WorldWideScience

Sample records for cesium isotope ratio

  1. Temporal variation of cesium isotope concentrations and atom ratios in zooplankton in the Pacific off the east coast of Japan

    Science.gov (United States)

    Ikenoue, Takahito; Takata, Hyoe; Kusakabe, Masashi; Kudo, Natsumi; Hasegawa, Kazuyuki; Ishimaru, Takashi

    2017-01-01

    After the Fukushima Daiichi Nuclear Power Plant accident in March 2011, concentrations of cesium isotopes (133Cs, 134Cs, and 137Cs) were measured in zooplankton collected in the Pacific off the east coast of Japan from May 2012 to February 2015. The time series of the data exhibited sporadic 137Cs concentration peaks in zooplankton. In addition, the atom ratio of 137Cs/133Cs in zooplankton was consistently high compared to that in ambient seawater throughout the sampling period. These phenomena cannot be explained fully by the bioaccumulation of 137Cs in zooplankton via ambient seawater intake, the inclusion of resuspended sediment in the plankton sample, or the taxonomic composition of the plankton. Autoradiography revealed highly radioactive particles within zooplankton samples, which could be the main factor underlying the sporadic appearance of high 137Cs concentrations in zooplankton as well as the higher ratio of 137Cs/133Cs in zooplankton than in seawater.

  2. Deciphering the measured ratios of Iodine-131 to Cesium-137 at the Fukushima reactors

    CERN Document Server

    Matsui, T

    2011-01-01

    We calculate the relative abundance of the radioactive isotopes Iodine-131 and Cesium-137 produced by nuclear fission in reactors and compare it with data taken at the troubled Fukushima Dai-ichi nuclear power plant. The ratio of radioactivities of these two isotopes can be used to obtain information about when the nuclear reactions terminated.

  3. Hanford Isotope Project strategic business analysis Cesium-137 (Cs-137)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-10-01

    The purpose of this business analysis is to address the beneficial reuse of Cesium 137 (Cs-137) in order to utilize a valuable national asset and possibly save millions of tax dollars. Food irradiation is the front runner application along with other uses. This business analysis supports the objectives of the Department of Energy National Isotope Strategy distributed in August 1994 which describes the DOE plans for the production and distribution of isotope products and services. As part of the Department`s mission as stated in that document. ``The Department of Energy will also continue to produce and distribute other radioisotopes and enriched stable isotopes for medical diagnostics and therapeutics, industrial, agricultural, and other useful applications on a businesslike basis. This is consistent with the goals and objectives of the National Performance Review. The Department will endeavor to look at opportunities for private sector to co-fund or invest in new ventures. Also, the Department will seek to divest from ventures that can more profitably or reliably be operated by the private sector.``

  4. Application of Cesium isotopes in daily life; Aplicacoes dos isotopos do Cesio no cotidiano

    Energy Technology Data Exchange (ETDEWEB)

    Jordao, B.O.; Quaresma, D.S.; Carvalho, R.J., E-mail: bjordan@on.br, E-mail: dansq@on.br, E-mail: carvalho@on.br [Observatorio Nacional (ON/LPTF), Rio de Janeiro, RJ (Brazil). Lab. Nacional de Tempo e Frequencia; Peixoto, J.G.P., E-mail: guilherm@ird.gov.br [Instituto de Radioprotecao e Dosimetria, (IRD/CNEN-RJ), Rio de Janeiro, RJ (Brazil). Lab. de Metrologia das Radiacoes Ionizantes

    2014-07-01

    In the world of science, the desire of the scientific community to discover new chemical elements is crucial for the development of new technologies in various fields of knowledge. And the main chemical element addressed by this article is Cesium, but specifically {sup 133}Cesium isotope and radioisotope {sup 137}Cesium, exemplifying their physical and chemical characteristics, and their applications. This article will also show how these isotopes have provided researchers a breakthrough in the field of radiological medicine and in time and frequency metrology. (author)

  5. Carbon, cesium and iodine isotopes in Japanese cedar leaves from Iwaki, Fukushima

    DEFF Research Database (Denmark)

    Xu, Sheng; Cook, Gordon T.; Cresswell, Alan J.;

    2016-01-01

    Japanese cedar leaves from Iwaki, Fukushima were analyzed for carbon, cesium and iodine isotopic compositions before and after the 2011 nuclear accident. The Δ14C values reflect ambient atmospheric 14C concentrations during the year the leaves were sampled/defoliated, and also previous year...

  6. Concentration Ratios for Cesium and Strontium in Produce Near Los Alamos

    Energy Technology Data Exchange (ETDEWEB)

    S. Salazar, M.McNaughton, P.R. Fresquez

    2006-03-01

    The ratios of the concentrations of radionuclides in produce (fruits, vegetables, and grains) to the concentrations in the soil have been measured for cesium and strontium at locations near Los Alamos. The Soil, Foodstuffs, and Biota Team of the Meteorology and Air Quality Group of the Los Alamos National Laboratory (LANL) obtained the data at locations within a radius of 50 miles of LANL. The concentration ratios are in good agreement with previous measurements: 0.01 to 0.06 for cesium-137 and 0.1 to 0.5 for strontium-90 (wet-weight basis).

  7. Analysis of high burnup pressurized water reactor fuel using uranium, plutonium, neodymium, and cesium isotope correlations with burnup

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jung Suk; Jeon, Young Shin; Park, Soon Dal; Ha, Yeong Keong; Song, Kyu Seok [Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2015-12-15

    The correlation of the isotopic composition of uranium, plutonium, neodymium, and cesium with the burnup for high burnup pressurized water reactor fuels irradiated in nuclear power reactors has been experimentally investigated. The total burnup was determined by Nd-148 and the fractional {sup 235}U burnup was determined by U and Pu mass spectrometric methods. The isotopic compositions of U, Pu, Nd, and Cs after their separation from the irradiated fuel samples were measured using thermal ionization mass spectrometry. The contents of these elements in the irradiated fuel were determined through an isotope dilution mass spectrometric method using {sup 233}U, {sup 242}Pu, {sup 150}Nd, and {sup 133}Cs as spikes. The activity ratios of Cs isotopes in the fuel samples were determined using gamma-ray spectrometry. The content of each element and its isotopic compositions in the irradiated fuel were expressed by their correlation with the total and fractional burnup, burnup parameters, and the isotopic compositions of different elements. The results obtained from the experimental methods were compared with those calculated using the ORIGEN-S code.

  8. Measuring Isotope Ratios Across the Solar System

    Science.gov (United States)

    Webster, Chris R.; Mahaffy, Paul R.

    2012-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biology [1]. For the Allan Hills 84001 meteorite, for example, the (sup 1)(sup 3)C/(sup 1)(sup 2)C ratio identifies it as a Mars (SNC) meteorite; the ??K/??Ar ratio tells us the last time the rock cooled to solid, namely 4 Gya; isotope ratios in (sup 3)He, (sup 2)(sup 1)Ne and (sup 3)?Ar show it was in space (cosmic ray exposure) for 10-20 million years; (sup 1)?C dating that it sat in Antarctica for 13,000 years before discovery; and clumped isotope analysis of (sup 1)?O(sup 1)(sup 3)C(sup 1)?O in its carbonate that it was formed at 18+/-4 ?C in a near-surface aqueous environment [2]. Solar System Formation

  9. Determination of fission gas yields from isotope ratios

    DEFF Research Database (Denmark)

    Mogensen, Mogens Bjerg

    1983-01-01

    This paper describes a method of calculating the actual fission yield of Kr and Xe in nuclear fuel including the effect of neutron capture reactions and decay. The bases for this calculation are the cumulative yields (ref. 1) of Kr and Xe isotopes (or pairs of isotopes) which are unaffected...... by neutron capture reactions, and measured Kr and Xe isotope ratios. Also the burnup contribution from the different fissile heavy isotopes must be known in order to get accurate fission gas yields....

  10. THE ATOMIC WEIGHTS COMMISSION AND ISOTOPIC ABUNDANCE RATIO DETERMINATIONS.

    Energy Technology Data Exchange (ETDEWEB)

    HOLDEN, N.E.

    2005-08-07

    Following Thomson's discovery of stable isotopes in non-radioactive chemical elements, the derivation of atomic weight values from mass spectrometric measurements of isotopic abundance ratios moved very slowly. Forty years later, only 3 1/2 % of the recommended values were based on mass spectrometric measurements and only 38% in the first half century. It might be noted that two chemical elements (tellurium and mercury) are still based on chemical measurements, where the atomic weight value calculated from the relative isotopic abundance measurement either agrees with the value from the chemical measurement or the atomic weight value calculated from the relative isotopic abundance measurement falls within the uncertainty of the chemical measurement of the atomic weight. Of the 19 chemical elements, whose atomic weight is based on non-corrected relative isotopic abundance measurements, five of these are two isotope systems (indium, iridium, lanthanum, lutetium and tantalum) and one is a three-isotope system (oxygen).

  11. Advances in laser-based isotope ratio measurements: selected applications

    OpenAIRE

    Kerstel, E; Gianfrani, L.

    2008-01-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are be...

  12. Stable carbon isotope ratios of ambient aromatic volatile organic compounds

    Science.gov (United States)

    Kornilova, Anna; Huang, Lin; Saccon, Marina; Rudolph, Jochen

    2016-09-01

    Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, ∫ [OH]dt) of the different VOC. It is found that ∫ [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform ∫ [OH]dt for VOC with different reactivity is not justified and that the observed values for ∫ [OH]dt are the result of mixing of VOC from air masses with different values for ∫ [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine ∫ [OH]dt would result in values for ∫ [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform ∫ [OH]dt for an air mass has to be replaced by the concept of individual values of an average ∫ [OH]dt for VOC with different reactivity.

  13. Combination of carbon isotope ratio with hydrogen isotope ratio determinations in sports drug testing.

    Science.gov (United States)

    Piper, Thomas; Emery, Caroline; Thomas, Andreas; Saugy, Martial; Thevis, Mario

    2013-06-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully applied to doping control analysis for many years to uncover the misuse of endogenous steroids such as testosterone. Over the years, several challenges and limitations of this approach became apparent, e.g., the influence of inadequate chromatographic separation on CIR values or the emergence of steroid preparations comprising identical CIRs as endogenous steroids. While the latter has been addressed recently by the implementation of hydrogen isotope ratios (HIR), an improved sample preparation for CIR avoiding co-eluting compounds is presented herein together with newly established reference values of those endogenous steroids being relevant for doping controls. From the fraction of glucuronidated steroids 5β-pregnane-3α,20α-diol, 5α-androst-16-en-3α-ol, 3α-Hydroxy-5β-androstane-11,17-dione, 3α-hydroxy-5α-androstan-17-one (ANDRO), 3α-hydroxy-5β-androstan-17-one (ETIO), 3β-hydroxy-androst-5-en-17-one (DHEA), 5α- and 5β-androstane-3α,17β-diol (5aDIOL and 5bDIOL), 17β-hydroxy-androst-4-en-3-one and 17α-hydroxy-androst-4-en-3-one were included. In addition, sulfate conjugates of ANDRO, ETIO, DHEA, 3β-hydroxy-5α-androstan-17-one plus 17α- and androst-5-ene-3β,17β-diol were considered and analyzed after acidic solvolysis. The results obtained for the reference population encompassing n = 67 males and females confirmed earlier findings regarding factors influencing endogenous CIR. Variations in sample preparation influenced CIR measurements especially for 5aDIOL and 5bDIOL, the most valuable steroidal analytes for the detection of testosterone misuse. Earlier investigations on the HIR of the same reference population enabled the evaluation of combined measurements of CIR and HIR and its usefulness regarding both steroid metabolism studies and doping control analysis. The combination of both stable isotopes would allow for lower reference limits providing the same statistical

  14. Direct path integral estimators for isotope fractionation ratios

    CERN Document Server

    Cheng, Bingqing

    2014-01-01

    Fractionation of isotopes among distinct molecules or phases is a quantum effect which is often exploited to obtain insights on reaction mechanisms, biochemical, geochemical and atmospheric phenomena. Accurate evaluation of isotope ratios in atomistic simulations is challenging, because one needs to perform a thermodynamic integration with respect to the isotope mass, along with time-consuming path integral calculations. By re-formulating the problem as a particle exchange in the ring polymer partition function, we derive new estimators giving direct access to the differential partitioning of isotopes, which can simplify the calculations by avoiding thermodynamic integration. We demonstrate the efficiency of these estimators by applying them to investigate the isotope fractionation ratios in the gas-phase Zundel cation, and in a few simple hydrocarbons.

  15. Worldwide lead-isotope ratio in bivalves and sediments

    DEFF Research Database (Denmark)

    Larsen, Martin Mørk; Jacobsen, Gitte; Strand, Jakob;

    The lead-isotope ratio have been used to assess and identify impact of leaded gasoline, coal combustion and  mineral activities[ref 1] due to the difference in 206Pb (~52%), 207Pb (~24%) and 208Pb (~23%) isotope ratios. The source of these differences is the decaying of the parent isotopes of 238U...... to 206Pb, 235U to 207Pb and 232Th to 208Pb. 204Pb is the only stable Pb isotope usually contributing 1% of the total Pb. Differences in 206Pb/207Pb ratio ranges from 1.06 to 1.10 in old Pb ores (e.g. the time of the roman empire), whereas recent mining from radiogenic (high U and Th contents) ores can...

  16. Plutonium isotope ratio variations in North America

    Energy Technology Data Exchange (ETDEWEB)

    Steiner, Robert E [Los Alamos National Laboratory; La Mont, Stephen P [Los Alamos National Laboratory; Eisele, William F [Los Alamos National Laboratory; Fresquez, Philip R [Los Alamos National Laboratory; Mc Naughton, Michael [Los Alamos National Laboratory; Whicker, Jeffrey J [Los Alamos National Laboratory

    2010-12-14

    Historically, approximately 12,000 TBq of plutonium was distributed throughout the global biosphere by thermo nuclear weapons testing. The resultant global plutonium fallout is a complex mixture whose {sup 240}Pu/{sup 239}Pu atom ratio is a function of the design and yield of the devices tested. The average {sup 240}Pu/{sup 239}Pu atom ratio in global fallout is 0.176 + 014. However, the {sup 240}Pu/{sup 239}Pu atom ratio at any location may differ significantly from 0.176. Plutonium has also been released by discharges and accidents associated with the commercial and weapons related nuclear industries. At many locations contributions from this plutonium significantly alters the {sup 240}Pu/{sup 239}Pu atom ratios from those observed in global fallout. We have measured the {sup 240}Pu/{sup 239}Pu atom ratios in environmental samples collected from many locations in North America. This presentation will summarize the analytical results from these measurements. Special emphasis will be placed on interpretation of the significance of the {sup 240}Pu/{sup 239}Pu atom ratios measured in environmental samples collected in the Arctic and in the western portions of the United States.

  17. LITERATURE SURVEY ON ISOTOPIC ABUNDANCE RATIO MEASUREMENTS - 2001-2005

    Energy Technology Data Exchange (ETDEWEB)

    HOLDEN, N.E.

    2005-08-13

    Along with my usual weekly review of the published literature for new nuclear data, I also search for new candidates for best measurements of isotopic abundances from a single source. Most of the published articles, that I previously had found in the Research Library at the Brookhaven Lab, have already been sent to the members of the Atomic Weights Commission, by either Michael Berglund or Thomas Walczyk. In the last few days, I checked the published literature for any other articles in the areas of natural variations in isotopic abundance ratios, measurements of isotopic abundance ratios on samples of extra-terrestrial material and isotopic abundance ratio measurements performed using ICPMS instruments. Hopefully this information will be of interest to members of the Commission, the sub-committee on isotopic abundance measurements (SIAM), members of the former sub-committee on natural isotopic fractionation (SNIF), the sub-committee on extra-terrestrial isotope ratios (SETIR), the RTCE Task Group and the Guidelines Task Group, who are dealing with ICPMS and TIMS comparisons. In the following report, I categorize the publications in one of four areas. Measurements performed using either positive or negative ions with Thermal Ionization Mass Spectrometer, TIMS, instruments; measurements performed on Inductively Coupled Plasma Mass Spectrometer, ICPMS, instruments; measurements of natural variations of the isotopic abundance ratios; and finally measurements on extra-terrestrial samples with instrumentation of either type. There is overlap in these areas. I selected out variations and ET results first and then categorized the rest of the papers by TIMS and ICPMS.

  18. Isotope Ratio Monitoring Gas Chromatography Mass Spectrometry (IRM-GCMS)

    Science.gov (United States)

    Freeman, K. H.; Ricci, S. A.; Studley, A.; Hayes, J. M.

    1989-01-01

    On Earth, the C-13 content of organic compounds is depleted by roughly 13 to 23 permil from atmospheric carbon dioxide. This difference is largely due to isotope effects associated with the fixation of inorganic carbon by photosynthetic organisms. If life once existed on Mars, then it is reasonable to expect to observe a similar fractionation. Although the strongly oxidizing conditions on the surface of Mars make preservation of ancient organic material unlikely, carbon-isotope evidence for the existence of life on Mars may still be preserved. Carbon depleted in C-13 could be preserved either in organic compounds within buried sediments, or in carbonate minerals produced by the oxidation of organic material. A technique is introduced for rapid and precise measurement of the C-13 contents of individual organic compounds. A gas chromatograph is coupled to an isotope-ratio mass spectrometer through a combustion interface, enabling on-line isotopic analysis of isolated compounds. The isotope ratios are determined by integration of ion currents over the course of each chromatographic peak. Software incorporates automatic peak determination, corrections for background, and deconvolution of overlapped peaks. Overall performance of the instrument was evaluated by the analysis of a mixture of high purity n-alkanes of know isotopic composition. Isotopic values measured via IRM-GCMS averaged withing 0.55 permil of their conventionally measured values.

  19. Calcium isotope ratios in animal and human bone

    Science.gov (United States)

    Reynard, L. M.; Henderson, G. M.; Hedges, R. E. M.

    2010-07-01

    Calcium isotopes in tissues are thought to be influenced by an individual's diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ 44/42Ca) of modern and archaeological animal and human bone ( n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ 44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ 44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ 44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ 44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ 44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.

  20. Oxygen isotopic ratios in intermediate-mass red giants

    CERN Document Server

    Lebzelter, Thomas; Hinkle, Kenneth; Nowotny, Walter; Aringer, Bernhard

    2015-01-01

    Context. The abundances of the three main isotopes of oxygen are altered in the course of the CNO-cycle. When the first dredge-up mixes the burning products to the surface, the nucleosynthesis processes can be probed by measuring oxygen isotopic ratios. Aims. By measuring 16O/17O and 16O/18O in red giants of known mass we compare the isotope ratios with predictions from stellar and galactic evolution modelling. Methods. Oxygen isotopic ratios were derived from the K-band spectra of six red giants. The sample red giants are open cluster members with known masses of between 1.8 and 4.5 Msun . The abundance determination employs synthetic spectra calculated with the COMARCS code. The effect of uncertainties in the nuclear reaction rates, the mixing length, and of a change in the initial abundance of the oxygen isotopes was determined by a set of nucleosynthesis and mixing models using the FUNS code. Results. The observed 16O/17O ratios are in good agreement with the model results, even if the measured values do ...

  1. Heavy element stable isotope ratios: analytical approaches and applications.

    Science.gov (United States)

    Tanimizu, Masaharu; Sohrin, Yoshiki; Hirata, Takafumi

    2013-03-01

    Continuous developments in inorganic mass spectrometry techniques, including a combination of an inductively coupled plasma ion source and a magnetic sector-based mass spectrometer equipped with a multiple-collector array, have revolutionized the precision of isotope ratio measurements, and applications of inorganic mass spectrometry for biochemistry, geochemistry, and marine chemistry are beginning to appear on the horizon. Series of pioneering studies have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn, Sr, Ce, Nd, Mo, Cd, W, Tl, and U) are common on Earth, and it had been widely recognized that most physicochemical reactions or biochemical processes induce mass-dependent isotope fractionation. The variations in isotope ratios of the heavy elements can provide new insights into past and present biochemical and geochemical processes. To achieve this, the analytical community is actively solving problems such as spectral interference, mass discrimination drift, chemical separation and purification, and reduction of the contamination of analytes. This article describes data calibration and standardization protocols to allow interlaboratory comparisons or to maintain traceability of data, and basic principles of isotope fractionation in nature, together with high-selectivity and high-yield chemical separation and purification techniques for stable isotope studies.

