions of DHA in benthic species were more negative than those of pelagic species at the same trophic level. The fact that the diet of benthic species contains more degraded items, the carbon isotopes of which are derived from a large biochemical fraction, may be the reason for this variation. A comparative study of benthic and pelagic species demonstrated the diff erent carbon sources in potential food items and the presence of a more complex system at the water-sediment interface.

Hydraulic lift in a neotropical savanna.

Treesearch

M.Z. Moreira; F.G. Scholz; S.J. Bucci; L.S. Sternberg; G. Goldstein; F.C. Meinzer; A.C. Franco

2003-01-01

We report hydraulic lift in the sawmlia vegetation of central Brazil (Cerrado). Both heat-pulse measurements and isotopic (deuterium) labelling were used to determine whether hydraulic lift occurred in two common species, and whether neighbouring small shrubs and trees were utilizing this water.Both techniques showed water uptake by tap-...

A precise few-nucleon size difference by isotope shift measurements of helium

NASA Astrophysics Data System (ADS)

Rezaeian, Nima Hassan

We perform high precision measurements of an isotope shift between the two stable isotopes of helium. We use laser excitation of the 23 S1 -- 23P0 transition at 1083 .... in a metastable beam of 3He and 4He atoms. A newly developed tunable laser frequency selector along with our previous electro-optic frequency modulation technique provides extremely reliable, adaptable, and precise frequency and intensity control. The intensity control contributes negligibly to overall experimental uncertainty by selecting (t selection < 50 ) and stabilizing the intensity of the required sideband and eliminating (˜10-5) the unwanted frequencies generated during the modulation of 1083 nm laser carrier frequency. The selection technique uses a MEMS based fiber switch (tswitch ≈ 10 ms) and several temperature stabilized narrow band (˜3 GHz) fiber gratings. A fiber based optical circulator and an inline fiber amplifier provide the desired isolation and the net gain for the selected frequency. Also rapid (˜2 sec.) alternating measurements of the 23 S1 -- 23P0 interval for both species of helium is achieved with a custom fiber laser for simultaneous optical pumping. A servo-controlled retro-reflected laser beam eliminates residual Doppler effects during the isotope shift measurement. An improved detection design and software control makes negligible subtle potential biases in the data collection. With these advances, combined with new internal and external consistency checks, we are able to obtain results consistent with the best previous measurements, but with substantially improved precision. Our measurement of the 23S 1 -- 23P0 isotope shift between 3He and 4He is 31 097 535.2 (5)kHz. The most recent theoretic calculation combined with this measuremen. yields a new determination for nuclear size differences between 3He and 4He: Deltarc = 0.292 6 (1)exp (8)th(52)expfm, with a precision of less than a part in 104 coming from the experimental uncertainty (first parenthesis), and a part in 10 3 coming from theory. This value is consistent with electron scattering measurement, but a factor of 10 more precise. It is inconsistent (4 sigma) with a recent isotope shift measurement on another helium transition (2 1S0 -- 23 S1). Comparisons with ongoing muonic helium measurements may provide clues to the origin of what is currently called the proton puzzle: electronic and muonic measurements of the proton size do not agree. In the future, the experimental improvements described here can be used for higher precision tests of atomic theory and quantum electrodynamics, as well as an important atomic physics source of the fine structure constant.

The Ortles ice cores: uncovering an extended climate archive from the Eastern Alps

NASA Astrophysics Data System (ADS)

Dreossi, Giuliano; Barbante, Carlo; Bertò, Michele; Carturan, Luca; De Blasi, Fabrizio; Gabrieli, Jacopo; Gabrielli, Paolo; Seppi, Roberto; Spolaor, Andrea; Stenni, Barbara; Zanoner, Thomas