  2. Stable isotope ratios in hair and teeth reflect biologic rhythms.

    Directory of Open Access Journals (Sweden)

    Otto Appenzeller

    Full Text Available Biologic rhythms give insight into normal physiology and disease. They can be used as biomarkers for neuronal degenerations. We present a diverse data set to show that hair and teeth contain an extended record of biologic rhythms, and that analysis of these tissues could yield signals of neurodegenerations. We examined hair from mummified humans from South America, extinct mammals and modern animals and people, both healthy and diseased, and teeth of hominins. We also monitored heart-rate variability, a measure of a biologic rhythm, in some living subjects and analyzed it using power spectra. The samples were examined to determine variations in stable isotope ratios along the length of the hair and across growth-lines of the enamel in teeth. We found recurring circa-annual periods of slow and fast rhythms in hydrogen isotope ratios in hair and carbon and oxygen isotope ratios in teeth. The power spectra contained slow and fast frequency power, matching, in terms of normalized frequency, the spectra of heart rate variability found in our living subjects. Analysis of the power spectra of hydrogen isotope ratios in hair from a patient with neurodegeneration revealed the same spectral features seen in the patient's heart-rate variability. Our study shows that spectral analysis of stable isotope ratios in readily available tissues such as hair could become a powerful diagnostic tool when effective treatments and neuroprotective drugs for neurodegenerative diseases become available. It also suggests that similar analyses of archaeological specimens could give insight into the physiology of ancient people and animals.

  3. A continuous flow isotope ratio mass spectrometry method for high precision determination of dissolved gas ratios and isotopic composition

    DEFF Research Database (Denmark)

    Charoenpong, C. N.; Bristow, L. A.; Altabet, M. A.

    2014-01-01

    Dissolved gas ratios and isotopic compositions provide essential information about the biological and physical mechanisms influencing N-2, O-2, and Ar in aquatic systems. Current methods available are either limited by overall cost, labor-intensive sample collection and analysis, or insufficient ...

  4. Finite mixture models for the computation of isotope ratios in mixed isotopic samples

    Science.gov (United States)

    Koffler, Daniel; Laaha, Gregor; Leisch, Friedrich; Kappel, Stefanie; Prohaska, Thomas

    2013-04-01

    Finite mixture models have been used for more than 100 years, but have seen a real boost in popularity over the last two decades due to the tremendous increase in available computing power. The areas of application of mixture models range from biology and medicine to physics, economics and marketing. These models can be applied to data where observations originate from various groups and where group affiliations are not known, as is the case for multiple isotope ratios present in mixed isotopic samples. Recently, the potential of finite mixture models for the computation of 235U/238U isotope ratios from transient signals measured in individual (sub-)µm-sized particles by laser ablation - multi-collector - inductively coupled plasma mass spectrometry (LA-MC-ICPMS) was demonstrated by Kappel et al. [1]. The particles, which were deposited on the same substrate, were certified with respect to their isotopic compositions. Here, we focus on the statistical model and its application to isotope data in ecogeochemistry. Commonly applied evaluation approaches for mixed isotopic samples are time-consuming and are dependent on the judgement of the analyst. Thus, isotopic compositions may be overlooked due to the presence of more dominant constituents. Evaluation using finite mixture models can be accomplished unsupervised and automatically. The models try to fit several linear models (regression lines) to subgroups of data taking the respective slope as estimation for the isotope ratio. The finite mixture models are parameterised by: • The number of different ratios. • Number of points belonging to each ratio-group. • The ratios (i.e. slopes) of each group. Fitting of the parameters is done by maximising the log-likelihood function using an iterative expectation-maximisation (EM) algorithm. In each iteration step, groups of size smaller than a control parameter are dropped; thereby the number of different ratios is determined. The analyst only influences some control

  5. Accurate and precise zinc isotope ratio measurements in urban aerosols.

    Science.gov (United States)

    Gioia, Simone; Weiss, Dominik; Coles, Barry; Arnold, Tim; Babinski, Marly

    2008-12-15

    We developed an analytical method and constrained procedural boundary conditions that enable accurate and precise Zn isotope ratio measurements in urban aerosols. We also demonstrate the potential of this new isotope system for air pollutant source tracing. The procedural blank is around 5 ng and significantly lower than published methods due to a tailored ion chromatographic separation. Accurate mass bias correction using external correction with Cu is limited to Zn sample content of approximately 50 ng due to the combined effect of blank contribution of Cu and Zn from the ion exchange procedure and the need to maintain a Cu/Zn ratio of approximately 1. Mass bias is corrected for by applying the common analyte internal standardization method approach. Comparison with other mass bias correction methods demonstrates the accuracy of the method. The average precision of delta(66)Zn determinations in aerosols is around 0.05 per thousand per atomic mass unit. The method was tested on aerosols collected in Sao Paulo City, Brazil. The measurements reveal significant variations in delta(66)Zn(Imperial) ranging between -0.96 and -0.37 per thousand in coarse and between -1.04 and 0.02 per thousand in fine particular matter. This variability suggests that Zn isotopic compositions distinguish atmospheric sources. The isotopic light signature suggests traffic as the main source. We present further delta(66)Zn(Imperial) data for the standard reference material NIST SRM 2783 (delta(66)Zn(Imperial) = 0.26 +/- 0.10 per thousand).

  6. High-accuracy mass determination of unstable cesium and barium isotopes

    CERN Document Server

    Ames, F; Beck, D; Bollen, G; De Saint-Simon, M; Jertz, R; Kluge, H J; Kohl, A; König, M; Lunney, M D; Martel, I; Moore, R B; Otto, T; Patyk, Z; Raimbault-Hartmann, H; Rouleau, G; Savard, G; Schark, E; Schwarz, S; Schweikhard, L; Stolzenberg, H; Szerypo, J

    1999-01-01

    Direct mass measurements of short-lived Cs and Ba isotopes have been performed with the tandem Penning trap mass spectrometer ISOLTRAP installed at the on-line isotope separator ISOLDE at CERN. Typically, a mass resolving power of 600 000 and an accuracy of $\\delta \\mbox{m} \\approx 13$ keV have been obtained. The masses of $^{123,124,126}$Ba and $^{122m}$Cs were measured for the first time. A least-squares adjustment has been performed and the experimental masses are compared with theoretical ones, particularly in the frame of a macroscopic-microscopic model.

  7. Carbon and Oxygen Isotope Ratios in Rona Limestone, Romania

    Directory of Open Access Journals (Sweden)

    Stela Cuna

    2001-04-01

    Full Text Available The carbon and oxygen isotopic compositions of limestones provide criteria for the evaluation of the depositional environment. For Jurassic and younger samples, the best discrimination between marine and fresh-water limestones is given by Z parameter, calculated as a linear correlation between δ13C and δ18O (‰ PDB. Rona Limestone (Upper Paleocene - Lower Eocene, outcropping on a small area in NW Transylvania (Meseş area is a local lacustrine facies. There, it divides Jibou Formation into the Lower Red Member and the Upper Variegated Member, respectively. Recently, a sequence containing a marine nannoplankton assemblage was identified in the base of Rona deposits. The main goal of our study was to characterize, based on the isotopic record, the primary environment of formation of the deposit, as well as that in which some diagenetic processes (the formation of dolomite and of green clay around the siliceous chert nodules took place. Ten samples representing limestones, dolomitic limestone, marls and the green carbonate-rich clay were studied from petrographical and mineralogical points of view, and the carbon and oxygen isotopic ratios from the carbonate (calcite component were measured. In conclusion, it was found that the procedure of extraction of CO2 we used enabled the discrimination between the isotopic prints of calcite vs. dolomite. This pleads for considering our results as a primary isotopic pattern in the bulk rock. The oxygen and carbon isotope data indicate a fresh-water depositional environment with Z<120. The δ13C mean value (-4.96 ‰ PDB is, generally, representative for fresh-water carbonates of the Tertiary period. The same environment characterized also the formation of carbonates within the green clay.

  8. Role of mesoscale eddies in transport of Fukushima-derived cesium isotopes in the ocean

    Science.gov (United States)

    Budyansky, M. V.; Goryachev, V. A.; Kaplunenko, D. D.; Lobanov, V. B.; Prants, S. V.; Sergeev, A. F.; Shlyk, N. V.; Uleysky, M. Yu.

    2015-02-01

    We present the results of in situ measurements of 134Cs and 137Cs released from the Fukushima Nuclear Power Plant (FNPP) collected at surface and different depths in the western North Pacific in June and July 2012. It was found that 15 month after the incident concentrations of radiocesium in the Japan and Okhotsk seas were at background or slightly increased level, while they had increased values in the subarctic front area east of Japan. The highest concentrations of 134Cs and 137Cs up to 13.5±0.9 and 22.7±1.5 Bq m-3 have been found to exceed ten times the background levels before the accident. Maximal content of radiocesium was observed within subsurface and intermediate water layers inside the cores of anticyclonic eddies (100-500 m). Even slightly increased content of radiocesium was found at some eddies at depth of 1000 m. It is expected that convergence and subduction of surface water inside eddies are main mechanisms of downward transport of radionuclides. In situ observations are compared with the results of simulated advection of these radioisotopes by the AVISO altimetric velocity field. Different Lagrangian diagnostics are used to reconstruct the history and origin of synthetic tracers imitating measured seawater samples collected in each of those eddies. The results of observations are consistent with the simulated results. It is shown that the tracers, simulating water samples with increased radioactivity to be measured in the cruise, really visited the areas with presumably high level of contamination. Fast water advection between anticyclonic eddies and convergence of surface water inside eddies makes them responsible for spreading, accumulation and downward transport of cesium rich water to the intermediate depth in the frontal zone.

  9. Isotopic ratio of nitrogen on Titan: Photochemical interpretation

    Science.gov (United States)

    Krasnopolsky, Vladimir A.

    2016-12-01

    Nitrogen isotope fractionation in predissociation of N2 (Liang et al., 2007) is combined with production of N(4S), N(2D), and N+ in dissociation and dissociative ionization by the solar EUV photons, photoelectrons, magnetospheric electrons and protons, and cosmic rays from the photochemical model. The calculated 14N/15N ratio in nitriles is 57, in excellent agreement with the observed ratio in HCN. Loss of nitrogen in condensation and polymerization of nitriles is 392 g cm-2 Byr-1 with nitrogen isotope fractionation factor of 2.8. Loss of nitrogen by sputtering is 57 g cm-2 Byr-1 (De La Haye et al., 2007) with fractionation factor of 0.73 (Mandt et al., 2014). If the current loss was constant throughout the age of the Solar System, then the initial 14N/15N ratio on Titan is 129, similar to 127±32 for ammonia in comets (Rousselot et al., 2014). However, the solar EUV and wind were stronger from the young Sun, and this tends to further reduce the initial 14N/15N ratio. Nevertheless uncertainties of the problem and of the ratio in comets support the idea that nitrogen on Titan appeared as ammonia ice with 14N/15N similar to that in comets.

  10. Radium-based estimates of cesium isotope transport and total direct ocean discharges from the Fukushima Nuclear Power Plant accident

    Directory of Open Access Journals (Sweden)

    M. A. Charette

    2012-11-01

    Full Text Available Radium has four naturally occurring isotopes that have proven useful in constraining water mass source, age, and mixing rates in the coastal and open ocean. In this study, we used radium isotopes to determine the fate and flux of runoff-derived cesium from the Fukushima Nuclear Power Plant (NPP. During a June 2011 cruise, the highest Cs concentrations were found along the eastern shelf of northern Japan, from Fukushima south, to the edge of the Kuroshio current, and in an eddy ∼ 130 km from the NPP site. Locations with the highest cesium also had some of the highest radium activities, suggesting much of the direct ocean discharges of Cs remained in the coastal zone 2–3 months after the accident. We used a short-lived Ra isotope (223Ra, t1/2 = 11.4 d to derive an average water mass age (Tr in the coastal zone of 32 days. To ground-truth the Ra age model, we conducted a direct, station-by-station comparison of water mass ages with a numerical oceanographic model and found them to be in excellent agreement (model avg. Tr = 27 days. From these independent Tr values and the inventory of Cs within the water column at the time of our cruise, we were able to calculate an offshore 134Cs flux of 3.9–4.6 × 1013 Bq d−1. Radium-228 (t1/2 = 5.75 yr was used to derive a vertical eddy diffusivity (Kz of 0.7 m2 d−1 (0.1 cm2 s−1; from this Kz and 134Cs inventory, we estimated a 134Cs flux across the pycnocline of 1.8 × 104 Bq d−1 for the same time period. On average, our results show that horizontal mixing loss of Cs from the coastal zone was ∼ 109 greater than vertical exchange below the surface mixed layer. Finally, a mixing/dilution model that utilized our Ra-based and

  11. TOWARD A UNIQUE NITROGEN ISOTOPIC RATIO IN COMETARY ICES

    Energy Technology Data Exchange (ETDEWEB)

    Rousselot, Philippe; Cordier, Daniel; Mousis, Olivier [Institut UTINAM-UMR CNRS 6213, Observatoire des Sciences de l' Univers THETA, University of Franche-Comté, BP 1615, F-25010 Besançon Cedex (France); Pirali, Olivier; Vervloet, Michel; Martin-Drumel, Marie-Aline; Gruet, Sébastien [Synchrotron SOLEIL, ligne AILES, UMR 8214 CNRS, L' orme des Merisiers, Saint-Aubin, F-91192 Gif-Sur-Yvette (France); Jehin, Emmanuël; Hutsemékers, Damien; Manfroid, Jean; Arpigny, Claude; Decock, Alice, E-mail: rousselot@obs-besancon.fr [Département d' Astrophysique, de Géophysique et d' Océanographie, Université de Liège, Allée du Six Août, B-4000 Liège (Belgium)

    2014-01-10

    Determination of the nitrogen isotopic ratios in different bodies of the solar system provides important information regarding the solar system's origin. We unambiguously identified emission lines in comets due to the {sup 15}NH{sub 2} radical produced by the photodissociation of {sup 15}NH{sub 3}. Analysis of our data has permitted us to measure the {sup 14}N/{sup 15}N isotopic ratio in comets for a molecule carrying the amine (-NH) functional group. This ratio, within the error, appears similar to that measured in comets in the HCN molecule and the CN radical, and lower than the protosolar value, suggesting that N{sub 2} and NH{sub 3} result from the separation of nitrogen into two distinct reservoirs in the solar nebula. This ratio also appears similar to that measured in Titan's atmospheric N{sub 2}, supporting the hypothesis that, if the latter is representative of its primordial value in NH{sub 3}, these bodies were assembled from building blocks sharing a common formation location.

  12. Stable strontium isotopic ratios from archaeological organic remains from the Thorsberg peat bog

    DEFF Research Database (Denmark)

    Nosch, Marie-Louise Bech; von Carnap-Bornheim, Claus; Grupe, Gisela;

    2007-01-01

    Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog.......Pilot study analysing stable strontium isotopic ratios from Iron Age textile and leather finds from the Thorsberg peat bog....

  13. Carbon isotope ratios and isotopic correlations between components in fruit juices

    Science.gov (United States)

    Wierzchnicki, Ryszard

    2013-04-01

    Nowadays food products are defined by geographical origin, method of production and by some regulations concerning terms of their authenticity. Important data for confirm the authenticity of product are providing by isotopic methods of food control. The method checks crucial criteria which characterize the authenticity of inspected product. The European Union Regulations clearly show the tendency for application of the isotopic methods for food authenticity control (wine, honey, juice). The aim of the legislation steps is the protection of European market from possibility of the commercial frauds. Method of isotope ratio mass spectrometry is very effective tool for the use distinguishably the food products of various geographical origin. The basic problem for identification of the sample origin is the lack of databases of isotopic composition of components and information about the correlations of the data. The subject of the work was study the isotopic correlations existing between components of fruits. The chemical and instrumental methods of separation: water, sugars, organic acids and pulp from fruit were implemented. IRMS technique was used to measure isotopic composition of samples. The final results for original samples of fruits (apple, strawberry etc.) will be presented and discussed. Acknowledgement: This work was supported by the Polish Ministry of Science and Higher Education under grant NR12-0043-10/2010.

  14. Estimating the Isotope Ratio of Ecosystem Respiration Using the Keeling Plot and the Flux Ratio Method

    Science.gov (United States)

    Zhang, J.; Griffis, T. J.; Baker, J. M.

    2004-12-01

    Stable carbon isotope analyses have been used in identifying global carbon sources and sinks and in partitioning ecosystem CO2 exchange into component fluxes. The isotope ratio of ecosystem respiration (δ 13Cr) is a critical parameter in applying stable isotope techniques to carbon cycle problems. The commonly used Keeling plot method in estimating δ 13Cr has limitations related to: 1) insufficient range of CO2 mixing ratio; 2) high sensitivity to curve-fitting techniques; and 3) extrapolation of CO2 mixing ratio beyond observations. In this study, the Keeling plot method was examined and compared with the flux ratio approach using continuous measurements of the mixing ratios of 12CO2 and 13CO2 over an extensive corn canopy during the 2003 growing season. The seasonal variation of δ 13Cr estimated from both methods harmonized with the ecosystem phenology. The δ 13Cr started to increase (became more positive) from mid June and peaked in early August, followed by a decrease into October. The Keeling plot method agreed well with the flux ratio method in the seasonal pattern of δ 13Cr, but tended to give lower values (more negative). The discrepancy between the two approaches was significant in July and August (about 5 per mil) and relatively small in June and September (about 1 to 2 per mil). We examined this discrepancy with respect to wind direction/advection and measurement footprints. In addition, our analysis of high-frequency data (every two minutes) using the flux ratio method indicates that δ 13Cr may vary significantly at short time-scales (e.g., hourly), which could have significant implications for flux partitioning studies.

  15. The lithium isotopic ratio in very metal-poor stars

    CERN Document Server

    Lind, Karin; Asplund, Martin; Collet, Remo; Magic, Zazralt

    2013-01-01

    Un-evolved, very metal-poor stars are the most important tracers of the cosmic abundance of lithium in the early universe. Combining the standard Big Bang nucleosynthesis model with Galactic production through cosmic ray spallation, these stars at [Fe/H]<-2 are expected to show an undetectably small 6Li/7Li isotopic signature. Evidence to the contrary may necessitate an additional pre-galactic production source or a revision of the standard model of Big Bang nucleosynthesis. We revisit the isotopic analysis of four halo stars, two with claimed 6Li-detections in the literature, to investigate the influence of improved model atmospheres and line formation treatment. For the first time, a combined 3D, NLTE (non-local thermodynamic equilibrium) modelling technique for Li, Na, and Ca lines is utilised to constrain the intrinsic line-broadening and to determine the Li isotopic ratio. We discuss the influence of 3D NLTE effects on line profile shapes and assess the realism of our modelling using the Ca excitation...

  16. Measurement system analysis (MSA) of the isotopic ratio for uranium isotope enrichment process control

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Josue C. de; Barbosa, Rodrigo A.; Carnaval, Joao Paulo R., E-mail: josue@inb.gov.br, E-mail: rodrigobarbosa@inb.gov.br, E-mail: joaocarnaval@inb.gov.br [Industrias Nucleares do Brasil (INB), Rezende, RJ (Brazil)

    2013-07-01

    Currently, one of the stages in nuclear fuel cycle development is the process of uranium isotope enrichment, which will provide the amount of low enriched uranium for the nuclear fuel production to supply 100% Angra 1 and 20% Angra 2 demands. Determination of isotopic ration n({sup 235}U)/n({sup 238}U) in uranium hexafluoride (UF{sub 6} - used as process gas) is essential in order to control of enrichment process of isotopic separation by gaseous centrifugation cascades. The uranium hexafluoride process is performed by gas continuous feeding in separation unit which uses the centrifuge force principle, establishing a density gradient in a gas containing components of different molecular weights. The elemental separation effect occurs in a single ultracentrifuge that results in a partial separation of the feed in two fractions: an enriched on (product) and another depleted (waste) in the desired isotope ({sup 235}UF{sub 6}). Industrias Nucleares do Brasil (INB) has used quadrupole mass spectrometry (QMS) by electron impact (EI) to perform isotopic ratio n({sup 235}U)/n({sup 238}U) analysis in the process. The decision of adjustments and change te input variables are based on the results presented in these analysis. A study of stability, bias and linearity determination has been performed in order to evaluate the applied method, variations and systematic errors in the measurement system. The software used to analyze the techniques above was the Minitab 15. (author)

  17. Carbon and oxygen isotopic ratios for nearby miras

    CERN Document Server

    Hinkle, K H; Straniero, O

    2016-01-01

    C and O isotopic ratios are reported for a sample of 46 Mira and SRa-type variable AGB stars. Vibration-rotation 1st and 2nd overtone CO lines in 1.5 to 2.5 $\\mu$m spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of the M stars had main sequence masses < 2 Msun and have not experienced sizable third dredge-up episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the 6 C stars in the sample three have clear evidence relating their origin to the occurrence of the third dredge-up. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars...

  18. Understanding radioxenon isotopical ratios originating from radiopharmaceutical facilities

    Science.gov (United States)

    Saey, P. R. J.; Ringbom, A.; Bowyer, T. W.; Becker, A.; de Geer, L.-E.; Nikkinen, M.; Payne, R. F.

    2009-04-01

    It was recently shown that radiopharmaceutical facilities (RPF) are major contributors to the general background of 133Xe and other xenon isotopes both in the northern and southern hemisphere. To distinguish a nuclear explosion signal from releases from civil nuclear facilities, not only the activity concentrations but also the ratios of the four different CTBT relevant radioxenon isotopes (131mXe, 133mXe, 133Xe and 135Xe) have to be well understood. First measurements taken recently in and around two of the world's largest RPF's: NTP at Pelindaba, South Africa and IRE at Fleurus, Belgium have been presented. At both sites, also stack samples were taken in close cooperation with the facility operators. The radioxenon in Belgium could be classified in four classes: the normal European background (133Xe activity between 0 - 5 mBq/m3) on one hand and then the samples where all four isotopes were detected with 133mXe/131mXe > 1. In northern South Africa the Pelindaba RPF is in practice the sole source of radioxenon. It generated a background of 133Xe at the measurement site some 230 km to the west of the RPF of 0 - 5 mBq/m3. In the cases where the air from the Pelindaba facility reached the measurement site directly and in a short time period, the 133Xe was higher, also 135Xe was present and in some samples 133mXe as well. The ratios of the activity concentrations of 135Xe/133Xe vs. 133mXe/131mXe (Multiple Isotope Ratio Plot - MIRC) have been analysed. For both facilities, the possible theoretical ratio's for different scenarios were calculated with the information available and compared with the measurements. It was found that there is an excess of 131mXe present in the European samples compared to theoretical calculations. A similar excess has also been seen in samples measured in northern America. In South Africa, neither the environmental samples nor the stack ones contained 131mXe at measurable levels. This can probably be explained by different processes and

  19. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae : implications for palaeoclimate reconstruction.

    OpenAIRE

    Brett, M.J.; Baldini, J. U. L.; Gröcke, D. R.

    2014-01-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand mode...

  20. Forensic applications of light-element stable isotope ratios of Ricinus communis seeds and ricin preparations.

    Science.gov (United States)

    Kreuzer, Helen W; West, Jason B; Ehleringer, James R

    2013-01-01

    Seeds of the castor plant Ricinus communis are of forensic interest because they are the source of the poison ricin. We tested whether stable isotope ratios of castor seeds and ricin preparations can be used as a forensic signature. We collected over 300 castor seed samples worldwide and measured the C, N, O, and H isotope ratios of the whole seeds and oil. We prepared ricin by three different procedures, acetone extraction, salt precipitation, and affinity chromatography, and compared their isotope ratios to those of the source seeds. The N isotope ratios of the ricin samples and source seeds were virtually identical. Therefore, N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pairwise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  1. Examining Changes in Radioxenon Isotope Activity Ratios during Subsurface Transport

    Science.gov (United States)

    Annewandter, Robert

    2014-05-01

    The Non-Proliferation Experiment (NPE) has demonstrated and modelled the usefulness of barometric pumping induced gas transport and subsequent soil gas sampling during On-Site inspections. Generally, gas transport has been widely studied with different numerical codes. However, gas transport of radioxenons and radioiodines in the post-detonation regime and their possible fractionation is still neglected in the open peer-reviewed literature. Atmospheric concentrations of the radioxenons Xe-135, Xe-133m, Xe-133 and Xe-131m can be used to discriminate between civilian releases (nuclear power plants or medical isotope facilities), and nuclear explosion sources. It is based on the multiple isotopic activity ratio method. Yet it is not clear whether subsurface migration of the radionuclides, with eventual release into the atmosphere, can affect the activity ratios due to fractionation. Fractionation can be caused by different mass diffusivities due to mass differences between the radionuclides. Cyclical changes in atmospheric pressure can drive subsurface gas transport. This barometric pumping phenomenon causes an oscillatoric flow in upward trending fractures or highly conductive faults which, combined with diffusion into the porous matrix, leads to a net transport of gaseous components - a so-called ratcheting effect. We use a general purpose reservoir simulator (Complex System Modelling Platform, CSMP++) which is recognized by the oil industry as leading in Discrete Fracture-Matrix (DFM) simulations. It has been applied in a range of fields such as deep geothermal systems, three-phase black oil simulations, fracture propagation in fractured, porous media, and Navier-Stokes pore-scale modelling among others. It is specifically designed to account for structurally complex geologic situation of fractured, porous media. Parabolic differential equations are solved by a continuous Galerkin finite-element method, hyperbolic differential equations by a complementary finite

  2. Carbon and Oxygen Isotopic Ratios for Nearby Miras

    Science.gov (United States)

    Hinkle, Kenneth H.; Lebzelter, Thomas; Straniero, Oscar

    2016-07-01

    Carbon and oxygen isotopic ratios are reported for a sample of 46 Mira and SRa-type variable asymptotic giant branch (AGB) stars. Vibration-rotation first and second-overtone CO lines in 1.5-2.5 μm spectra were measured to derive isotopic ratios for 12C/13C, 16O/17O, and 16O/18O. Comparisons with previous measurements for individual stars and with various samples of evolved stars, as available in the extant literature, are discussed. Models for solar composition AGB stars of different initial masses are used to interpret our results. We find that the majority of M-stars have main sequence masses ≤2 M ⊙ and have not experienced sizable third dredge-up (TDU) episodes. The progenitors of the four S-type stars in our sample are slightly more massive. Of the six C-stars in the sample three have clear evidence relating their origin to the occurrence of TDU. Comparisons with O-rich presolar grains from AGB stars that lived before the formation of the solar system reveal variations in the interstellar medium chemical composition. The present generation of low-mass AGB stars, as represented by our sample of long period variables (LPVs), shows a large spread of 16O/17O ratios, similar to that of group 1 presolar grains and in agreement with theoretical expectations for the composition of mass 1.2-2 M ⊙ stars after the first dredge-up. In contrast, the 16O/18O ratios of present-day LPVs are definitely smaller than those of group 1 grains. This is most probably a consequence of the the decrease with time of the 16O/18O ratio in the interstellar medium due to the chemical evolution of the Milky Way. One star in our sample has an O composition similar to that of group 2 presolar grains originating in an AGB star undergoing extra-mixing. This may indicate that the extra-mixing process is hampered at high metallicity, or, equivalently, favored at low metallicity. Similarly to O-rich grains, no star in our sample shows evidence of hot bottom burning, which is expected for

  3. Water isotopic ratios from a continuously melted ice core sample

    Directory of Open Access Journals (Sweden)

    V. Gkinis

    2011-06-01

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

  4. Water isotopic ratios from a continuously melted ice core sample

    Directory of Open Access Journals (Sweden)

    V. Gkinis

    2011-11-01

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

  5. Expanding the isotopic toolbox: Applications of hydrogen and oxygen stable isotope ratios to food web studies

    Directory of Open Access Journals (Sweden)

    Hannah B Vander Zanden

    2016-03-01

    Full Text Available The measurement of stable carbon (δ13C and nitrogen (δ15N isotopes in tissues of organisms has formed the foundation of isotopic food web reconstructions, as these values directly reflect assimilated diet. In contrast, stable hydrogen (δ2H and oxygen (δ18O isotope measurements have typically been reserved for studies of migratory origin and paleoclimate reconstruction based on systematic relationships between organismal tissue and local environmental water. Recently, innovative applications using δ2H and, to a lesser extent, δ18O values have demonstrated potential for these elements to provide novel insights in modern food web studies. We explore the advantages and challenges associated with three applications of δ2H and δ18O values in food web studies. First, large δ2H differences between aquatic and terrestrial ecosystem end members can permit the quantification of energy inputs and nutrient fluxes between these two sources, with potential applications for determining allochthonous vs. autochthonous nutrient sources in freshwater systems and relative aquatic habitat utilization by terrestrial organisms. Next, some studies have identified a relationship between δ2H values and trophic position, which suggests that this marker may serve as a trophic indicator, in addition to the more commonly used δ15N values. Finally, coupled measurements of δ2H and δ18O values are increasing as a result of reduced analytical challenges to measure both simultaneously and may provide additional ecological information over single element measurements. In some organisms, the isotopic ratios of these two elements are tightly coupled, whereas the isotopic disequilibrium in other organisms may offer insight into the diet and physiology of individuals. Although a coherent framework for interpreting δ2H and δ18O data in the context of food web studies is emerging, many fundamental uncertainties remain. We highlight directions for targeted research that

  6. On-site isotopic analysis of dissolved inorganic carbon using an isotope ratio infrared spectrometer

    Science.gov (United States)

    Stoltmann, Tim; Mandic, Magda; Stöbener, Nils; Wapelhorst, Eric; Aepfler, Rebecca; Hinrichs, Kai-Uwe; Taubner, Heidi; Jost, Hj; Elvert, Marcus

    2016-04-01

    An Isotope Ratio Infrared Spectrometer (IRIS) has been adapted to perform measurements of δ13C of dissolved inorganic carbon (DIC) in marine pore waters. The resulting prototype allowed highly automated analysis of δ13C isotopic ratios and CO2 concentration. We achieved a throughput of up to 70 samples per day with DIC contents as low as 1.7 μmol C. We achieved an internal precision of 0.066 ‰ and an external precision of 0.16 ‰, which is comparable to values given for Isotope Ratio Mass Spectrometers (IRMS). The prototype instrument is field deployable, suitable for shipboard analysis of deep sea core pore waters. However, the validation of the prototype was centered around a field campaign in Eckernförde Bay, NW- Baltic Sea. As a proof of concept, a shallow site within an area of submarine groundwater discharge (SGD) and a site outside this area was investigated. We present profiles of δ13C of DIC over 50 cm exhibiting well understood methane turnover processes (anaerobic oxidation of methane). At the lowest point below the seafloor, microbial reduction of CO2 to CH4 dominates. 12CO2 is reduced preferentially over 13CO2, leading to more positive δ13C values in the remaining DIC pool; in layers closer to the surface, the oxidation of CH4 to CO2 becomes more prominent. Since the CH4 pool is enriched in 12C a shift to more negative δ13C can be observed in the DIC pool. In the upper 15 cm, the pore water DIC mixes with the sea water DIC, increasing δ13C again. Finally, we will present recent developments to further improve performance and future plans for deployments on research cruises.

  7. Isotopic Ratios in Titan's Methane: Measurements and Modeling

    Science.gov (United States)

    Nixon, C. A.; Temelso, B.; Vinatier, S.; Teanby, N. A.; Bezard, B.; Achterberg, R. K.; Mandt, K. E.; Sherrill, C. D.; Irwin, P. G.; Jennings, D. E.; Romani, P. N.; Coustenis, A.; Flasar, F. M.

    2012-01-01

    The existence of methane in Titan's atmosphere (approx. 6% level at the surface) presents a unique enigma, as photochemical models predict that the current inventory will be entirely depleted by photochemistry in a timescale of approx 20 Myr. In this paper, we examine the clues available from isotopic ratios (C-12/C-13 and D/H) in Titan's methane as to the past atmosphere history of this species. We first analyze recent infrared spectra of CH4 collected by the Cassini Composite Infrared Spectrometer, measuring simultaneously for the first time the abundances of all three detected minor isotopologues: (13)CH4, (12)CH3D, and (13)CH3D. From these we compute estimates of C-12/C-13 = 86.5 +/- 8.2 and D/H = (1.59 +/- 0.33) x 10(exp -4) , in agreement with recent results from the Huygens GCMS and Cassini INMS instruments. We also use the transition state theory to estimate the fractionation that occurs in carbon and hydrogen during a critical reaction that plays a key role in the chemical depletion of Titan's methane: CH4 + C2H yields CH3 + C2H2. Using these new measurements and predictions we proceed to model the time evolution of C-12/C-13 and D/H in Titan's methane under several prototypical replenishment scenarios. In our Model 1 (no resupply of CH4), we find that the present-day C-12/C-13 implies that the CH4 entered the atmosphere 60-1600 Myr ago if methane is depleted by chemistry and photolysis alone, but much more recently-most likely less than 10 Myr ago-if hydrodynamic escape is also occurring. On the other hand, if methane has been continuously supplied at the replenishment rate then the isotopic ratios provide no constraints, and likewise for the case where atmospheric methane is increasing, We conclude by discussing how these findings may be combined with other evidence to constrain the overall history of the atmospheric methane.

  8. Development, optimisation, and application of ICP-SFMS methods for the measurement of isotope ratios

    Energy Technology Data Exchange (ETDEWEB)

    Stuerup, S

    2000-07-01

    The measurement of isotopic composition and isotope ratios in biological and environmental samples requires sensitive, precise, and accurate analytical techniques. The analytical techniques used are traditionally based on mass spectrometry, among these techniques is the ICP-SFMS technique, which became commercially available in the mid 1990s. This technique is characterised by high sensitivity, low background, and the ability to separate analyte signals from spectral interferences. These features are beneficial for the measurement of isotope ratios and enable the measurement of isotope ratios of elements, which it has not previously been possible to measure due to either spectral interferences or poor sensitivity. The overall purpose of the project was to investigate the potential of the single detector ICP-SFMS technique for the measurement of isotope ratios in biological and environmental samples. One part of the work has focused on the fundamental aspects of the ICP-SFMS technique with special emphasize on the features important to the measurement of isotope ratios, while another part has focused on the development, optimisation and application of specific methods for the measurement of isotope ratios of elements of nutritional interest and radionuclides. The fundamental aspects of the ICP-SFMS technique were investigated theoretically and experimentally by the measurement of isotope ratios applying different experimental conditions. It was demonstrated that isotope ratios could be measured reliably using ICP-SFMS by educated choice of acquisition parameters, scanning mode, mass discrimination correction, and by eliminating the influence of detector dead time. Applying the knowledge gained through the fundamental study, ICP-SFMS methods for the measurement of isotope ratios of calcium, zinc, molybdenum and iron in human samples and a method for the measurement of plutonium isotope ratios and ultratrace levels of plutonium and neptunium in environmental samples

  9. Big Bang Nucleosynthesis and the Helium Isotope Ratio

    CERN Document Server

    Cooke, Ryan

    2015-01-01

    The conventional approach to search for departures from the standard model of physics during Big Bang Nucleosynthesis involves a careful, and subtle measurement of the mass fraction of baryons consisting of helium. Recent measurements of this quantity tentatively support new physics beyond the standard model but, historically, this method has suffered from hidden systematic uncertainties. In this letter, I show that a combined measurement of the primordial deuterium abundance and the primordial helium isotope ratio has the potential to provide a complementary and reliable probe of new physics beyond the standard model. Using the recent determination of the primordial deuterium abundance and assuming that the measured pre-solar 3He/4He meteoritic abundance reflects the primordial value, a bound can be placed on the effective number of neutrino species, Neff(BBN) = 3.01 (+0.95 -0.76, with 95 per cent confidence). Although this value of Neff supports the standard model, it is presently unclear if the pre-solar 3...

  10. Effects of carbonate leaching on foraminifer stable isotopes ratios

    Science.gov (United States)

    Obrochta, S.; Yokoyama, Y.; Sakai, S.; Ishimura, T.

    2011-12-01

    Stable carbon and oxygen isotope ratios were measured on 125 individual epifaunal and infaunal benthic foraminifers from two discrete Holocene intervals in a shallow-water sediment core (~ 450 m) from the Timor Sea. Methane seeps are common in the area, resulting in significant precipitation of secondary calcite that is confirmed by SEM photomicrographs and has likely resulted in inconsistent downcore results. To assess the degree of removal of contaminants, individual Uvigerina peregrina were subjected to varying degrees of pretreatment prior to analysis. All foraminifers received standard cleaning with ethanol and brief sonication. A subset were further cleaned and sonicated in a dilute HCl solution (~ 0.003 M). Foraminifer tests were photographed using both reflected light and scanning electron microscopes during the course of treatment to monitor the changing degree of contaminant removal as increasingly aggressive cleaning methods were employed. Visible contamination remained on individuals not subjected to HCl treatment. The leached individuals exhibit a lower overall relative standard deviation and consistent results within morphotype groups. Based on these results, a 2% value is expected to be typical of the Holocene, though further downcore analyses are pending restoration of equipment adversely effected by the Eastern Japan 3/11 earthquake.

  11. An analytical system for stable isotope analysis on carbon monoxide using continuous-flow isotope-ratio mass spectrometry

    NARCIS (Netherlands)

    Pathirana, S. L.; Van Der Veen, C.; Popa, M. E.; Röckmann, T.

    2015-01-01

    A fully automated system for the determination of δ13C and δ18O in atmospheric CO has been developed. CO is extracted from an air sample and converted into carbon dioxide (CO2) using the Schütze reagent. The isotopic composition is determined with an isotope-ratio mass spectrometer (IRMS) technique.

  12. Environmental controls on stable isotope ratios in New Zealand Podocarpaceae: Implications for palaeoclimate reconstruction

    Science.gov (United States)

    Brett, Marianne J.; Baldini, James U. L.; Gröcke, Darren R.

    2014-09-01

    Stable isotope ratios of various proxies are widely used for palaeoclimate reconstruction, and it is often assumed that isotope ratios reflect vegetation abundance or type. However, very little research exists on the isotopic equilibration of extant biomes under variable environmental conditions. In this study, carbon and oxygen isotope ratios from leaves of various Podocarpaceae genera, endemic to New Zealand, are linked to environmental parameters from the Land Environments New Zealand model. The dominant influence on stable isotope ratios within the majority of Podocarpaceae studied here is vapour pressure deficit (VPD). A simple latitudinal trend does not exist, and neither temperature nor rainfall (decoupled from VPD) controls the stable isotope ratios. The results suggest that modern spatial heterogeneity in VPD affects the stable isotope values of vegetation, and that historic VPD variability would change the stable isotope ratios of Podocarpaceae without necessitating a change in vegetation type, density, or productivity. This represents an alternative model for temporal isotope change within geochemical proxies and reinforces the need for increased stable isotopic research in modern plant ecosystems to better understand modern, and eventually palaeoclimatic processes affecting the terrestrial biosphere.

  13. Isotopic ratios at z=0.68 from molecular absorption lines toward B 0218+357

    CERN Document Server

    Wallstrom, S H J; Guelin, M

    2016-01-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z=0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z=0.89 absorber in front of PKS1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models.