2017-04-01

During the last half century, oxygen and hydrogen stable isotope content of ice cores has been extensively used for air temperature reconstructions. The most suitable glaciers of the Alpine area, most exclusively in the Western Alps, have been utilized for ice coring for more than four decades. The paleoclimatic potential of the Eastern Alps is still largely unexploited and was scarcely utilized in the past mainly because of the lower elevation (compared to Western Alps) and hence the difficulty to find glaciers in cold conditions. The warming temperature trend appears to be particularly pronounced in the Alps, threatening the preservation of the glaciated areas and creating a sense of urgency in retrieving climatic archives before it is too late. In autumn 2011, four deep cores were drilled on Mt Ortles, South Tyrol, Italy, at 3859 m a.s.l. An extensive reconstructed temperature record for the Ortles summit, based on the surrounding meteorological station data, is available for the last 150 years, while an automatic weather station had been operating from 2011 to 2015 in proximity of the drilling site. The new ice core chronology, based on 210Pb, tritium, beta emissions analysis and 14C measurements of the particulate organic carbon, indicates that the bottom ice is 7000 years old, making it the second most extended glaciological archive ever retrieved in the Alps. The three equally long ice cores have been analyzed for oxygen and hydrogen stable isotopes throughout their length, and the goal is to create an Ortles stacked record for d18O and dD and compare the isotopic data to instrumental temperatures and to other Alpine records. Since 2008, several snow pits were dug in proximity of the drilling site during summer, when the temperature can often exceed the melting point. The isotopic profiles of the 2015 snow pit, dug at the end of an exceptionally warm summer, show how the isotope signal is now affected by the post-depositional processes that have occurred during that summer.

A novel methodology to investigate isotopic biosignatures

NASA Astrophysics Data System (ADS)

Horner, T. J.; Lee, R. B. Y.; Henderson, G. M.; Rickaby, R. E. M.

2012-04-01

An enduring goal of trace metal isotopic studies of Earth History is to find isotopic 'fingerprints' of life or of life's individual physiochemical processes. Generally, such signatures are sought by relating an isotopic effect observed in controlled laboratory conditions or a well-characterized environment to a more complex system or the geological record. However, such an approach is ultimately limited because life exerts numerous isotopic fractionations on any one element so it is hard to dissect the resultant net fractionation into its individual components. Further, different organisms, often with the same apparent cellular function, can express different isotopic fractionation factors. We have used a novel method to investigate the isotopic fractionation associated with a single physiological process-enzyme specific isotopic fractionation. We selected Cd isotopes since only one biological use of Cd is known, CdCA (a Cd/Zn carbonic anhydrase from the coastal diatom T. Weissflogii). Thus, our investigation can also inform the long standing mystery as to why this generally toxic element appears to have a nutrient-like dissolved isotopic and concentration profile in the oceans. We used the pET-15b plasmid to insert the CdCA gene into the E. coli genome. There is no known biochemical function for Cd in E. coli, making it an ideal vector for studying distinct physiological processes within a single organism. The uptake of Cd and associated isotopic fractionation was determined for both normal cells and those expressing CdCA. It was found that whole cells always exhibited a preference for the light isotopes of Cd, regardless of the expression of CdCA; adsorption of Cd to cell surfaces was not seen to cause isotopic fractionation. However, the cleaning procedure employed exerted a strong control on the observed isotopic composition of cells. Using existing protein purification techniques, we measured the Cd isotopic composition of different subcellular fractions of E. coli (e.g. membranes, cytosol, etc.), including the catalytic metal atoms within CdCA. These experiments allow isotopic exchange reactions to be observed in biological systems at an unparalleled resolution, demonstrating that isotopic fractionation can occur, in vivo, on length scales as small as a few Å. We will explore future applications of this technique using the marine geochemistry of Cd as a case study. This experimental approach has great promise for studying the individual isotopic biosignatures of other biochemical reactions, in particular those which may have been active during early Earth History.

[Water utilization characteristics of the degraded poplar shelterbelts in Zhangbei, Hebei, China.

PubMed

Zhang, Huan; Cao, Jun; Wang, Hua Bing; Song, Bo; Jia, Guo Dong; Liu, Zi Qiang; Yu, Xin Xiao; Zeng, Jia

2018-05-01

In Zhangbei County, Hebei Province, poplar-dominated shelterbelts are degraded to different extents. Water availability is the main limiting factor for plant survival in arid areas. The purpose of this study was to reveal the relationship between water availability and poplar degradation. Based on the hydrogen and oxygen stable isotope techniques, we explored the water sources of Populus simonii under different degradation degrees by comparing the isotopic values of P. simonii xylem water with that in potential water source, and calculated the utilization ratio of each water source. The results showed that the water sources of poplar trees varied with degradation degree. The water sources of P. simonii gradually transferred from the deep layer to the surface layer with the increases of degradation. P. simonii with no degradation mainly absorbed soil water in the range of 320-400 cm, with the utilization rate being 25.1%. P. simonii with slight degradation mainly used soil water at depth of 120-180, 180-240 and 240-320 cm. The total utilization rate of three layers was close to 50.0%, with less utilization of water from other layers. The moderately degraded P. simonii mainly used soil water at depth of 20-40, 40-60 and 60-80 cm. The utilization rate of each layer was 17.5%-20.9%, and the contribution rate of soil water under 120 cm was less than 10.0%. The severely degraded P. simonii mainly used water from surface soil layer (0-20 cm), with the utilization rate being 30.4%, which was significantly higher than that of other water sources. The water sources of poplar shelter forests were gradually shallower during the process of degradation. However, the low soil water content in the shallow layer could not meet the normal water demand of poplar, which would accelerate the degradation and even decline of poplar.

Empirical calibration of the clinopyroxene-garnet magnesium isotope geothermometer and implications

NASA Astrophysics Data System (ADS)

Li, Wang-Ye; Teng, Fang-Zhen; Xiao, Yilin; Gu, Hai-Ou; Zha, Xiang-Ping; Huang, Jian

2016-07-01

The large equilibrium Mg isotope fractionation between clinopyroxene and garnet observed in eclogites makes it a potential high-precision geothermometer, but calibration of this thermometer by natural samples is still limited. Here, we report Mg isotopic compositions of eclogite whole rocks as well as Mg and O isotopic compositions of clinopyroxene and garnet separates from 16 eclogites that formed at different temperatures from the Dabie orogen, China. The whole-rock δ26Mg values vary from -1.20 to +0.10 ‰. Among them, 11 samples display limited δ26Mg variations from -0.36 to -0.17 ‰, similar to those of their protoliths. The mineral separates exhibit very different δ26Mg values, from -0.39 to +0.39 ‰ for clinopyroxenes and from -1.94 to -0.81 ‰ for garnets. The clinopyroxene-garnet Mg isotope fractionation (Δ26Mgclinopyroxene-garnet = δ26Mgclinopyroxene-δ26Mggarnet) varies from 1.05 to 2.15 ‰. The clinopyroxene-garnet O isotope fractionation (Δ18Oclinopyroxene-garnet = δ18Oclinopyroxene-δ18Ogarnet) varies from -1.01 to +0.98 ‰. Equilibrium Mg isotope fractionation between clinopyroxene and garnet in the investigated samples is selected based on both the δ26Mgclinopyroxene versus δ26Mggarnet plot and the state of O isotope equilibrium between clinopyroxene and garnet. The equilibrium Δ26Mgclinopyroxene-garnet and corresponding temperature data obtained in this study, together with those available so far in literatures for natural eclogites, are used to calibrate the clinopyroxene-garnet Mg isotope thermometer. This yields a function of Δ26Mgclinopyroxene-garnet = (0.99 ± 0.06) × 106/ T 2, where T is temperature in Kelvin. The refined function not only provides the best empirically calibrated clinopyroxene-garnet Mg isotope thermometer for precise constraints of temperatures of clinopyroxene- and garnet-bearing rocks, but also has potential applications in high-temperature Mg isotope geochemistry.

Historical and contemporary stable isotope tracer approaches to studying mammalian protein metabolism

PubMed Central

2016-01-01

Over a century ago, Frederick Soddy provided the first evidence for the existence of isotopes; elements that occupy the same position in the periodic table are essentially chemically identical but differ in mass due to a different number of neutrons within the atomic nucleus. Allied to the discovery of isotopes was the development of some of the first forms of mass spectrometers, driven forward by the Nobel laureates JJ Thomson and FW Aston, enabling the accurate separation, identification, and quantification of the relative abundance of these isotopes. As a result, within a few years, the number of known isotopes both stable and radioactive had greatly increased and there are now over 300 stable or radioisotopes presently known. Unknown at the time, however, was the potential utility of these isotopes within biological disciplines, it was soon discovered that these stable isotopes, particularly those of carbon (13C), nitrogen (15N), oxygen (18O), and hydrogen (2H) could be chemically introduced into organic compounds, such as fatty acids, amino acids, and sugars, and used to “trace” the metabolic fate of these compounds within biological systems. From this important breakthrough, the age of the isotope tracer was born. Over the following 80 yrs, stable isotopes would become a vital tool in not only the biological sciences, but also areas as diverse as forensics, geology, and art. This progress has been almost exclusively driven through the development of new and innovative mass spectrometry equipment from IRMS to GC‐MS to LC‐MS, which has allowed for the accurate quantitation of isotopic abundance within samples of complex matrices. This historical review details the development of stable isotope tracers as metabolic tools, with particular reference to their use in monitoring protein metabolism, highlighting the unique array of tools that are now available for the investigation of protein metabolism in vivo at a whole body down to a single protein level. Importantly, it will detail how this development has been closely aligned to the technological development within the area of mass spectrometry. Without the dedicated development provided by these mass spectrometrists over the past century, the use of stable isotope tracers within the field of protein metabolism would not be as widely applied as it is today, this relationship will no doubt continue to flourish in the future and stable isotope tracers will maintain their importance as a tool within the biological sciences for many years to come. © 2016 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc. Mass Spec Rev PMID:27182900