  14. Advances in laser-based isotope ratio measurements : selected applications

    NARCIS (Netherlands)

    Kerstel, E.; Gianfrani, L.

    2008-01-01

    Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseou

  15. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates

    NARCIS (Netherlands)

    Krajko, J.; Varga, Z.; Yalcintas, E.; Wallenius, M.; Mayer, K.

    2014-01-01

    A novel procedure has been developed for the measurement of 143Nd/144Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of 143Nd/144Nd isotope ratio for provenance assessment in nu

  16. Quantification and isotope ratio determination of uranium in particles of environmental samples using isotope dilution thermal ionization mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jong-Ho [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of); Choi, Eun-Ju [Chungnam National University, Daejeon (Korea, Republic of)

    2015-10-15

    Highly accurate and precise quantitative and qualitative analysis of nuclear materials in environmental samples plays essential roles in monitoring undeclared nuclear activities of corresponding facilities. The former focuses on the quantification of uranium (U) and plutonium (Pu) contained in a whole sample, while the latter enables us to acquire the isotopic ratios, which serve as the crucial basis to trace the nuclear histories of a facility. However, the quantity of nuclear materials in a single-particle has not been acquired from the particle analysis, but has been estimated by the size of the particles. This report is to describe the method developed to determine the quantity and the isotopic ratios of uranium in a micro-particle simultaneously. Complete dissolution of particle-spike mixture by repeated addition of nitric acid on a rhenium filament was performed to ensure the homogeneity of the mixture. Thermal ionization mass spectrometry (TIMS) was utilized to measure the U isotope ratios of the mixture with high accuracy. The isotopic ratios of the uranium in the particle sample were determined by mathematical deconvolution of U isotopic ratios of the mixture. Verification using particles of a certified reference material showed that the newly developed method can be used to quantify and to determine the isotopic ratios of U in a particle simultaneously. The development of a method for simultaneous determination of the quantity and the isotope ratios of uranium contained in particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS) was described. For homogeneity of the mixture of particles and spike, repeated dissolution using nitric acid for five times was performed.

  17. Forensic Applications of Light-Element Stable Isotope Ratios of Ricinus communis Seeds and Ricin Preparations

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-01

    Seeds of the castor plant Ricinus communis, also known as castor beans, are of forensic interest because they are the source of the poison ricin. We have tested whether stable isotope ratios of castor seeds and ricin prepared by various methods can be used as a forensic signature. We collected over 300 castor seed samples from locations around the world and measured the C, N, O, and H stable isotope ratios of the whole seeds, oil, and three types of ricin preparations. Our results demonstrate that N isotope ratios can be used to correlate ricin prepared by any of these methods to source seeds. Further, stable isotope ratios distinguished >99% of crude and purified ricin protein samples in pair-wise comparison tests. Stable isotope ratios therefore constitute a valuable forensic signature for ricin preparations.

  18. MS fragment isotope ratio analysis for evaluation of citrus essential oils by HRGC-MS.

    Science.gov (United States)

    Satake, Atsushi; Furukawa, Kiyoshi; Ueno, Takao; Ukeda, Hiroyuki; Sawamura, Masayoshi

    2004-02-01

    To evaluate the origin of citrus essential oils, the isotope ratio of fragment peaks on HRGC-MS of the volatile compounds from various citrus oils was measured. The MS fragment ratio was found by the ratio of fragment peak intensity, m+1/m (m/z). This ratio reflects the isotope effect of volatile compounds, that is, it provides information about locality, quality, and species for essential oils. Multivariate analysis based on the MS fragment ratio of monoterpene hydrocarbons clearly distinguished three citrus species, yuzu, lemon, and lime. The carbonyl fractions were also extracted from citrus essential oils by the sodium hydrogensulfite method. The isotope ratio of MS fragments of octanal, nonanal, and decanal was also examined. The results suggest that there was no significant difference in the individual fragment isotope ratios of the three aldehydes.

  19. Uranium Isotope Ratios in Modern and Precambrian Soils

    Science.gov (United States)

    DeCorte, B.; Planavsky, N.; Wang, X.; Auerbach, D. J.; Knudsen, A. C.

    2015-12-01

    Uranium isotopes (δ238U values) are an emerging paleoredox proxy that can help to better understand the redox evolution of Earth's surface environment. Recently, uranium isotopes have been used to reconstruct ocean and atmospheric redox conditions (Montoya-Pino et al., 2010; Brennecka et al., 2011; Kendall et al., 2013; Dahl et al., 2014). However, to date, there have not been studies on paleosols, despite that paleosols are, arguably better suited to directly tracking the redox conditions of the atmosphere. Sedimentary δ238U variability requires the formation of the soluble, oxidized form of U, U(VI). The formation of U(VI) is generally thought to require oxygen levels orders of magnitude higher than prebiotic levels. Without significant U mobility, it would have been impossible to develop isotopically distinct pools of uranium in ancient Earth environments. Conversely, an active U redox cycle leads to significant variability in δ238U values. Here we present a temporally and geographically expansive uranium isotope record from paleosols and modern soils to better constrain atmospheric oxygen levels during the Precambrian. Preliminary U isotope measurements of paleosols are unfractionated (relative to igneous rocks), possibly because of limited fractionation during oxidation (e.g., {Wang, 2015 #478}) or insufficient atmospheric oxygen levels to oxidize U(IV)-bearing minerals in the bedrock. Further U isotope measurements of paleosols with comparison to modern soils will resolve this issue.

  20. Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results.

    Science.gov (United States)

    Coplen, Tyler B

    2011-09-15

    To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

  1. Guidelines and recommended terms for expression of stable-isotope-ratio and gas-ratio measurement results

    Science.gov (United States)

    Coplen, Tyler B.

    2011-01-01

    To minimize confusion in the expression of measurement results of stable isotope and gas-ratio measurements, recommendations based on publications of the Commission on Isotopic Abundances and Atomic Weights of the International Union of Pure and Applied Chemistry (IUPAC) are presented. Whenever feasible, entries are consistent with the Système International d'Unités, the SI (known in English as the International System of Units), and the third edition of the International Vocabulary of Basic and General Terms in Metrology (VIM, 3rd edition). The recommendations presented herein are approved by the Commission on Isotopic Abundances and Atomic Weights and are designed to clarify expression of quantities related to measurement of isotope and gas ratios to ensure that quantity equations instead of numerical value equations are used for quantity definitions. Examples of column headings consistent with quantity calculus (also called the algebra of quantities) and examples of various deprecated usages connected with the terms recommended are presented.

  2. Stable hydrogen and oxygen isotope ratios of bottled waters of the world.

    Science.gov (United States)

    Bowen, Gabriel J; Winter, David A; Spero, Howard J; Zierenberg, Robert A; Reeder, Mathew D; Cerling, Thure E; Ehleringer, James R

    2005-01-01

    Bottled and packaged waters are an increasingly significant component of the human diet. These products are regulated at the regional, national, and international levels, and determining the authenticity of marketing and labeling claims represents a challenge to regulatory agencies. Here, we present a dataset of stable isotope ratios for bottled waters sampled worldwide, and consider potential applications of such data for regulatory, forensic and geochemical standardization applications. The hydrogen and oxygen isotope ratios of 234 samples of bottled water range from -147 per thousand to +15 per thousand and from -19.1 per thousand to +3.0 per thousand, respectively. These values fall within and span most of the normal range for meteoric waters, indicating that these commercially available products represent a source of waters for use as laboratory working standards in applications requiring standardization over a large range of isotope ratios. The measured values of bottled water samples cluster along the global meteoric water line, suggesting that bottled water isotope ratios preserve information about the water sources from which they were derived. Using the dataset, we demonstrate how bottled water isotope ratios provide evidence for substantial evaporative enrichment of water sources prior to bottling and for the marketing of waters derived from mountain and lowland sources under the same name. Comparison of bottled water isotope ratios with natural environmental water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, suggesting that in many cases bottled water need not be considered as an isotopically distinct component of the human diet. Our findings suggest that stable isotope ratios of bottled water have the power to distinguish ultimate (e.g., recharge) and proximal (e.g., reservoir) sources of bottled water and constitute a potential

  3. A Test of Carbon and Oxygen Stable Isotope Ratio Process Models in Tree Rings.

    Science.gov (United States)

    Roden, J. S.; Farquhar, G. D.

    2008-12-01

    Stable isotopes ratios of carbon and oxygen in tree ring cellulose have been used to infer environmental change. Process-based models have been developed to clarify the potential of historic tree ring records for meaningful paleoclimatic reconstructions. However, isotopic variation can be influenced by multiple environmental factors making simplistic interpretations problematic. Recently, the dual isotope approach, where the variation in one stable isotope ratio (e.g. oxygen) is used to constrain the interpretation of variation in another (e.g. carbon), has been shown to have the potential to de-convolute isotopic analysis. However, this approach requires further testing to determine its applicability for paleo-reconstructions using tree-ring time series. We present a study where the information needed to parameterize mechanistic models for both carbon and oxygen stable isotope ratios were collected in controlled environment chambers for two species (Pinus radiata and Eucalyptus globulus). The seedlings were exposed to treatments designed to modify leaf temperature, transpiration rates, stomatal conductance and photosynthetic capacity. Both species were grown for over 100 days under two humidity regimes that differed by 20%. Stomatal conductance was significantly different between species and for seedlings under drought conditions but not between other treatments or humidity regimes. The treatments produced large differences in transpiration rate and photosynthesis. Treatments that effected photosynthetic rates but not stomatal conductance influenced carbon isotope discrimination more than those that influenced primarily conductance. The various treatments produced a range in oxygen isotope ratios of 7 ‰. Process models predicted greater oxygen isotope enrichment in tree ring cellulose than observed. The oxygen isotope ratios of bulk leaf water were reasonably well predicted by current steady-state models. However, the fractional difference between models that

  4. BOREAS TE-5 Tree Ring and Carbon Isotope Ratio Data

    Science.gov (United States)

    Hall, Forrest G. (Editor); Curd, Shelaine (Editor); Ehleriinger, Jim; Brooks, J. Renee; Flanagan, Larry

    2000-01-01

    The BOREAS TE-5 team collected several data sets to investigate the vegetation-atmosphere CO2 and H2O exchange processes. These data include tree ring widths and cellulose carbon isotope data from coniferous trees collected at the BOREAS NSA and SSA in 1993 and 1994 by the BOREAS TE-5 team. Ring width data are provided for both Picea mariana and Pinus banksiana. The carbon isotope data are provided only for Pinus banksiana. The data are provided in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC).

  5. Online stable carbon isotope ratio measurement in formic acid, acetic acid, methanol and ethanol in water by high performance liquid chromatography-isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Tagami, Keiko [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)], E-mail: k_tagami@nirs.go.jp; Uchida, Shigeo [National Institute of Radiological Sciences, 4-9-1, Anagawa, Inage-ku, Chiba 263-8555 (Japan)

    2008-05-05

    A suitable analysis condition was determined for high performance liquid chromatography-isotope ratio mass spectrometry (HPLC-IRMS) while making sequential measurements of stable carbon isotope ratios of {delta}{sup 13}C in formic acid, acetic acid, methanol and ethanol dissolved in water. For this online column separation method, organic reagents are not applicable due to carbon contamination; thus, water and KH{sub 2}PO{sub 4} at low concentrations were tested as mobile phase in combination with a HyPURITY AQUASTAR{sup TM} column. Formic acid, acetic acid, methanol and ethanol were separated when 2 mM KH{sub 2}PO{sub 4} aqueous solution was used. Under the determined analysis condition for HPLC-IRMS, carbon concentrations could be measured quantitatively as well as carbon isotope ratio when carbon concentration was higher than 0.4 mM L for each chemical.

  6. Chlorine Isotope Effects from Isotope Ratio Mass Spectrometry Suggest Intramolecular C-Cl Bond Competition in Trichloroethene (TCE Reductive Dehalogenation

    Directory of Open Access Journals (Sweden)

    Stefan Cretnik

    2014-05-01

    Full Text Available Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (biochemical 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.

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2015-01-01

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

  9. Influence of isotopic re-equilibration on speleothem and fluid inclusion isotope ratios after primary calcite precipitation

    Science.gov (United States)

    Kluge, Tobias; Haderlein, Astrid; Weißbach, Therese

    2016-04-01

    Oxygen isotope ratios in speleothems (notably stalagmites) have been used since decades to successfully infer paleotemperatures and deduce paleo-environmental information. In addition, recent technical developments allow to increasingly use fluid inclusions as an archive for drip-water and together with the surrounding calcite as paleothermometer. A basic requirement for isotope data interpretation is the complete knowledge of the fractionation between calcite and fluid. Most laboratory and in-situ cave experiments focus on calcite growth and the isotope fractionation between calcite and feed solution. Potential isotope exchange and re-equilibration processes after the initial deposition have mostly been neglected. However, experiments of Oelkers et al. (2015) showed that the isotope exchange between minerals and fluid can proceed rapidly (within days), even at chemical equilibrium. In hydrous Mg carbonates a similar process of continuous isotope exchange between carbonate and fluid was observed after the carbonate precipitation was completed (Mavromatis et al., 2015). These observations suggest that the isotope ratios of speleothem calcite may be affected by this continuous exchange, likely driving the isotope composition continuously towards equilibrium at the respective cave conditions. In addition, fluid inclusions are suspected to be sensitive to an isotope exchange with the surrounding carbonate highlighting the need to precisely understand and quantify this effect. We assessed the oxygen isotope exchange between calcite and solution at chemical equilibrium conditions with theoretical estimates and laboratory experiments over an intermediate time scale (hours-weeks). A large isotope gradient (~20 ‰)) between solution and calcite was prepared in the experiment to investigate the dynamics of this re-equilibration process. We used a theoretical model based on a Rayleigh fractionation approach and the direct comparison with the experiment to determine

  10. Tracing lead pollution sources in abandoned mine areas using stable Pb isotope ratios.

    Science.gov (United States)

    Yoo, Eun-Jin; Lee, Jung-A; Park, Jae-Seon; Lee, Khanghyun; Lee, Won-Seok; Han, Jin-Seok; Choi, Jong-Woo

    2014-02-01

    This study focused on Pb isotope ratios of sediments in areas around an abandoned mine to determine if the ratios can be used as a source tracer. For pretreatment, sediment samples were dissolved with mixed acids, and a multi-collector inductively coupled plasma mass spectrometer (MC-ICP-MS, Nu plasma II) was used to investigate the Pb isotopic composition of the samples. The measured isotope ratios were then corrected for instrumental mass fractionation by measuring the (203)Tl/(205)Tl ratio. Repeated measurements with the NIST SRM 981 reference material showed that the precision of all ratios was below 104 ppm (±2σ) for 50 ng/g. The isotope ratios ((207)Pb/(206)Pb) found were 0.85073 ± 0.0004~0.85373 ± 0.0003 for the main stream, while they were 0.83736 ± 0.0010 for the tributary and 0.84393 ± 0.0002 for the confluence. A binary mixing equation for isotope ratios showed that the contributions of mine lead to neighboring areas were up to 60%. Therefore, Pb isotope ratios can be a good source tracer for areas around abandoned mines.

  11. Platinum stable isotope ratio measurements by double-spike multiple collector ICPMS

    DEFF Research Database (Denmark)

    Creech, J.; Baker, J.; Handler, M.

    2013-01-01

    We present a new technique for the precise determination of platinum (Pt) stable isotope ratios by multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) using two different Pt double-spikes ( Pt-Pt and Pt-Pt). Results are expressed relative to the IRMM-010 Pt isotope standard...

  12. Methods and limitations of 'clumped' CO2 isotope (Delta47) analysis by gas-source isotope ratio mass spectrometry.

    Science.gov (United States)

    Huntington, K W; Eiler, J M; Affek, H P; Guo, W; Bonifacie, M; Yeung, L Y; Thiagarajan, N; Passey, B; Tripati, A; Daëron, M; Came, R

    2009-09-01

    The geochemistry of multiply substituted isotopologues ('clumped-isotope' geochemistry) examines the abundances in natural materials of molecules, formula units or moieties that contain more than one rare isotope (e.g. (13)C(18)O(16)O, (18)O(18)O, (15)N(2), (13)C(18)O(16)O(2) (2-)). Such species form the basis of carbonate clumped-isotope thermometry and undergo distinctive fractionations during a variety of natural processes, but initial reports have provided few details of their analysis. In this study, we present detailed data and arguments regarding the theoretical and practical limits of precision, methods of standardization, instrument linearity and related issues for clumped-isotope analysis by dual-inlet gas-source isotope ratio mass spectrometry (IRMS). We demonstrate long-term stability and subtenth per mil precision in 47/44 ratios for counting systems consisting of a Faraday cup registered through a 10(12) ohm resistor on three Thermo-Finnigan 253 IRMS systems. Based on the analyses of heated CO(2) gases, which have a stochastic distribution of isotopes among possible isotopologues, we document and correct for (1) isotopic exchange among analyte CO(2) molecules and (2) subtle nonlinearity in the relationship between actual and measured 47/44 ratios. External precisions of approximately 0.01 per thousand are routinely achieved for measurements of the mass-47 anomaly (a measure mostly of the abundance anomaly of (13)C-(18)O bonds) and follow counting statistics. The present technical limit to precision intrinsic to our methods and instrumentation is approximately 5 parts per million (ppm), whereas precisions of measurements of heterogeneous natural materials are more typically approximately 10 ppm (both 1 s.e.). These correspond to errors in carbonate clumped-isotope thermometry of +/-1.2 degrees C and +/-2.4 degrees C, respectively.

  13. Multi-collector Isotope Ratio Mass Spectrometer -- Operational Performance Report

    Energy Technology Data Exchange (ETDEWEB)

    Appelhans, Anthony D; Olson, John E; Watrous, Matthew G; Ward, Michael B.; Dahl, David A.

    2010-12-01

    This report describes the operational testing of a new magnetic sector mass spectrometer that utilizes seven full-sized discrete dynode electron multipliers operating simultaneously. The instrument includes a newly developed ion dispersion lens that enables the mass dispersed individual isotope beams to be separated sufficiently to allow a full-sized discrete dynode pulse counting multiplier to be used to measure each isotope beam. The performance of the instrument was measured using SRM 996 (244Pu spike) at loadings of 2.4 and 12 fg on resin beads and with SRM 4350B Columbia River Sediment samples. The measured limit of detection (3s) for 240Pu was 3.4 attograms for SRM 996. The limit of quantitation (LOQ), defined as 10 s, was 11.2 attograms. The measured concentration of 239Pu in the CRS standard was 152 ± 6 fg/g.

  14. Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto

    Science.gov (United States)

    Saccon, M.; Kornilova, A.; Huang, L.; Moukhtar, S.; Rudolph, J.

    2015-09-01

    A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all with substantial secondary formation from the photooxidation of aromatic volatile organic compounds (VOCs), was conducted in the gas phase and particulate matter (PM) together and in PM alone. Their concentrations in the atmosphere are in the low ng m-3 range and, consequently, a large volume of air (> 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between -34 and -33 ‰, which is well within the range predicted by mass balance. However, the observed carbon isotope ratios cover a range of nearly 9 ‰ and approximately 20 % of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban center with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This

  15. Lead isotope ratios as a tracer for lead contamination sources: A lake Andong case study

    Directory of Open Access Journals (Sweden)

    Kim Y. H

    2013-04-01

    Full Text Available The objective of this study was to evaluate stable Pb isotope signatures as a tracer for Pb contamination in Lake Andong. For Pb isotope analysis, we collected water and sediment from Lake Andong, particles in the air, soils, and stream water, mine tailings, sludge and wastewater from zinc smelting around lake Andong watershed. The results showed that Pb isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for zinc concentrate were 18.809 ± 0.322, 15.650 ± 0.062, and 38.728 ± 0.421, respectively. In wastewater, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb were 17.363 ± 0.133, 15.550 ± 0.025, and 37.217 ± 0.092, respectively. Additionally, isotopic ratio values (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb for sludge were 17.515 ± 0.155, 15.537 ± 0.018, and 37.357 ± 0.173, respectively. These values were similar to those in zinc and lead concentrate originated from Canada and South America. In contrast, Pb isotope ratios of soil, tailings and sediment from Lake Andong were similar to those of Korean ore. Atmospheric particles showed different patterns of Pb isotope ratios from sediments, soils, and zinc smelting and this needs further investigation in order to identify atmospheric Pb sources.

  16. Stable Carbon Isotope Ratios of Phenolic Compounds in Secondary Particulate Organic Matter Formed by Photooxidation of Toluene

    CERN Document Server

    Irei, Satoshi; Huang, Lin; Auld, Janeen; Collin, Fabrice; Hastie, Donald

    2014-01-01

    Compound-specific stable carbon isotope ratios for phenolic compounds in secondary particulate organic matter (POM) formed by photooxidation of toluene were studied. Secondary POM generated by photooxidation of toluene using a continuous-flow reactor and an 8 cubic meter indoor smog chamber was collected, and then extracted with acetonitrile. Eight phenolic compounds were identified in the extracts by a gas chromatograph coupled with a mass spectrometer, and their compound-specific stable carbon isotope ratios were determined by a gas chromatograph coupled with a combustion furnace followed by an isotope ratio mass spectrometer. The majority of the products, including methylnitrophenols and methylnitrocatechols, were isotopically depleted by 5 to 6 permil compared to the initial isotope ratio for toluene, whereas the isotope ratio for 4_nitrophenol remained the same as the initial isotope ratio for toluene. Based on the reaction mechanisms postulated in literature, stable carbon isotope ratios of these produc...

  17. Accuracy of delta 18O isotope ratio measurements on the same sample by continuous-flow isotope-ratio mass spectrometry

    Science.gov (United States)

    The doubly labeled water method is considered the reference method to measure energy expenditure. Conventional mass spectrometry requires a separate aliquot of the same sample to be prepared and analyzed separately. With continuous-flow isotope-ratio mass spectrometry, the same sample could be analy...

  18. Implications of the Nitrogen Isotope Ratio in Titan's Atmosphere for the Nitrogen Ratio in Ammonia in Comets

    Science.gov (United States)

    Mandt, K.; Mousis, O.

    2013-12-01

    The D/H ratio of water measured in solar system bodies has been established as a tool for determining the conditions under which bodies such as comets or icy moons formed. This ratio varies significantly and indicates complex thermal and chemical evolution of the solar nebula during solar system and planetary formation. Nitrogen isotope ratios also vary significantly, and in some but not all cases correlate to D/H ratios, but are poorly understood. Nitrogen in the solar nebula was primarily in the form of atomic and molecular nitrogen. The isotope ratio (14N/15N) of this reservoir is expected to be ~435 based on the ratio measured in Jupiter's atmosphere, because the atmosphere of Jupiter is made up of gas captured from the solar nebula (Owen et al., 2001). The terrestrial atmospheric ratio is 272, which is close to the ratio measured in the Earth's mantle. This may be the primordial ratio for nitrogen delivered to Earth depending on the amount of exchange between the atmosphere and the mantle and any atmospheric fractionation processes that may have influenced the ratio over time. Comets are a possible source of nitrogen in the Earth's atmosphere (Hutsmekers et al., 2009), although chondrites have also been suggested as a source (Marty, 2012). In the case of comets, nitrogen would have been essentially retained in the form of ammonia (Mousis et al., 2012), which is the most abundant form of nitrogen in comets. The nitrogen in Titan's atmosphere is expected to have originated as ammonia hydrates and converted to N2 early in Titan's history (Atreya et al., 1978). The nitrogen ratio in Titan's atmosphere is ~170, which is significantly enriched in the heavy isotope compared to the terrestrial value. We will discuss the evolution of the nitrogen ratio in Titan's atmosphere (Mandt et al., 2009), the limits of the primordial ratio in ammonia, and the implications for this ratio for the isotope ratio in ammonia in comets that should be measured by the ROSINA instrument

  19. Stable isotope ratio method for the characterisation of the poultry house environment.

    Science.gov (United States)

    Skipitytė, Raminta; Mašalaitė, Agnė; Garbaras, Andrius; Mickienė, Rūta; Ragažinskienė, Ona; Baliukonienė, Violeta; Bakutis, Bronius; Šiugždaitė, Jūratė; Petkevičius, Saulius; Maruška, Audrius Sigitas; Remeikis, Vidmantas

    2017-06-01

    Stable isotope analysis was applied to describe the poultry house environment. The poultry house indoor environment was selected for this study due to the relevant health problems in animals and their caretakers. Air quality parameters including temperature, relative humidity, airflow rate, NH3, CO2 and total suspended particles, as well as mean levels of total airborne bacteria and fungi count, were measured. Carbon isotope ratios ((13)C/(12)C) were obtained in size-segregated aerosol particles. The carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) isotope ratios were measured in feed, litter, scrapings from the ventilation system, feathers and eggs. Additionally, the distribution of δ(13)C and δ(15)N values in different tissues of the chicken was examined. The airborne bacteria and fungi extracted from the air filters collected from poultry farms were grown in the laboratory in media with known isotope values and measured for stable isotope ratios. Analysis of isotope fractionation between microorganisms and their media indicated the applicability of stable isotope analysis in bulk samples for the identification of source material. The analysed examples imply that stable isotope analysis can be used to examine the indoor environment along with its biology and ecology, and serve as an informative bioanalytical tool.

  20. Zinc Isotope Ratios as Indicators of Diet and Trophic Level in Arctic Marine Mammals.

    Science.gov (United States)

    Jaouen, Klervia; Szpak, Paul; Richards, Michael P

    2016-01-01

    Carbon and nitrogen stable isotope ratios of bone collagen are an established method for dietary reconstruction, but this method is limited by the protein preservation. Zinc (Zn) is found in bioapatite and the isotopic compositions of this element constitute a very promising dietary indicator. The extent of fractionation of Zn isotopes in marine environments, however, remains unknown. We report here on the measurement of zinc, carbon and nitrogen isotopes in 47 marine mammals from the archaeological site of Arvik in the Canadian Arctic. We undertook this study to test and demonstrate the utility of Zn isotopes in recent mammal bone minerals as a dietary indicator by comparing them to other isotopic dietary tracers. We found a correlation between δ66Zn values and trophic level for most species, with the exception of walruses, which may be caused by their large seasonal movements. δ6Zn values can therefore be used as a dietary indicator in marine ecosystems for both modern and recent mammals.

  1. Mare basalt genesis - Modeling trace elements and isotopic ratios

    Science.gov (United States)

    Binder, A. B.

    1985-11-01

    Various types of mare basalt data have been synthesized, leading to the production of an internally consistent model of the mare basalt source region and mare basalt genesis. The model accounts for the mineralogical, major oxide, compatible siderophile trace element, incompatible trace element, and isotopic characteristics of most of the mare basalt units and of all the pyroclastic glass units for which reliable data are available. Initial tests of the model show that it also reproduces the mineralogy and incompatible trace element characteristics of the complementary highland anorthosite suite of rocks and, in a general way, those of the lunar granite suite of rocks.

  2. The thermal history of char as disclosed by carbon isotope ratios

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Ambus, Per; Ahrenfeldt, Jesper

    In laboratory experiments, biomass char was produced under controlled conditions using wood chips from French pinewood. Different char qualities were obtained by pyrolysing the biomass at similar heating rates with end-temperatures ranging from 250 to 1000 o C. The char was analysed by flash...... pyrolysis and isotope ratio mass spectrometry. The results demonstrate that the temperature history of the char is reflected in the fine variation of carbon isotopes. The compound classes responsible for the variation were identified. Key words: Isotope ratio, flash pyrolysis, hot gas cleaning...

  3. Water isotopic ratios from a continuously melted ice core sample

    CERN Document Server

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

    2014-01-01

    A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneous water isotopic analysis of $\\delta^{18}$O and $\\delta$D on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub ${\\mu}$l amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a home made oven. A calibration procedure allows for proper reporting of the data on the VSMOW--SLAP scale. Application of spectral methods yields the combined uncertainty of the system at below 0.1 permil and 0.5 permil for $\\delta^{18}$O and $\\delta$D, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sampl...

  4. Continuous-flow isotope ratio mass spectrometry method for carbon and hydrogen isotope measurements on atmospheric methane

    NARCIS (Netherlands)

    Brass, M.; Roeckmann, T.

    2010-01-01

    We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS) technique for high-precision δD and δ13C measurements of atmospheric methane on 40 mL air samples. CH4 is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve

  5. Bayesian Integration of Isotope Ratios for Geographic Sourcing of Castor Beans

    Energy Technology Data Exchange (ETDEWEB)

    Webb-Robertson, Bobbie-Jo M.; Kreuzer, Helen W.; Hart, Garret L.; Ehleringer, James; West, Jason B.; Gill, Gary A.; Duckworth, Douglas C.

    2012-08-15

    Recent years have seen an increase in the forensic interest associated with the poison ricin, which is extracted from the seeds of the Ricinus communis plant. Both light element (C, N, O, and H) and strontium (Sr) isotope ratios have previously been used to associate organic material with geographic regions of origin. We present a Bayesian integration methodology that can more accurately predict the region of origin for a castor bean than individual models developed independently for light element stable isotopes or Sr isotope ratios. Our results demonstrate a clear improvement in the ability to correctly classify regions based on the integrated model with a class accuracy of 6 0 . 9 {+-} 2 . 1 % versus 5 5 . 9 {+-} 2 . 1 % and 4 0 . 2 {+-} 1 . 8 % for the light element and strontium (Sr) isotope ratios, respectively. In addition, we show graphically the strengths and weaknesses of each dataset in respect to class prediction and how the integration of these datasets strengthens the overall model.

  6. Isotope ratio analysis by HRGC-MS of monoterpene hydrocarbons from citrus essential oils.

    Science.gov (United States)

    Satake, Atsushi; Une, Akitoshi; Ueno, Takao; Ukeda, Hiroyuki; Sawamura, Masayoshi

    2003-03-01

    The isotope ratio of monoterpene hydrocarbons in citrus essential oils of different origins was measured by ordinary high-resolution gas chromatography-mass spectrometry (HRGC-MS). The isotope ratio (Ir) was determined by the ratio of the isotope peak intensity (m/z 137) to the molecular mass peak intensity (m/z 136) of the monoterpene hydrocarbons. The accuracy of Ir was examined by measuring monoterpene hydrocarbon standards and 13C-labeled compounds. The isotope fingerprints based on the values of monoterpene hydrocarbons from lemon, lime and yuzu essential oils were determined. These citrus essential oils were also discriminated by a principal component analysis of their Ir data. The characteristic vectors showed that alpha-terpinene, beta-pinene and beta-phellandrene were important components for distinguishing between the citrus species. It is suggested that this technique will be applicable to evaluate the quality, genuineness and origin of citrus fruits and their products.

  7. Application of lead and strontium isotope ratio measurements for the origin assessment of uranium ore concentrates.

    Science.gov (United States)

    Varga, Zsolt; Wallenius, Maria; Mayer, Klaus; Keegan, Elizabeth; Millet, Sylvain

    2009-10-15

    Lead and strontium isotope ratios were used for the origin assessment of uranium ore concentrates (yellow cakes) for nuclear forensic purposes. A simple and low-background sample preparation method was developed for the simultaneous separation of the analytes followed by the measurement of the isotope ratios by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). The lead isotopic composition of the ore concentrates suggests applicability for the verification of the source of the nuclear material and by the use of the radiogenic (207)Pb/(206)Pb ratio the age of the raw ore material can be calculated. However, during data interpretation, the relatively high variation of the lead isotopic composition within the mine site and the generally high contribution of natural lead as technological contamination have to be carefully taken into account. The (87)Sr/(86)Sr isotope ratio is less prone to the variation within one mine site and less affected by the production process, thus it was found to be a more purposeful indicator for the origin assessment and source verification than the lead. The lead and strontium isotope ratios measured and the methodology developed provide information on the initial raw uranium ore used, and thus they can be used for source attribution of the uranium ore concentrates.

  8. Investigating controls on boron isotope ratios in shallow marine carbonates

    Science.gov (United States)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

    2017-01-01

    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

  9. D/H Isotope Ratio Measurements of Atmospheric Volatile Organic Compounds

    Science.gov (United States)

    Meisehen, Thomas; Bühler, Fred; Koppmann, Ralf; Krebsbach, Marc

    2015-04-01

    Analysis of isotope ratios in atmospheric volatile organic compounds (VOC) is a reliable method to allocate their sources, to estimate atmospheric residence times and investigate physical and chemical processes on various temporal and spatial scales. Most investigations yet focus on carbon isotope ratios. Certainly more detailed information can be gained by the ratio of deuterium (D) to hydrogen (H) in VOC, especially due to the high mass ratio. Combining measurements of carbon and hydrogen isotopes could lead to considerable improvement in our understanding of atmospheric processes. For this purpose we set up and thoroughly characterised a gas chromatograph pyrolysis isotope ratio mass spectrometer to measure the D/H ratio in atmospheric VOC. From a custom-made gas standard mixture VOC were adsorbed on Tenax®TA which has the advantage that CO2 is not preconcentrated when measuring ambient air samples. Our results show that the pyrolysis method has significant impact on the D/H ratios. A pyrolysis temperature of at least 1723 K and conditioning of the ceramic tube on a regular basis is essential to obtain reproducible D/H isotope ratios. For an independent comparison D/H ratios of the pure VOC used in the gas standard were determined using elemental analysis by Agroisolab (Jülich, Germany). Comparisons of 10 VOC show perfect agreement within the standard deviations of our measurements and the errors given by Agroisolab, e.g. for n-pentane, toluene, 4-methyl-2-pentanone and n-octane. A slight mean difference of 5.1 o was obtained for n-heptane while significant mean differences of 15.5 o and 20.3 o arose for 1,2,4-trimethylbenzene and isoprene, respectively. We further demonstrate the stability of our system and show that the sample preparation does not affect the isotope ratios. Moreover the applicability of our system to ambient air samples is demonstrated.

  10. CCQM-K140: carbon stable isotope ratio delta values in honey

    Science.gov (United States)

    Dunn, P. J. H.; Goenaga-Infante, H.; Goren, A. C.; Şimşek, A.; Bilsel, M.; Ogrinc, N.; Armishaw, P.; Hai, L.

    2017-01-01

    As there can be small but measureable differences in isotope ratios between different sources of the same element/compound/material, isotope ratio measurements are applied in a number of different fields including archaeology, environmental science, geochemistry, forensic science and ecology. Isotope ratios for the light elements (H, C, N, O and S) are typically reported as δ-values which are isotope ratios expressed relative to an internationally agreed standard (this standard is the zero-point on the scale), although absolute isotope ratios which are traceable to the SI have also been reported. The IAWG has been granted a traceability exception for the use of arbitrary delta scales until SI traceability can be established at the required level of uncertainty but this goal is some years away. While the CCQM IAWG has previously organised several pilot studies on isotope ratio determination (CCQM-P75: Stable isotope delta values in methionine, 2006; CCQM-P105: Sr isotope ratios in wine, 2008; CCQM-K98: Pb isotope ratios in bronze with additional delta values in CCQM-P134, 2011), it has been a number of years since delta values of light elements have been considered and there has been no key comparison (KC). Therefore, the IAWG has included the need for a KC (CCQM-K140) based on an arbitrary delta scale in its program to support ongoing requirements to demonstrate core capabilities as well as specific claims of measurement capability (CMCs) in this area. The performance of all five of the CCQM-K140 participants was very good, illustrating their ability to obtain accurate results for carbon isotope ratios, within the calibration range afforded by internationally agreed reference materials (δ13CVPDB-LSVEC between ‑47.32 % and +535.3 %) with measurement uncertainties of between 0.08 and 0.28 %. This was despite the fact that no two participants used exactly the same approach in terms of instrumentation or data treatment. Main text To reach the main text of this

  11. Isotopic ratios at z = 0.68 from molecular absorption lines toward B 0218+357

    Science.gov (United States)

    Wallström, S. H. J.; Muller, S.; Guélin, M.

    2016-11-01

    Isotopic ratios of heavy elements are a key signature of the nucleosynthesis processes in stellar interiors. The contribution of successive generations of stars to the metal enrichment of the Universe is imprinted on the evolution of isotopic ratios over time. We investigate the isotopic ratios of carbon, nitrogen, oxygen, and sulfur through millimeter molecular absorption lines arising in the z = 0.68 absorber toward the blazar B 0218+357. We find that these ratios differ from those observed in the Galactic interstellar medium, but are remarkably close to those in the only other source at intermediate redshift for which isotopic ratios have been measured to date, the z = 0.89 absorber in front of PKS 1830-211. The isotopic ratios in these two absorbers should reflect enrichment mostly from massive stars, and they are indeed close to the values observed toward local starburst galaxies. Our measurements set constraints on nucleosynthesis and chemical evolution models. The reduced spectra are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/595/A96

  12. Recent developments in the use of isotope ratio mass spectrometry in sports drug testing.

    Science.gov (United States)

    Piper, Thomas; Emery, Caroline; Saugy, Martial

    2011-08-01

    According to the annual report of the World Anti-Doping Agency, steroids are the most frequently detected class of doping agents. Detecting the misuse of endogenously occurring steroids, i.e. steroids such as testosterone that are produced naturally by humans, is one of the most challenging issues in doping control analysis. The established thresholds for urinary concentrations or concentration ratios such as the testosterone/epitestosterone quotient are sometimes inconclusive owing to the large biological variation in these parameters.For more than 15 years, doping control laboratories focused on the carbon isotope ratios of endogenous steroids to distinguish between naturally elevated steroid profile parameters and illicit administration of steroids. A variety of different methods has been developed throughout the last decade and the number of different steroids under investigation by isotope ratio mass spectrometry has recently grown considerably. Besides norandrosterone, boldenone was found to occur endogenously in rare cases and the misuse of corticosteroids or epitestosterone can now be detected with the aid of carbon isotope ratios as well. In addition, steroids excreted as sulfoconjugates were investigated, and the first results regarding hydrogen isotope ratios recently became available.All of these will be presented in detail within this review together with some considerations on validation issues and on identification of parameters influencing steroidal isotope ratios in urine.

  13. Final report of the key comparison CCQM-K98: Pb isotope amount ratios in bronze

    Science.gov (United States)

    Vogl, Jochen; Yim, Yong-Hyeon; Lee, Kyoung-Seok; Goenaga-Infante, Heidi; Malinowskiy, Dmitriy; Ren, Tongxiang; Wang, Jun; Vocke, Robert D., Jr.; Murphy, Karen; Nonose, Naoko; Rienitz, Olaf; Noordmann, Janine; Näykki, Teemu; Sara-Aho, Timo; Ari, Betül; Cankur, Oktay

    2014-01-01

    Isotope amount ratios are proving useful in an ever increasing array of applications that range from studies unravelling transport processes, to pinpointing the provenance of specific samples as well as trace element quantification by using isotope dilution mass spectrometry (IDMS). These expanding applications encompass fields as diverse as archaeology, food chemistry, forensic science, geochemistry, medicine and metrology. However, to be effective tools, the isotope ratio data must be reliable and traceable to enable the comparability of measurement results. The importance of traceability and comparability in isotope ratio analysis has already been recognized by the Inorganic Analysis Working Group (IAWG) within the CCQM. While the requirements for isotope ratio accuracy and precision in the case of IDMS are generally quite modest, 'absolute' Pb isotope ratio measurements for geochemical applications as well as forensic provenance studies require Pb isotope ratio measurements of the highest quality. To support present and future CMCs on isotope ratio determinations, a key comparison was urgently needed and therefore initiated at the IAWG meeting in Paris in April 2011. The analytical task within such a comparison was decided to be the measurement of Pb isotope amount ratios in water and bronze. Measuring Pb isotope amount ratios in an aqueous Pb solution tested the ability of analysts to correct for any instrumental effects on the measured ratios, while the measurement of Pb isotope amount ratios in a metal matrix sample provided a real world test of the whole chemical and instrumental procedure. A suitable bronze material with a Pb mass fraction between 10 and 100 mg•kg-1 and a high purity solution of Pb with a mass fraction of approximately 100 mg•kg-1 was available at the pilot laboratory (BAM), both offering a natural-like Pb isotopic composition. The mandatory measurands, the isotope amount ratios n(206Pb)/n(204Pb), n(207Pb)/n(204Pb) and n(208Pb)/n(204Pb

  14. Carbon isotopic ratio analysis by gas chromatography/combustion/isotope ratio mass spectrometry for the detection of gamma-hydroxybutyric acid (GHB) administration to humans.