A Tale of Two Gases: Isotope Effects Associated with the Enzymatic Production of H2 and N2O

NASA Astrophysics Data System (ADS)

Yang, H.; Gandhi, H.; Kreuzer, H. W.; Moran, J.; Hill, E. A.; McQuarters, A.; Lehnert, N.; Ostrom, N. E.; Hegg, E. L.

2014-12-01

Stable isotopes can provide considerable insight into enzymatic mechanisms and fluxes in various biological processes. In our studies, we used stable isotopes to characterize both enzyme-catalyzed H2 and N2O production. H2 is a potential alternative clean energy source and also a key metabolite in many microbial communities. Biological H2 production is generally catalyzed by hydrogenases, enzymes that combine protons and electrons to produce H2 under anaerobic conditions. In our study, H isotopes and fractionation factors (α) were used to characterize two types of hydrogenases: [FeFe]- and [NiFe]-hydrogenases. Due to differences in the active site, the α associated with H2 production for [FeFe]- and [NiFe]-hydrogenases separated into two distinct clusters (αFeFe > αNiFe). The calculated kinetic isotope effects indicate that hydrogenase-catalyzed H2 production has a preference for light isotopes, consistent with the relative bond strengths of O-H and H-H bonds. Interestingly, the isotope effects associated with H2 consumption and H2-H2O exchange reactions were also characterized, but in this case no specific difference was observed between the different enzymes. N2O is a potent greenhouse gas with a global warming potential 300 times that of CO2, and the concentration of N2O is currently increasing at a rate of ~0.25% per year. Thus far, bacterial and fungal denitrification processes have been identified as two of the major sources of biologically generated N2O. In this study, we measured the δ15N, δ18O, δ15Nα (central N atom in N2O), and δ15Nβ (terminal N atom in N2O) of N2O generated by purified fungal P450 nitric oxide reductase (P450nor) from Histoplasma capsulatum. We observed normal isotope effects for δ18O and δ15Nα, and inverse isotope effects for bulk δ15N (the average of Nα and Nβ) and δ15Nβ. The observed isotope effects have been used in conjunction with DFT calculations to provide important insight into the mechanism of P450nor. Similar experiments were performed with bacterial nitric oxide reductase from Paracoccus denitrificans (cNOR). In this case both Nα and Nβ exhibited inverse isotope effects, while O had a normal isotope effect. Together, these data highlight the utility in using stable isotopes as both tracers and mechanistic probes when studying metabolic processes.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

Assessment of marine-derived nutrients in the Copper River Delta, Alaska, using natural abundance of the stable isotopes of nitrogen, sulfur, and carbon

USGS Publications Warehouse

Kline, Thomas C.; Woody, Carol Ann; Bishop, Mary Anne; Powers, Sean P.; Knudsen, E. Eric

2007-01-01

We performed nitrogen, sulfur, and carbon stable isotope analysis (SIA) on maturing and juvenile anadromous sockeye and coho salmon, and periphyton in two Copper River delta watersheds of Alaska to trace salmonderived nutrients during 2003–2004. Maturing salmon were isotopically enriched relative to alternate freshwater N, S, and C sources as expected, with differences consistent with species trophic level differences, and minor system, sex, and year-to-year differences, enabling use of SIA to trace these salmon-derived nutrients. Periphyton naturally colonized, incubated, and collected using Wildco Periphtyon Samplers in and near spawning sites was 34S- and 15N-enriched, as expected, and at all freshwater sites was 13C-depleted. At nonspawning and coho-only sites, periphyton 34S and 15N was generally low. However, 34S was low enough at some sites to be suggestive of sulfate reduction, complicating the use of S isotopes. Juvenile salmon SIA ranged in values consistent with using production derived from re-mineralization as well as direct utilization, but only by a minority fraction of coho salmon. Dependency on salmon-derived nutrients ranged from relatively high to relatively low, suggesting a space-limited system. No one particular isotope was found to be superior for determining the relative importance of salmon-derived nutrients.