    Science.gov (United States)

    Saudan, Christophe; Augsburger, Marc; Mangin, Patrice; Saugy, Martial

    2007-01-01

    Since GHB (gamma-hydroxybutyric acid) is naturally produced in the human body, clinical and forensic toxicologists must be able to discriminate between endogenous levels and a concentration resulting from exposure. To suggest an alternative to the use of interpretative concentration cut-offs, the detection of exogenous GHB in urine specimens was investigated by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). GHB was isolated from urinary matrix by successive purification on Oasis MCX and Bond Elute SAX solid-phase extraction (SPE) cartridges prior to high-performance liquid chromatography (HPLC) fractioning using an Atlantis dC18 column eluted with a mixture of formic acid and methanol. Subsequent intramolecular esterification of GHB leading to the formation of gamma-butyrolactone (GBL) was carried out to avoid introduction of additional carbon atoms for carbon isotopic ratio analysis. A precision of 0.3 per thousand was determined using this IRMS method for samples at GHB concentrations of 10 mg/L. The (13)C/(12)C ratios of GHB in samples of subjects exposed to the drug ranged from -32.1 to -42.1 per thousand, whereas the results obtained for samples containing GHB of endogenous origin at concentration levels less than 10 mg/L were in the range -23.5 to -27.0 per thousand. Therefore, these preliminary results show that a possible discrimination between endogenous and exogenous GHB can be made using carbon isotopic ratio analyses.

  15. A Plant-Based Proxy for the Oxygen Isotope Ratio of Atmospheric Water Vapor

    Science.gov (United States)

    Helliker, B.

    2007-12-01

    Atmospheric water vapor is a major component of the global hydrological cycle, but the isotopic balance of vapor is largely unknown. It is shown here that the oxygen isotope ratio of leaf water in the epiphytic Crassulacean acid metabolism (CAM) plant Tillandsia usneoides (Spanish Moss) is controlled by the oxygen isotope ratio of atmospheric water vapor in both field and lab studies. Assuming that the leaf-water isotopic signature (and hence the atmospheric water vapor signature) is recorded in plant organic material, the atmospheric water vapor oxygen isotope ratios for Miami, Florida (USA) were reconstructed for several years from 1878 to 2005 using contemporary and herbarium specimens. T. usneoides ranges from Virginia, USA southwards through the tropics to Argentina, and the CAM epiphytic lifeform is widespread in other species. Therefore, epiphytes may be used to reconstruct the isotope ratio of atmospheric water for spatial scales that span over 60° of latitude and temporal scales that cover the last century of global temperature increase.

  16. Development and application of liquid chromatography coupled to isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lijun

    2014-02-19

    Stable isotope analysis has found widespread applications in various disciplines such as archaeology, geochemistry, biology, food authenticity, and forensic science. Coupling chromatography to isotope ratio mass spectrometry for compound-specific isotope analysis (CSIA) is a trend, as it provides several advantages over bulk isotope analysis, e.g., relatively simple sample preparation, the ability to measure individual compounds in a complex mixture in one run, and the reduced sample size required for precise isotope analysis. Gas chromatography coupled to isotope ratio mass spectrometry (GC/IRMS) has been well-established for compound-specific isotope analysis of volatile organic compounds within the last two decades. However, an interface combining liquid chromatography with isotope ratio mass spectrometry (LC/IRMS) was not commercially available until 2004. The current design of the interface requires using a carbon-free eluent in chromatographic separation. This requirement limits the application of the most frequently used reversed-phase liquid chromatography in CSIA, because the elution strength of water at room temperature is too low to serve as mobile phase in reversed-phase separations. In order to increase the elution strength of water, we propose using high temperature water for chromatographic elution. The polarity of water decreases with an increase of temperature, yielding increased elution strength in reversed-phase columns. Therefore, high temperature water can be used as eluent instead of organic solvent for combining reversed-phase liquid chromatography with isotope ratio mass spectrometry (RPLC/IRMS). Additionally, temperature gradients can replace organic solvent gradients to increase chromatographic resolution. This is very important for LC/IRMS analysis, as precise isotope analysis requires baseline separation of analytes. In this thesis, high-temperature reversed-phase liquid chromatography was coupled to, and for the first time carefully

  17. Invited review article: Recent developments in isotope-ratio mass spectrometry for geochemistry and cosmochemistry.

    Science.gov (United States)

    Ireland, Trevor R

    2013-01-01

    Mass spectrometry is fundamental to measurements of isotope ratios for applications in isotope geochemistry, geochronology, and cosmochemistry. Magnetic-sector mass spectrometers are most common because these provide the best precision in isotope ratio measurements. Where the highest precision is desired, chemical separation followed by mass spectrometric analysis is carried out with gas (noble gas and stable isotope mass spectrometry), liquid (inductively coupled plasma mass spectrometry), or solid (thermal ionization mass spectrometry) samples. Developments in in situ analysis, including ion microprobes and laser ablation inductively coupled plasma mass spectrometry, have opened up issues concerning homogeneity according to domain size, and allow ever smaller amounts of material to be analyzed. While mass spectrometry is built solidly on developments in the 20th century, there are new technologies that will push the limits in terms of precision, accuracy, and sample efficiency. Developments of new instruments based on time-of-flight mass spectrometers could open up the ultimate levels of sensitivity per sample atom.

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

    Science.gov (United States)

    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.

  19. Atmospheric circulation controls on the inter-annual variability in precipitation isotope ratio in Japan

    Directory of Open Access Journals (Sweden)

    N. Kurita

    2014-10-01

    Full Text Available This study explored the primary driver of variations of precipitation isotopes at multiple temporal scales (event, seasonal and inter-annual scales to provide a greater depth of interpretation for isotope proxy records in Japan. A one-year record of the isotopic composition of event-based precipitation at Nagoya in central Japan showed less seasonal variation, but there is large isotopic variability on a storm-to-storm basis. In the summer, southerly flows transport isotopically enriched moisture from subtropical marine regions with the result that the rainfall produced by the subtropical air, or warm rainfall, was relatively enriched in heavy isotopes in comparison with the other rainfall events. In the winter, storm tracks are the dominant driver of storm-to-storm isotopic variation, and relatively lower isotopic values occurred when northerly winds in association with extratropical cyclones passing off the south coast of Japan (Nangan cyclone brings cold precipitation. Using the historical 17 year record of monthly isotopes in precipitation at Tokyo station, we explored if the factors controlling event-scale isotopic variability can account for inter-annual isotopic variability. The relatively higher isotopes in summer precipitation were attributed to the higher contribution of the warm rainfall to the total summer precipitation. On the other hand, year-to-year variation of isotopic values in winter precipitation was negatively correlated with the relative ratio of the Nangan cyclone rainfall to the total winter precipitation. The 17 year precipitation history demonstrates that event-scale isotopic variability related to changes in meridional moisture transport is the primary driver of inter-annual isotopic variability in winter and summer precipitation. The meridional moisture transport to central Japan is likely linked to the activity of the western North Pacific subtropical high in summer and the intensity of the East Asian winter monsoon

  20. Research Progress of Series of Uranium Isotope Ratios Measured by AMS

    Institute of Scientific and Technical Information of China (English)

    LIN; De-yu; WANG; Chen; HUANG; Guo-rui; DONG; Ke-jun; HE; Ming; RUAN; Xiang-dong; WU; Shao-yong; ZHAO; Yong-gang; LI; Li-li; DOU; Liang; XIE; Lin-bo; WANG; Xiao-bo; YANG; Xu-ran; WANG; Xiao-ming; LAN; Xiao-xi; JIANG; Shan

    2012-01-01

    <正>The nuclear safeguards system which is used to monitor compliance with the Nuclear Non-proliferation Treaty relies to a significant degree on the analysis of environmental samples. Undeclared nuclear activities can be detected through determination of the isotopic ratios of uranium and plutonium in such samples. It is necessary to be able to measure the full suite of uranium isotopes (234U,

  1. Helium Isotopic Ratios of Core Samples from IODP Exp. 319 (NanTroSEIZE Stage 2)

    Science.gov (United States)

    Horiguchi, K.; Matsuda, J.; Wiersberg, T.; Shimo, Y.; Tamura, H.; Kumagai, H.; Suzuki, K.; Saito, S.; Kinoshita, M.; Araki, E.; Byrne, T.; McNeill, L. C.; Saffer, D.; Takahashi, K.; Eguchi, N. O.; Toczko, S.

    2009-12-01

    IODP Exp.319 of Nankai Trough Seismogenic Zone Drilling Program Stage 2 started at May 2009. Various advanced technologies including first riser-based scientific ocean drilling were carried out at this cruise. The Hole C0009A (Site C0009/ Hole A) recovered cutting and partly core samples from 703.9-1604 mbsf by riser-drilling. The core samples were collected between the depth of 1510.5 and 1593.9 mbsf. Here we report preliminary helium isotopic ratios of these cores. We collected three types of samples for our study: (1) gas of cores, (2) whole round cores (100 cc) and (3) small whole round cores (10 cc). The gas samples were taken immediately after the core recovery. The gas samples were collected from each core section by using a syringe, and it was transferred to the glass bottle using the water displacement method. The glass bottle was made by Pyrex glass with vacuum valve at each end. We collected two sizes of whole round core samples (100 cc and 10 cc) The 100 cc cores were collected from the bottom and top sections of coring. The 10 cc cores were taken from the other sections. The outer parts of these samples were carefully removed to avoid contaminations from drilling fluid. After the removal of contamination, we immediately stored the 100 cc samples into vacuum container and 10 cc samples into plastic bag under a dry condition, respectively. The gas samples were measured for helium isotopic ratios. The noble gas measurement was carried out at Osaka University by using VG5400 mass spectrometer. We measured helium isotopic ratio and 4He/20Ne ratio. The latter is useful for making correction of the air contamination. The obtained result of helium isotopic ratios shows that the radiogenic helium is prominent in all samples. In addition, the helium isotope ratios show a trend that the ratio at shallower part is slightly higher than that at deeper part. It is conceivable that this trend is due to the larger radiogenic ingrowths at the deeper part. However, the

  2. Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

    Science.gov (United States)

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

    2011-01-01

    We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. 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 reactions [8,9]. 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 [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

  3. Detailed analysis of isotopic ratio of radioactive iodine in surface soil around Fukushima Daiichi Nuclear Power Plant

    Science.gov (United States)

    Miyake, Yasuto; Matsuzaki, Hiroyuki; Fujiwara, Takeshi; Saito, Takumi; Yamagata, Takeyasu; Honda, Maki

    2013-04-01

    In March 2011, there was an accident at the Fukushima Daiichi Nuclear Power Plant (FDNPP) and a lot of radionuclides were discharged into the environment, resulting from a powerful earthquake and tsunami. Considering the impact on human health, the radiation dosimetry is the most important for Iodine-131 among radionuclides in the initial stage immediately following the release of radionuclides. However, Iodine-131 cannot be detected after several months owing to its short half-life (8 days). Cesium-137 was also leaked out from the FDNPP and this can be detected now. But this did not identically act with Iodine-131 and be suitable for the reconstruction of Iodine-131 distribution at the initial stage. Since Iodine-129 (half-life: 1.57E7 yrs) can be detected in the future and it act chemically identically with Iodine-131, the reconstruction by Iodine-129 analysis is important. For this reconstruction, it is necessary to know the isotopic ratio of radioactive iodine (129I/131I) released from the FDNPP. In this study, the Iodine-129 concentration was measured by accelerator mass spectrometry (AMS) in several surface soil samples collected around the FDNPP for which the Iodine-131level had already been determined. Soil samples were put into a U8 standard vessel after being roughly homogenized and dried. Then, samples were homogenized again more completely and several grams were taken for Iodine-129 measurement. Each sample was combusted in a quartz tube and outgas was trapped in alkali solution. An aliquot was taken from the trap solution for the determination of the Iodine-127 concentration by inductively coupled plasma mass spectrometry (ICP-MS). The iodine carrier was added to the trap solution, from which the iodine fraction was purified by solvent extraction and back extraction. Finally, silver iodide precipitation was obtained by adding silver nitrate solution. After dried, the precipitation was mixed with niobium powder and pressed into a cathode for the target

  4. Determination of the geographical origin of Chinese teas based on stable carbon and nitrogen isotope ratios

    Institute of Scientific and Technical Information of China (English)

    Long ZHANG; Jia-rong PAN; Cheng ZHU

    2012-01-01

    The objective of this study was to investigate the geographical origin of Chinese teas using carbon and nitrogen stable isotope ratio technology.The results showed that inter-provincial dispersion of teas in Guangdong (GD),Guangxi (GX),Hainan (HA),Fujian (F J),Shandong (SD),Sichuan (SC),Chongqing (CQ),and Henan (HN) provinces was high,while in Zhejiang (ZJ),Hubei (HB),Yunnan (YN),and Anhui (AH) provinces,it was low.Tea samples from GD,GX,HA,and FJ provinces were clustered in one group and separated from those from AH and HB provinces.Thus,carbon and nitrogen stable isotope ratio technology could discriminate teas from among some provinces of China,but not from among others.Better separation might be obtained with a combination of isotopic ratios and other indexes,such as elemental data and organic components.

  5. The puzzle of the CNO isotope ratios in asymptotic giant branch carbon stars

    Science.gov (United States)

    Abia, C.; Hedrosa, R. P.; Domínguez, I.; Straniero, O.

    2017-02-01

    Context. The abundance ratios of the main isotopes of carbon, nitrogen and oxygen are modified by the CNO-cycle in the stellar interiors. When the different dredge-up events mix the burning material with the envelope, valuable information on the nucleosynthesis and mixing processes can be extracted by measuring these isotope ratios. Aims: Previous determinations of the oxygen isotopic ratios in asymptotic giant branch (AGB) carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Methods: Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in local thermodynamic equillibrium (LTE) with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M⊙) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. Results: For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the first dredge-up (FDU) according to the initial stellar mass. This fact, as far as the oxygen isotopic ratios are concerned, leaves little space for the operation of any extra mixing mechanism during the AGB phase. Nevertheless, for a few stars with large 16O/17O/18O, the operation of such a mechanism might be required, although their observed 12C/13C and 14N/15N ratios would be difficult to reconcile within this scenario. Furthermore, J-type stars tend to have lower 16O/17O ratios than the normal carbon stars, as already indicated in previous studies

  6. Application of neodymium isotope ratio measurements for the origin assessment of uranium ore concentrates.

    Science.gov (United States)

    Krajkó, Judit; Varga, Zsolt; Yalcintas, Ezgi; Wallenius, Maria; Mayer, Klaus

    2014-11-01

    A novel procedure has been developed for the measurement of (143)Nd/(144)Nd isotope ratio in various uranium-bearing materials, such as uranium ores and ore concentrates (UOC) in order to evaluate the usefulness and applicability of variations of (143)Nd/(144)Nd isotope ratio for provenance assessment in nuclear forensics. Neodymium was separated and pre-concentrated by extraction chromatography and then the isotope ratios were measured by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method was validated by the measurement of standard reference materials (La Jolla, JB-2 and BCR-2) and the applicability of the procedure was demonstrated by the analysis of uranium samples of world-wide origin. The investigated samples show distinct (143)Nd/(144)Nd ratio depending on the ore type, deposit age and Sm/Nd ratio. Together with other characteristics of the material in question, the Nd isotope ratio is a promising signature for nuclear forensics and suggests being indicative of the source material, the uranium ore.

  7. The puzzle of the CNO isotope ratios in AGB carbon stars

    CERN Document Server

    Abia, Carlos; Domínguez, Inma; Straniero, Oscar

    2016-01-01

    Previous determinations of the oxygen isotopic ratios in AGB carbon stars were at odds with the existing theoretical predictions. We aim to redetermine the oxygen ratios in these stars using new spectral analysis tools and further develop discussions on the carbon and nitrogen isotopic ratios in order to elucidate this problem. Oxygen isotopic ratios were derived from spectra in the K-band in a sample of galactic AGB carbon stars of different spectral types and near solar metallicity. Synthetic spectra calculated in LTE with spherical carbon-rich atmosphere models and updated molecular line lists were used. The CNO isotope ratios derived in a homogeneous way, were compared with theoretical predictions for low-mass (1.5-3 M_o) AGB stars computed with the FUNS code assuming extra mixing both during the RGB and AGB phases. For most of the stars the 16O/17O/18O ratios derived are in good agreement with theoretical predictions confirming that, for AGB stars, are established using the values reached after the FDU a...

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

    KAUST Repository

    Parkes, Stephen

    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

  9. Isotope analytics for the evaluation of the feeding influence on the isotope ratio in beef samples; Isotopenanalytik zur Bestimmung des Einflusses der Ernaehrung auf die Isotopenzusammensetzung in Rinderproben

    Energy Technology Data Exchange (ETDEWEB)

    Herwig, Nadine

    2010-11-17

    Information about the origin of food and associated production systems has a high significance for food control. An extremely promising approach to obtain such information is the determination of isotope ratios of different elements. In this study the correlation of the isotope ratios C-13/C-12, N-15/N-14, Mg-25/Mg-24, and Sr-87/Sr-86 in bovine samples (milk and urine) and the corresponding isotope ratios in feed was investigated. It was shown that in the bovine samples all four isotope ratios correlate with the isotope composition of the feed. The isotope ratios of strontium and magnesium have the advantage that they directly reflect the isotope ratios of the ingested feed since there is no isotope fractionation in the bovine organism which is in contrast to the case of carbon and nitrogen isotope ratios. From the present feeding study it is evident, that a feed change leads to a significant change in the delta C-13 values in milk and urine within 10 days already. For the deltaN-15 values the feed change was only visible in the bovine urine after 49 days. Investigations of cows from two different regions (Berlin/Germany and Goestling/Austria) kept at different feeding regimes revealed no differences in the N-15/N-14 and Mg-26/Mg-24 isotope ratios. The strongest correlation between the isotope ratio of the bovine samples and the kind of ingested feed was observed for the carbon isotope ratio. With this ratio even smallest differences in the feed composition were traceable in the bovine samples. Since different regions usually coincide with different feeding regimes, carbon isotope ratios can be used to distinguish bovine samples from different regions if the delta C-13 values of the ingested feed are different. Furthermore, the determination of strontium isotope ratios revealed significant differences between bovine and feed samples of Berlin and Goestling due to the different geologic realities. Hence the carbon and strontium isotope ratios allow the best

  10. Spectral analysis software improves confidence in plant and soil water stable isotope analyses performed by isotope ratio infrared spectroscopy (IRIS).

    Science.gov (United States)

    West, A G; Goldsmith, G R; Matimati, I; Dawson, T E

    2011-08-30

    Previous studies have demonstrated the potential for large errors to occur when analyzing waters containing organic contaminants using isotope ratio infrared spectroscopy (IRIS). In an attempt to address this problem, IRIS manufacturers now provide post-processing spectral analysis software capable of identifying samples with the types of spectral interference that compromises their stable isotope analysis. Here we report two independent tests of this post-processing spectral analysis software on two IRIS systems, OA-ICOS (Los Gatos Research Inc.) and WS-CRDS (Picarro Inc.). Following a similar methodology to a previous study, we cryogenically extracted plant leaf water and soil water and measured the δ(2)H and δ(18)O values of identical samples by isotope ratio mass spectrometry (IRMS) and IRIS. As an additional test, we analyzed plant stem waters and tap waters by IRMS and IRIS in an independent laboratory. For all tests we assumed that the IRMS value represented the "true" value against which we could compare the stable isotope results from the IRIS methods. Samples showing significant deviations from the IRMS value (>2σ) were considered to be contaminated and representative of spectral interference in the IRIS measurement. Over the two studies, 83% of plant species were considered contaminated on OA-ICOS and 58% on WS-CRDS. Post-analysis, spectra were analyzed using the manufacturer's spectral analysis software, in order to see if the software correctly identified contaminated samples. In our tests the software performed well, identifying all the samples with major errors. However, some false negatives indicate that user evaluation and testing of the software are necessary. Repeat sampling of plants showed considerable variation in the discrepancies between IRIS and IRMS. As such, we recommend that spectral analysis of IRIS data must be incorporated into standard post-processing routines. Furthermore, we suggest that the results from spectral analysis be

  11. Irradiated Xenon Isotopic Ratio Measurement for Failed Fuel Detection and Location in Fast Reactor

    Science.gov (United States)

    Ito, Chikara; Iguchi, Tetsuo; Harano, Hideki

    2009-08-01

    The accuracy of xenon isotopic ratio burn-up calculations used for failed fuel identification was evaluated by an irradiation test of xenon tag gas samples in the Joyo test reactor. The experiment was carried out using pressurized steel capsules containing unique blend ratios of stable xenon tag gases in an on-line creep rupture experiment in Joyo. The tag gas samples were irradiated to total neutron fluences of 1.6 to 4.8 × 1026 n/m2. Laser resonance ionization mass spectrometry was used to analyze the cover gas containing released tag gas diluted to isotopic ratios of 100 to 102 ppb. The isotopic ratios of xenon tag gases after irradiation were calculated using the ORIGEN2 code. The neutron cross sections of xenon nuclides were based on the JENDL-3.3 library. These cross sections were collapsed into one group using the neutron spectra of Joyo. The comparison of measured and calculated xenon isotopic ratios provided C/E values that ranged from 0.92 to 1.10. The differences between calculation and measurement were considered to be mainly due to the measurement errors and the xenon nuclide cross section uncertainties.

  12. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric PM

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-05-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter (PM is presented. It has been found in numerous laboratory studies that these compounds are photooxidation products of toluene in PM. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. PM was collected on quartz fibre filters using dichotomous high volume air samplers for PM 2.5. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography (HPLC and solid phase extraction (SPE. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide (BSTFA, was added to the solution for Gas Chromatography/Mass Spectroscopy (GC/MS analysis. The second half of the sample was stored at low temperature. When GC/MS analysis showed high enough concentrations the remaining sample was derivatized with BSTFA and analysed for stable isotope ratio using a Gas Chromatography/Isotope Ratio Mass Spectrometry (GC-IRMS.

    In all atmospheric PM samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol. Nevertheless, due to low pollution levels occurring in the rural area, no samples had concentrations high enough to perform stable carbon isotope composition measurements of the methylnitrophenols. Samples collected in the suburban area could be analysed for carbon stable isotope ratio using GC-IRMS.

    The procedure described in this paper provides a very sensitive and selective method for the analysis of methylnitrophenols in atmospheric PM at concentrations as low as 1 pg m−3. For accurate (within ±0.5‰ stable isotope ratio analysis significantly higher concentrations in the range of 100 pg m−3 or more are required.

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

    Science.gov (United States)

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

    2013-12-01

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

  14. Proportions of convective and stratiform precipitation revealed in water isotope ratios

    Science.gov (United States)

    Aggarwal, Pradeep K.; Romatschke, Ulrike; Araguas-Araguas, Luis; Belachew, Dagnachew; Longstaffe, Frederick J.; Berg, Peter; Schumacher, Courtney; Funk, Aaron

    2016-08-01

    Tropical and midlatitude precipitation is fundamentally of two types, spatially limited and high-intensity convective or widespread and lower-intensity stratiform, owing to differences in vertical air motions and microphysical processes governing rain formation. These processes are difficult to observe or model and precipitation partitioning into rain types is critical for understanding how the water cycle responds to changes in climate. Here, we combine two independent data sets--convective and stratiform precipitation fractions, derived from the Tropical Rainfall Measuring Mission satellite or synoptic cloud observations, and stable isotope and tritium compositions of surface precipitation, derived from a global network--to show that isotope ratios reflect rain type proportions and are negatively correlated with stratiform fractions. Condensation and riming associated with boundary layer moisture produces higher isotope ratios in convective rain, along with higher tritium when riming in deep convection occurs with entrained air at higher altitudes. On the basis of our data, stable isotope ratios can be used to monitor changes in the character of precipitation in response to periodic variability or changes in climate. Our results also provide observational constraints for an improved simulation of convection in climate models and a better understanding of isotope variations in proxy archives, such as speleothems and tropical ice.

  15. Tracing contamination sources in soils with Cu and Zn isotopic ratios.

    Science.gov (United States)

    Fekiacova, Z; Cornu, S; Pichat, S

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ(65)Cu values vary from -0.15 to 0.44‰ and the δ(66)Zn from -0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from -0.95 to 0.44‰ for δ(65)Cu and from -0.53 to 0.64‰ for δ(66)Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case.

  16. A versatile method for stable carbon isotope analysis of carbohydrates by high-performance liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Boschker, H.T.S.; Moerdijk-Poortvliet, T.C.W.; Van Breugel, P.; Houtekamer, M.J.; Middelburg, J.J.

    2008-01-01

    We have developed a method to analyze stable carbon isotope (13C/12C) ratios in a variety of carbohydrates using high-performance liquid chromatography/isotope ratio mass spectrometry (HPLC/IRMS). The chromatography is based on strong anion-exchange columns with low strength NaOH eluents. An eluent

  17. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALE Liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (13C/12C) in biological metabolites, at their natural abundance. However, until now this technique coul

  18. A versatile method for simultaneous stable carbon isotope analysis of DNA and RNA nucleotides by liquid chromatography/isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Moerdijk-Poortvliet, T.C.W.; Brasser, J.; de Ruiter, G.; Houtekamer, M.; Bolhuis, H.; Stal, L.J.; Boschker, H.T.S.

    2014-01-01

    RATIONALELiquid chromatography/isotope ratio mass spectrometry (LC/IRMS) is currently the most accurate and precise technique for the measurement of compound-specific stable carbon isotope ratios (C-13/C-12) in biological metabolites, at their natural abundance. However, until now this technique cou

  19. Isotope ratio mass spectrometry as a tool for source inference in forensic science: A critical review.

    Science.gov (United States)

    Gentile, Natacha; Siegwolf, Rolf T W; Esseiva, Pierre; Doyle, Sean; Zollinger, Kurt; Delémont, Olivier

    2015-06-01

    Isotope ratio mass spectrometry (IRMS) has been used in numerous fields of forensic science in a source inference perspective. This review compiles the studies published on the application of isotope ratio mass spectrometry (IRMS) to the traditional fields of forensic science so far. It completes the review of Benson et al. [1] and synthesises the extent of knowledge already gathered in the following fields: illicit drugs, flammable liquids, human provenancing, microtraces, explosives and other specific materials (packaging tapes, safety matches, plastics, etc.). For each field, a discussion assesses the state of science and highlights the relevance of the information in a forensic context. Through the different discussions which mark out the review, the potential and limitations of IRMS, as well as the needs and challenges of future studies are emphasized. The paper elicits the various dimensions of the source which can be obtained from the isotope information and demonstrates the transversal nature of IRMS as a tool for source inference.

  20. Variation in strontium isotope ratios of archaeological fauna in the Midwestern United States: a preliminary study

    Science.gov (United States)

    Hedman, Kristin M.; Curry, B. Brandon; Johnson, Thomas M.; Fullagar, Paul D.; Emerson, Thomas E.

    2009-01-01

    Strontium isotope values (87Sr/86Sr) in bone and tooth enamel have been used increasingly to identify non-local individuals within prehistoric human populations worldwide. Archaeological research in the Midwestern United States has increasingly highlighted the role of population movement in affecting interregional cultural change. However, the comparatively low level of geologic variation in the Midwestern United States might suggest a corresponding low level of strontium variation, and calls into question the sensitivity of strontium isotopes to identify non-local individuals in this region. Using strontium isotopes of archaeological fauna, we explore the degree of variability in strontium ratios across this region. Our results demonstrate measurable variation in strontium ratios and indicate the potential of strontium analysis for addressing questions of origin and population movement in the Midwestern United States.

  1. Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates

    Science.gov (United States)

    Hippler, Dorothee; Buhl, Dieter; Witbaard, Rob; Richter, Detlev K.; Immenhauser, Adrian

    2009-10-01

    This study presents magnesium stable-isotope compositions of various biogenic carbonates of several marine calcifying organisms and an algae species, seawater samples collected from the western Dutch Wadden Sea, and reference materials. The aim of this study is to explore the influence of mineralogy, taxonomy and environmental factors (e.g., seawater isotopic composition, temperature, salinity) on magnesium-isotopic (δ 26Mg) ratios of skeletal carbonates. Using high-precision multi-collector inductively coupled plasma mass spectrometry, we observed that the magnesium-isotopic composition of seawater from the semi-enclosed Dutch Wadden Sea is identical to that of open marine seawater. We further found that a considerable component of the observed variability in δ 26Mg values of marine skeletal carbonates can be attributed to differences in mineralogy. Furthermore, magnesium-isotope fractionation is species-dependent, with all skeletal carbonates being isotopically lighter than seawater. While δ 26Mg values of skeletal aragonite and high-magnesium calcite of coralline red algae indicate the absence or negligibility of metabolic influences, the δ 26Mg values of echinoids, brachiopods and bivalves likely result from a taxon-specific level of control on Mg-isotope incorporation during biocalcification. Moreover, no resolvable salinity and temperature effect were observed for coralline red algae and echinoids. In contrast, Mg-isotope data of bivalves yield ambiguous results, which require further validation. The data presented here, point to a limited use of Mg isotopes as temperature proxy, but highlight the method's potential as tracer of seawater chemistry through Earth's history.

  2. A supercritical oxidation system for the determination of carbon isotope ratios in marine dissolved organic carbon

    NARCIS (Netherlands)

    Le Clercq, Martijn; Van der Plicht, Johannes; Meijer, Harro A.J.

    1998-01-01

    An analytical oxidation system employing supercritical oxidation has been developed. It is designed to measure concentration and the natural carbon isotope ratios (C-13, C-14) Of dissolved organic carbon (DOC) and is especially suited for marine samples. The oxidation takes place in a ceramic tube a

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

    Science.gov (United States)

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

    2016-09-01

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

  4. Lithologically inherited variation in Pb isotope ratios in sedimentary soils in The Netherlands

    NARCIS (Netherlands)

    Walraven, N.; Gaans, P.F.M. van; Veer, G. van der; Os, B.J.H. van; Klaver, G.T.; Vriend, S.P.; Middelburg, J.J.; Davies, G.R.

    2013-01-01

    Knowledge on the lithologically inherited variation in present day Pb isotope ratios in soils is remarkably limited. Such information is essential to determine the anthropogenic Pb fraction and anthropogenic Pb sources in Pb-polluted soils. This study presents results of a survey of subsoil samples

  5. Tracing contamination sources in soils with Cu and Zn isotopic ratios

    Energy Technology Data Exchange (ETDEWEB)

    Fekiacova, Z.; Cornu, S. [INRA, UR 1119 Géochimie des Sols et des Eaux, F-13100 Aix en Provence (France); Pichat, S. [Laboratoire de Géologie de Lyon (LGL-TPE), Ecole Normale Supérieure de Lyon, CNRS, UMR 5276, 69007 Lyon (France)

    2015-06-01

    Copper (Cu) and zinc (Zn) are naturally present and ubiquitous in soils and are important micronutrients. Human activities contribute to the input of these metals to soils in different chemical forms, which can sometimes reach a toxic level for soil organisms and plants. Isotopic signatures could be used to trace sources of anthropogenic Cu and Zn pollution. The aim of this paper is to determine whether it is possible to identify (i) Cu and Zn contamination in soils and their sources, on the basis of their isotopic signatures, and (ii) situations that are a priori favorable or not for tracing Cu and Zn pollution using the isotopic approach. Therefore, we compiled data from the literature on Cu and Zn isotopes in soils, rocks and pollutants and added to this database the results of our own research. As only a few studies have dealt with agricultural contamination, we also studied a soil toposequence from Brittany, France, that experienced spreading of pig slurry for tens of years. In the surface horizons of the natural soils, the δ{sup 65}Cu values vary from − 0.15 to 0.44‰ and the δ{sup 66}Zn from − 0.03 to 0.43‰. Furthermore, vertical variations along soil profiles range from − 0.95 to 0.44‰ for δ{sup 65}Cu and from − 0.53 to 0.64‰ for δ{sup 66}Zn values. We concluded that pedogenetic processes can produce isotopic fractionation, yet, it is not always discernible and can be overprinted by an exogenous isotopic signature. Furthermore, some contaminants are enriched in heavy Cu or in light Zn compared to the rock or soil, but no generalization can be made. The anthropogenic inputs can be identified based on stable Cu and Zn isotope ratios if the isotope ratios of the sources are different from those of the soil, which needs to be tested for each individual case. - Highlights: • Pedogenetic processes produce some Cu and Zn isotope fractionation. • Pollution with distinct isotopic signatures can be traced using Cu and Zn isotopes. • Tracing

  6. On-line determination of oxygen isotope ratios of water or ice by mass spectrometry.

    Science.gov (United States)

    Leuenberger, M; Huber, C

    2002-09-15

    Oxygen isotope ratio determination on any of the water phases (water vapor, water, ice) is of great relevance in different research fields such as climate and paleoclimate studies, geological surveys, and hydrological studies. The conventional technique for oxygen isotope measurement involves equilibration with carbon dioxide gas for a given time with a subsequent isotope determination. The equilibration technique is available in different layouts, but all of them are rather time-consuming. Here we report a new on-line technique that processes water samples as well as ice samples. The same principal, CO2 hydration, is used but speeded up by (i) a direct injection and full dissolution of CO2 in the water, (ii) an increased isotope exchange temperature at 50 degrees C, and (iii) a rapid gas extraction by means of an air-permeable membrane into a continuous helium flux supplying the isotope ratio mass spectrometer with the sample gas. The precision is better than 0.1/1000 which is only slightly larger than with the conventional equilibration technique. This on-line technique allows analysis of 1 m of ice with a resolution of 1-3 cm, depending on the meltwater flux, within 1 h. Similarly, continuous and fast analysis can be performed for aqueous samples for hydrological, geological, and perhaps medical applications.

  7. Simulating stable carbon and chlorine isotope ratios in dissolved chlorinated groundwater pollutants with BIOCHLOR-ISO

    Science.gov (United States)

    Höhener, Patrick

    2016-12-01

    BIOCHLOR is a well-known simple tool for evaluating the transport of dissolved chlorinated solvents in groundwater, ideal for rapid screening and teaching. This work extends the BIOCHLOR model for the calculation of stable isotope ratios of carbon and chlorine isotopes in chloroethenes. An exact solution for the three-dimensional reactive transport of a chain of degrading compounds including sorption is provided in a spreadsheet and applied for modeling the transport of individual isotopes 12C, 13C, 35Cl, 37Cl from a constant source. The model can consider secondary isotope effects that can occur in the breaking of Csbnd Cl bonds. The model is correctly reproducing results for δ13C and δ37Cl modeled by a previously published 1-D numerical model without secondary isotope effects, and is also reproducing results from a microcosm experiment with secondary chlorine isotope effects. Two applications of the model using field data from literature are further given and discussed. The new BIOCHLOR-ISO model is distributed as a spreadsheet (MS EXCEL) along with this publication.

  8. The application of isotope ratio mass spectrometry for discrimination and comparison of adhesive tapes.

    Science.gov (United States)

    Horacek, Micha; Min, Ji-Sook; Heo, Sangcheol; Park, Jongseo; Papesch, Wolfgang

    2008-06-01

    Forensic scientists are frequently requested to differentiate between, or compare, adhesive tapes from a suspect or a crime scene. The most common polymers used to back packaging tape are polypropylene and polyvinyl chloride. Much of the oriented polypropylene (OPP) needed to produce packaging tapes, regardless of the tape brand, is supplied by just a few polymer manufacturers. Consequently, the composition of the backing material varies little. Therefore, the discriminating power of classical methods (physical fit, tape dimensions, colour, morphology, FTIR, PyGC/MS, etc.) is limited. Analysis of stable isotopes using isotope ratio mass spectrometry (IRMS) has been applied in the broad area of forensics and it has been reported that isotope analysis is a valuable tool for the identification of adhesive tapes. We have tested the usefulness of this method by distinguishing different South Korean adhesive tapes produced by just a few manufacturers in the small South Korean market. Korean adhesive tapes were collected and analysed for their isotope signatures. The glue of the tapes was separated from the backing material and these sub-samples were analysed for their H- and C-isotope composition. The result shows the possibility for discriminating most tape samples, even from the same brand. Variations within single rolls have also been investigated, where no variations in H- and C-isotope composition significantly exceeding the standard deviation were found.

  9. Forensic utility of the carbon isotope ratio of PVC tape backings

    Science.gov (United States)

    Stern, L. A.; Thompson, A. H.; Mehltretter, A. H.; McLaskey, V.; Parish, A.; Aranda, R.

    2008-12-01

    Forensic interest in adhesive tapes with PVC-backings (polyvinyl chloride, electrical tapes) derives from their use in construction of improvised explosive devices, drug packaging and in a variety of other illicit activities. Due to the range of physical characteristics and chemical compositions of such tapes, traditional microscopic and chemical analysis of the tape backings and adhesives offer a high degree of discrimination between tapes from different manufacturers and products. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different tapes of the same product, we assessed the PVC-backings of 87 rolls of black electrical tape for their δ13C values. The adhesive on these tapes was physically removed with hexane, and plasticizers within the PVC tape backings were removed by three-20 minute extractions with chloroform. The δ13C values of the PVC tape backings ranged between -23.8 and -41.5 (‰ V-PDB). The carbon isotopic variation within a product (identical brand and product identification) is significant, based on five products with at least 3 rolls (ranges of 7.4‰ (n=3), 10.0‰ (n=6), 4.2‰ (n=16), 3.8‰ (n=6), and 11.5‰ (n=8), respectively). There was no measurable carbon isotope variation in regards to the following: a) along the length of a roll (4 samples from 1 roll); b) between the center and edge of a strip of tape (1 pair); c) between rolls assumed to be from the same lot of tape (2 pairs); d) between different rolls from the same batch of tape (same product purchased at the same time and place; 5 pairs); and e) between samples of a tape at room temperature, heated to 50° C and 80° C for 1 week. For each sample within the population of 87 tapes, carbon isotopes alone exclude 80 to 100% of the tapes as a potential match, with an average exclusion power of 92.5%, using a window of ± 0.4‰. Carbon isotope variations originate from variations in starting

  10. Dietary heterogeneity among Western industrialized countries reflected in the stable isotope ratios of human hair.

    Directory of Open Access Journals (Sweden)

    Luciano O Valenzuela

    Full Text Available Although the globalization of food production is often assumed to result in a homogenization of consumption patterns with a convergence towards a Western style diet, the resources used to make global food products may still be locally produced (glocalization. Stable isotope ratios of human hair can quantify the extent to which residents of industrialized nations have converged on a standardized diet or whether there is persistent heterogeneity and glocalization among countries as a result of different dietary patterns and the use of local food products. Here we report isotopic differences among carbon, nitrogen and sulfur isotope ratios of human hair collected in thirteen Western European countries and in the USA. European hair samples had significantly lower δ(13C values (-22.7 to -18.3‰, and significantly higher δ(15N (7.8 to 10.3‰ and δ(34S (4.8 to 8.3‰ values than samples from the USA (δ(13C: -21.9 to -15.0‰, δ(15N: 6.7 to 9.9‰, δ(34S: -1.2 to 9.9‰. Within Europe, we detected differences in hair δ(13C and δ(34S values among countries and covariation of isotope ratios with latitude and longitude. This geographic structuring of isotopic data suggests heterogeneity in the food resources used by citizens of industrialized nations and supports the presence of different dietary patterns within Western Europe despite globalization trends. Here we showed the potential of stable isotope analysis as a population-wide tool for dietary screening, particularly as a complement of dietary surveys, that can provide additional information on assimilated macronutrients and independent verification of data obtained by those self-reporting instruments.