Assigning king eiders to wintering regions in the Bering Sea using stable isotopes of feathers and claws

USGS Publications Warehouse

Oppel, S.; Powell, A.N.

2008-01-01

Identification of wintering regions for birds sampled during the breeding season is crucial to understanding how events outside the breeding season may affect populations. We assigned king eiders captured on breeding grounds in northern Alaska to 3 broad geographic wintering regions in the Bering Sea using stable carbon and nitrogen isotopes obtained from head feathers. Using a discriminant function analysis of feathers obtained from birds tracked with satellite transmitters, we estimated that 88 % of feathers were assigned to the region in which they were grown. We then assigned 84 birds of unknown origin to wintering regions based on their head feather isotope ratios, and tested the utility of claws for geographic assignment. Based on the feather results, we estimated that similar proportions of birds in our study area use each of the 3 wintering regions in the Bering Sea. These results are in close agreement with estimates from satellite telemetry and show the usefulness of stable isotope signatures of feathers in assigning marine birds to geographic regions. The use of claws is currently limited by incomplete understanding of claw growth rates. Data presented here will allow managers of eiders, other marine birds, and marine mammals to assign animals to regions in the Bering Sea based on stable isotope signatures of body tissues. ?? Inter-Research 2008.

Deposition Profile Analysis from DIII-D Metal Rings Campaign Outer-Midplane Collector Probe Diagnostic and Utilization of Enriched Isotopic Tungsten Tracer Particles

NASA Astrophysics Data System (ADS)

Donovan, D. C.; Duran, J.; Zamperini, S.; Lee, S.; Unterberg, E. A.; Wampler, W. R.; Rudakov, D. L.; Elder, D.; Stangeby, P. C.; Abrams, T.

2017-10-01

The DIII-D Metal Rings Campaign used isotopically-enriched, W-coated divertor tiles coupled with dual-facing midplane collector probes (CPs) in the far Scrape-off Layer (SOL). Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) results are presented characterizing the isotopic ratios of deposited W on the CPs and which give quantitative information on the transport of W from specific poloidal locations within the lower outer divertor region having different isotopically-marked tiles. Rutherford Backscattering Spectrometry (RBS) of these CPs has provided areal densities of elemental W content. These resultant W deposition profiles were compared with DIVIMP modelling of the far-SOL to better understand impurity transport in the edge plasma. CPs were exposed for 37 distinct operating configurations (L-mode/H-mode, forward/reverse Bt, strikepoint position). Radial decay lengths (RDL) between 5 and 50 mm were observed with consistently narrower RDL and higher peak W content on the side of the probes connected along field lines to the inner divertor, indicating a concentration of W in the upstream plasma. Correlations are discussed between peak W content, RDL, and isotopic profiles on the CPs over a wide range of conditions. Work supported by US DOE under DE-AC05-00OR22725, DE-FG02-07ER54917, DE-FC02-04ER54698, DE-NA0003525.

Diets of introduced predators using stable isotopes and stomach contents

USGS Publications Warehouse

Meckstroth, A.M.; Miles, A.K.; Chandra, S.

2007-01-01

In a study of predation on ground-nesting birds at South San Francisco Bay (South Bay), California, USA, we analyzed stomach contents and stable isotopes of carbon and nitrogen to identify commonly consumed prey. We obtained the stomach contents from 206 nonnative red foxes (Vulpes vulpes regalis) collected in the South Bay area and Monterey County during 1995-2001 and from 68 feral cats (Felis silvestris) from the South Bay area during 2001-2002. We determined prey identity, biomass, and frequency, described seasonal diet trends, and derived an Index of Relative Importance. Avian species were the most frequent prey we found in the stomachs of red foxes from South Bay (61%), whereas small rodents were most frequent for red foxes from Monterey County (62%). Small rodents were the most frequent prey we found in feral cats (63%). Carbon and nitrogen isotopic signatures for foxes supported stomach content findings. However, isotope results indicated that cats received a majority of their energy from a source other than rodents and outside the natural system, which differed from the stomach content analysis. We demonstrated the utility of both stable isotope and stomach content analyses to establish a more complete understanding of predators' diets. This information aids natural resource managers in planning and evaluating future predator-removal programs and increases our understanding of the impacts of nonnative foxes and cats on native species.

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

USGS Publications Warehouse

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

2016-01-01

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

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River, Oregon, USA

USGS Publications Warehouse

Poulson, S.R.; Sullivan, A.B.

2009-01-01

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes. Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen-??18O and dissolved inorganic carbon-??13C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO-??18O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer. Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems. ?? 2009 Elsevier B.V.

Silicon Isotopes of Marine Pore Water: Tracking the Destiny of Marine Biogenic Opal

NASA Astrophysics Data System (ADS)

Cassarino, L.; Hendry, K. R.

2017-12-01

Silicon isotopes (δ30Si) are a powerful tool for the studying of the past and present silicon cycles, which is closely linked to the carbon cycle. Siliceous phytoplankton, such as diatoms, as one of the major conveyors of carbon to marine sediments. δ30Si from fossil diatoms has been shown to represent past silicic acid (DSi) utilization in the photic zone, since the lighter isotope is preferentially incorporated in their skeleton, the frustule. This assumes that species in the sediments depict past blooms and that frustules are preserved in their initial state during burial. Here we present new silicon isotopes data of sea water and pore water of deep marine sediments from two contrasted environments, the Equatorial Atlantic and West Antarctic Peninsula. δ30Si and DSi concentration, of both sea water and pore water, are negatively correlated. Marine biogenic opal dissolution can be tracked using δ30Si signature of pore water as lighter signals and high DSi concentrations are associated with the biogenic silica. Our data enhances post depositional and diagenesis processes during burial with a clear highlight on the sediment water interface exchanges.

Osmium uptake, distribution, and 187Os/188Os and 187Re/188Os compositions in Phaeophyceae macroalgae, Fucus vesiculosus: Implications for determining the 187Os/188Os composition of seawater

NASA Astrophysics Data System (ADS)

Racionero-Gómez, B.; Sproson, A. D.; Selby, D.; Gannoun, A.; Gröcke, D. R.; Greenwell, H. C.; Burton, K. W.

2017-02-01

The osmium isotopic composition (187Os/188Os) of seawater reflects the balance of input from mantle-, continental- and anthropogenic-derived sources. This study utilizes the Phaeophyceae, Fucus vesiculosus, to analyse its Os abundance and uptake, as well as to assess if macroalgae records the Os isotope composition of the seawater in which it lives. The data demonstrates that Os is not located in one specific biological structure within macroalgae, but is found throughout the organism. Osmium uptake was measured by culturing F. vesiculosus non-fertile tips with different concentrations of Os with a known 187Os/188Os composition (∼0.16), which is significantly different from the background isotopic composition of local seawater (∼0.94). The Os abundance of cultured non-fertile tips show a positive correlation to the concentration of the Os doped seawater. Moreover, the 187Os/188Os composition of the seaweed equalled that of the culture medium, strongly confirming the possible use of macroalgae as a biological proxy for the Os isotopic composition of the seawater.

Shot-noise Limited Faraday Rotation Spectroscopy for Detection of Nitric Oxide Isotopes in Breath, Urine, and Blood

PubMed Central

Wang, Yin; Nikodem, Michal; Zhang, Eric; Cikach, Frank; Barnes, Jarrod; Comhair, Suzy; Dweik, Raed A.; Kao, Christina; Wysocki, Gerard

2015-01-01

Measurement of NO and/or its metabolites in the various body compartments has transformed our understanding of biology. The inability of the current NO measurement methods to account for naturally occurring and experimental NO isotopes, however, has prevented the scientific community from fully understating NO metabolism in vivo. Here we present a mid-IR Faraday rotation spectrometer (FRS) for detection of NO isotopes. The instrument utilizes a novel dual modulation/demodulation (DM) FRS method which exhibits noise performance at only 2 times the fundamental quantum shot-noise level and provides the record sensitivity in its class. This is achieved with a system that is fully autonomous, robust, transportable, and does not require cryogenic cooling. The DM-FRS enables continuous monitoring of nitric oxide isotopes with the detection limits of 3.72 ppbv/Hz1/2 to14NO and 0.53 ppbv/Hz1/2 to15NO using only 45 cm active optical path. This DM-FRS measurement method can be used to improve the performance of conventional FRS sensors targeting other radical species. The feasibility of the instrument to perform measurements relevant to studies of NO metabolism in humans is demonstrated. PMID:25767064