  11. Stable isotope ratios and uric acid preservation in termites belonging to three feeding habits in Thailand.

    Science.gov (United States)

    Tayasu, I; Hyodo, F; Takematsu, Y; Sugimoto, A; Inoue, T; Kirtibutr, N; Abe, T

    2000-01-01

    Nitrogen and carbon stable isotope ratios and uric acid concentrations in termites sampled from a dry evergreen forest in Thailand, were determined across three kinds of feeding habits. Feeding habits of Microcerotermes crassus, which is an abundant wood-feeder, and Dicuspiditermes makhamensis, a common soil-feeding termite, were confirmed by isotopic signatures. Lichen feeding termites (Hospitalitermes birmanicus, H. bicolor and H. ataramensis) were characterized by low delta15N values, suggesting that they assimilated nitrogen deposited from the atmosphere. There was also a significant difference in uric acid concentrations between termites representing different feeding habits. No significant relationships were found between uric acid concentrations and delta15N or delta13C in Hospitalitermes. However, delta15N values were correlated with C/N ratios in H. birmanicus, except in one colony of H. ataramensis. delta13C values in both species were negatively correlated with C/N ratios.

  12. Frontiers of QC Laser spectroscopy for high precision isotope ratio analysis of greenhouse gases

    Science.gov (United States)

    Emmenegger, Lukas; Mohn, Joachim; Harris, Eliza; Eyer, Simon; Ibraim, Erkan; Tuzson, Béla

    2016-04-01

    An important milestone for laser spectroscopy was achieved when isotope ratios of greenhouse gases were reported at precision levels that allow addressing research questions in environmental sciences. Real-time data with high temporal resolution at moderate cost and instrument size make the optical approach highly attractive, complementary to the well-established isotope-ratio mass-spectrometry (IRMS) method. Especially appealing, in comparison to IRMS, is the inherent specificity to structural isomers having the same molecular mass. Direct absorption in the MIR in single or dual QCL configuration has proven highly reliable for the sta-ble isotopes of CO2, N2O and CH4. The longest time series of real-time measurements is currently available for δ13C and δ18O in CO2 at the high-alpine station Jung-fraujoch. At this well-equipped site, QCL based direct absorption spectroscopy (QCLAS) measurements are ongoing since 2008 1,2. Applications of QCLAS for N2O and CH4 stable isotopes are considerably more challenging because of the lower atmospheric mixing ratios, especially for the less abundant species, such as N218O and CH3D. For high precision (air, QCLAS may be combined with a fully automated preconcentration unit yielding an up to 500 times concentration increase and the capability to separate the target gas from spectral interferants by se-quential desorption 3. Here, we review our recent developments on high precision isotope ratio analysis of greenhouse gases, with special focus on the isotopic species of N2O and CH4. Furthermore, we show environ-mental applications illustrating the highly valuable information that isotope ratios of atmospheric trace gases can carry. For example, the intramolecular distribution of 15N in N2O gives important information on the geochemical cycle of N2O4-6, while the analysis of δ13C and δ D in CH4 may be applied to disentangle microbial, fossil and landfill sources 7. 1 Sturm, P., Tuzson, B., Henne, S. & Emmenegger, L. Tracking

  13. Taking into account absorbed doses in tooth enamel due to internal irradiation of human body by radioactive cesium isotopes at analysis EPR dosimetry data: Calculation by Monte-Carlo method

    Energy Technology Data Exchange (ETDEWEB)

    Borysheva, N. [Medical Radiological Research Center, Korolyov str., 4, Obninsk 249020 (Russian Federation); Ivannikov, A. [Medical Radiological Research Center, Korolyov str., 4, Obninsk 249020 (Russian Federation)], E-mail: Ivannikov-Alexander@yandex.ru; Tikunov, D.; Orlenko, S.; Skvortsov, V.; Stepanenko, V. [Medical Radiological Research Center, Korolyov str., 4, Obninsk 249020 (Russian Federation); Hoshi, M. [Research Institute for Radiation Biology and Medicine, Hiroshima University, 1-2-3 Kasumi, Minami-ku, Hiroshima 734-8553 (Japan)

    2007-07-15

    By Monte-Carlo simulation of ionizing particles transport, for a realistic mathematical phantom of a man supplemented by a dental region, absorbed doses in teeth enamel and whole body doses are calculated for cases of internal irradiation by {sup 137}Cs and {sup 134}Cs isotopes incorporated in the human body resulted from staying in radioactive contaminated territory. It is shown that dose in enamel constitutes (40{+-}4)% and (59{+-}6)% of whole body dose resulted from the decay of {sup 137}Cs and {sup 134}Cs isotopes, respectively. The results of calculations may be used for conversion of absorbed dose in enamel obtained by the tooth enamel EPR spectroscopy method to whole body dose for dosimetric investigation of population of territories contaminated by the radioactive cesium, which is specific for the Chernobyl accident.

  14. Development of On-Line Direct Current Glow Discharge Source for Analysis of Isotope Ratio of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    <正>The present research is focused on the analysis of isotope ratio of the hydrogen by measuring an intensity ratio of hydrogen/deuterium/tritium fluxes. The direct current glow discharge tube may provide a

  15. Estimating the distribution of strontium isotope ratios (87Sr/86Sr) in the Precambrian of Finland

    OpenAIRE

    Lars Kaislaniemi

    2011-01-01

    A method to estimate the 87Sr/86Sr ratio of a rock based on its age and Rb/Sr ratio is presented. This method, together with data from the Rock Geochemical Database of Finland (n=6544) is used to estimate the 87Sr/86Sr ratios in the Precambrian of Finland and in its different major units. A generalization to cover the whole area of Finland is achieved by smoothing of estimation points. The estimation method is evaluated by comparing its results to published Rb-Sr isotope analyses (n=138) obta...

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

    Science.gov (United States)

    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

  17. Emerging Techniques in Vegetable Oil Analysis Using Stable Isotope Ratio Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Kelly, S. D.; Rhodes, C.

    2002-07-01

    As the practice of vegetable oil adulteration becomes more sophisticated, the possibility to subvert detection using established techniques such as capillary gas chromatography is increasing. One of the most powerful techniques to be used in food authenticity studies is stable isotope ratio mass spectrometry (SIRMS) which utilises differences in the natural abundance of the stable isotopes of the light bio elements hydrogen, nitrogen, carbon, oxygen and sulfur to detect food fraud. SIRMS has found application in the authentication of a wide range of foodstuffs, including fruit juices, wines, spirits, honey and to detect the adulteration of flavour compounds with synthetic analogues. This papers reviews the current state-of-the-art for the authentication of vegetable oils using SIRMS and highlights emergent techniques such as compound-an position specific-isotope mass spectrometry. These latter developments offer the potential to provide more rapid and improved detection of the economic adulteration of vegetable oils. (Author) 38 refs.

  18. Carbon Stable Isotope Analysis of Methylmercury Toxin in Biological Materials by Gas Chromatography Isotope Ratio Mass Spectrometry.

    Science.gov (United States)

    Masbou, Jeremy; Point, David; Guillou, Gaël; Sonke, Jeroen E; Lebreton, Benoit; Richard, Pierre

    2015-12-01

    A critical component of the biogeochemical cycle of mercury (Hg) is the transformation of inorganic Hg to neurotoxic monomethylmercury (CH3Hg). Humans are exposed to CH3Hg by consuming marine fish, yet the origin of CH3Hg in fish is a topic of debate. The carbon stable isotopic composition (δ(13)C) embedded in the methyl group of CH3Hg remains unexplored. This new isotopic information at the molecular level is thought to represent a new proxy to trace the carbon source at the origin of CH3Hg. Here, we present a compound-specific stable isotope analysis (CSIA) technique for the determination of the δ(13)C value of CH3Hg in biological samples by gas chromatography combustion isotope ratio mass spectrometry analysis (GC-C-IRMS). The method consists first of calibrating a CH3Hg standard solution for δ(13)C CSIA. This was achieved by comparing three independent approaches consisting of the derivatization and halogenation of the CH3Hg standard solution. The determination of δ(13)C(CH3Hg) values on natural biological samples was performed by combining a CH3Hg selective extraction, purification, and halogenation followed by GC-C-IRMS analysis. Reference δ(13)C values were established for a tuna fish certified material (ERM-CE464) originating from the Adriatic Sea (δ(13)C(CH3Hg) = -22.1 ± 1.5‰, ± 2 SD). This value is similar to the δ(13)C value of marine algal-derived particulate organic carbon (δ(13)CPOC = -21‰).

  19. The Effect of Aerosol Formation on Stable Isotopes Ratio in Titan's Atmosphere

    Science.gov (United States)

    Gautier, Thomas; Trainer, Melissa G.; Sebree, Joshua; Wold, Allison; Stern, Jennifer

    2016-10-01

    The formation of large amounts of aerosol in Titan atmosphere induces a significant sink for carbon and nitrogen in the atmosphere. Due to the high complexity of the chemistry leading to aerosol formation, there may be isotopic fractionation along the formation pathways of the aerosol. So far several stable isotopes have been measured in Titan atmosphere including the 13C/12C, 15N/14N and D/H ratios for different gaseous species. However, the fractionation effect of the aerosol formation and its impact on atmospheric stable isotope ratios has yet to be fully understood. Two experimental studies were recently published on the stable carbon [1] and nitrogen [1,2] isotope fractionation during aerosol formation in N2-CH4 reactant mixture. To better constrain the fractionation effect of aerosol formation on the Titan atmosphere we have measured the isotopic fractionation induced in laboratory aerosol analogues produced exploring the space of parameters that are expected to have an effect on fractionation processes. Parameters studied include pressure and temperature of aerosol formation and the reactant gas phase composition, including the standard "Titan" mixture of CH4/N2 as well as other trace species such as benzene (C6H6).[1] Sebree, J.A., Stern, J.C., Mandt, K.E., Domagal-Goldman, S.D., and Trainer, M.G.: C and N Fractionation of CH /N Mixtures during Photochemical Aerosol Formation: Relevance to Titan, (2016) Icarus 270:421-428[2] Kuga, M., Carrasco, N., Marty, B., Marrochi, Y., Bernard, S., Rigaudier, T., Fleury, B., Tissandier, L.: Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles, (2014) EPSL 393:2-13

  20. Boron abundances and isotopic ratios of olivine grains on Itokawa returned by the Hayabusa spacecraft

    Science.gov (United States)

    Fujiya, Wataru; Hoppe, Peter; Ott, Ulrich

    2016-09-01

    We report the B abundances and isotopic ratios of two olivine grains from the S-type asteroid Itokawa sampled by the Hayabusa spacecraft. Olivine grains from the Dar al Gani (DaG) 989 LL6 chondrite were used as a reference. Since we analyzed polished thin sections in both cases, we expect the contribution from the solar wind B (rich in 10B) to be minimal because the solar wind was implanted only within very thin layers of the grain surface. The Itokawa and DaG 989 olivine grains have homogeneous B abundances (~400 ppb) and 11B/10B ratios compatible with the terrestrial standard and bulk chondrites. The observed homogeneous B abundances and isotopic ratios of the Itokawa olivine grains are likely the result of thermal metamorphism which occurred in the parent asteroid of Itokawa, which had a similar composition as LL chondrites. The chondritic B isotopic ratios of the Itokawa samples suggest that they contain little cosmogenic B (from cosmic-ray spallation reactions) rich in 10B. This observation is consistent with the short cosmic-ray exposure ages of Itokawa samples inferred from the small concentrations of cosmogenic 21Ne. If other Itokawa samples have little cosmogenic B as well, the enrichment in 10B found previously on the surface of another Itokawa particle (as opposed to the bulk grain study here) may be attributed to implanted solar wind B.

  1. Forensic utility of carbon isotope ratio variations in PVC tape backings.

    Science.gov (United States)

    Dietz, Marianne E; Stern, Libby A; Mehltretter, Andria Hobbs; Parish, Ashley; McLasky, Velvet; Aranda, Roman

    2012-03-01

    Forensic interest in adhesive tapes with polyvinyl chloride (PVC) backings (electrical tape) derives from their use in a variety of illicit activities. Due to the range of physical characteristics, chemical compositions, and homogeneity within a single roll of tape, traditional microscopic and chemical analyses can offer a high degree of discrimination between tapes, permitting the assessment of potential associations between evidentiary tape samples. The carbon isotope ratios of tapes could provide additional discrimination among tape samples. To evaluate whether carbon isotope ratios may be able to increase discrimination of electrical tapes, particularly with regards to different rolls of tape of the same product, we assessed the δ(13)C values of backings from 87 rolls of PVC-based black electrical tape (~20 brands, >60 products) Prior to analysis, adhesives were removed to prevent contamination by adhering debris, and plasticizers were extracted because of concern over their potential mobility. This result is consistent with each of these tapes having approximately the same plasticizer δ(13)C value and proportion of carbon in these plasticizers. The δ(13)C values of the 87 PVC tape backings ranged between -23.5 and -41.3 (‰, V-PDB), with negligible carbon isotopic variation within single rolls of tape, yet large variations among tape brands and tape products. Within this tape population, carbon isotope ratios permitted an average exclusion power of 93.7%, using a window of +/-0.3‰; the combination of carbon isotope ratio measurement with additional chemical and physical analyses raises the discrimination power to over 98.9%, with only 41 out of a possible 3741 pairs of tape samples being indistinguishable. There was a linear relationship between the δ(13)C value of tape backings and the change in δ(13)C value with the extraction of plasticizers. Analyses of pre- and post-blast tape sample pairs show that carbon isotope signatures are within 0.3‰ of

  2. S Isotope Ratios of Central Italy Waters to Assess Their Origin

    Science.gov (United States)

    Castorina, Francesca; Masi, Umberto

    2010-05-01

    Sr isotopes have so far applied only occasionally to the study of the waters from central Italy. Therefore, we have analyzed more than 30 water samples from thermal and cold springs, and from the lakes located in the Quaternary K-alkaline volcanic districts of Latium, aimed at providing significant information on the sources of Sr and the hydrologic circulation. The 87Sr/86Sr composition of the waters shows a general correlation with the aquifer rocks, resulting in the waters from older carbonatic rocks having a less radiogenic signature than those from younger K-alkaline volcanic rocks. The Sr-isotope ratios of most thermal waters range narrowly by 0.708, indicating a common source of Sr, likely represented by the Upper Triassic Burano Anhydrites, i.e. the lowermost permeable formation in the study area. Moreover, the positive correlation between Sr and Ca suggests that bulk Ca was also supplied from that source. A minor number of thermal waters as well as all the waters from the lakes and cold springs display a larger Sr isotopic range (0.7085-0.7115), suggesting a relative large spectrum of sources for Sr. In particular, some waters derive their Sr from a singular source, but the most show isotopic signatures suggestive of mixed contributions from different aquifers. As a whole, the results from this study confirm that Sr isotopes are a useful tool contributing to explain the geochemical characteristics of surficial and groundwaters.

  3. Analysis of hydrogen isotope ratios by SIMS, and application to determining mineral-fluid isotope fractionation factors

    Energy Technology Data Exchange (ETDEWEB)

    Riciputi, L.R.; Chacko, T.; Cole, D.R.; Horita, J.

    1997-09-01

    Due to the large mass difference between the two isotopes, D/H ratios can be strongly affected by chemical processes. Thus, they can be sensitive monitors of fluid source, temperature, and fluid-rock interactions in geologic settings. The lack of confidence in fractionation factors has significantly hindered realization of the potential of D/H ratios in geochemical studies. The authors describe a new experimental method, relying on SIMS analysis, that allows the precise determination of mineral-water D/H fractionation factors, and the analytical considerations that are required to make both precise and accurate measurements. The development of this method is based on the fact that diffusion rates are markedly anisotropic in many hydrous minerals, varying by over five orders of magnitude depending on the crystallographic orientation. The diffusion rates can be determined by conducting controlled exchange experiments of fixed duration using isotopically labeled waters that are enriched (strongly) with D, and then measuring the depth profile by SIMS.

  4. Flow injection analysis-isotope ratio mass spectrometry for bulk carbon stable isotope analysis of alcoholic beverages.

    Science.gov (United States)

    Jochmann, Maik A; Steinmann, Dirk; Stephan, Manuel; Schmidt, Torsten C

    2009-11-25

    A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration.

  5. Maintaining high precision of isotope ratio analysis over extended periods of time.

    Science.gov (United States)

    Brand, Willi A

    2009-06-01

    Stable isotope ratios are reliable and long lasting process tracers. In order to compare data from different locations or different sampling times at a high level of precision, a measurement strategy must include reliable traceability to an international stable isotope scale via a reference material (RM). Since these international RMs are available in low quantities only, we have developed our own analysis schemes involving laboratory working RM. In addition, quality assurance RMs are used to control the long-term performance of the delta-value assignments. The analysis schemes allow the construction of quality assurance performance charts over years of operation. In this contribution, the performance of three typical techniques established in IsoLab at the MPI-BGC in Jena is discussed. The techniques are (1) isotope ratio mass spectrometry with an elemental analyser for delta(15)N and delta(13)C analysis of bulk (organic) material, (2) high precision delta(13)C and delta(18)O analysis of CO(2) in clean-air samples, and (3) stable isotope analysis of water samples using a high-temperature reaction with carbon. In addition, reference strategies on a laser ablation system for high spatial resolution delta(13)C analysis in tree rings is exemplified briefly.

  6. Technical Note: Calcium and carbon stable isotope ratios as paleodietary indicators.

    Science.gov (United States)

    Melin, Amanda D; Crowley, Brooke E; Brown, Shaun T; Wheatley, Patrick V; Moritz, Gillian L; Yit Yu, Fred Tuh; Bernard, Henry; DePaolo, Donald J; Jacobson, Andrew D; Dominy, Nathaniel J

    2014-08-01

    Calcium stable isotope ratios are hypothesized to vary as a function of trophic level. This premise raises the possibility of using calcium stable isotope ratios to study the dietary behaviors of fossil taxa and to test competing hypotheses on the adaptive origins of euprimates. To explore this concept, we measured the stable isotope composition of contemporary mammals in northern Borneo and northwestern Costa Rica, two communities with functional or phylogenetic relevance to primate origins. We found that bone collagen δ(13) C and δ(15) N values could differentiate trophic levels in each assemblage, a result that justifies the use of these systems to test the predicted inverse relationship between bioapatite δ(13) C and δ(44) Ca values. As expected, taxonomic carnivores (felids) showed a combination of high δ(13) C and low δ(44) Ca values; however, the δ(44) Ca values of other faunivores were indistinguishable from those of primary consumers. We suggest that the trophic insensitivity of most bioapatite δ(44) Ca values is attributable to the negligible calcium content of arthropod prey. Although the present results are inconclusive, the tandem analysis of δ(44) Ca and δ(13) C values in fossils continues to hold promise for informing paleodietary studies and we highlight this potential by drawing attention to the stable isotope composition of the Early Eocene primate Cantius.

  7. Ultratrace and isotope ratios analyses of some radionuclides by ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Helal, A.I.; Zahran, N.F.; Abd El-Lateef, A.M.; Mohsen, H.T. [Central Lab. for Elemental and Isotopic Analysis, N.R.C. Atomic Energy Authority, Cairo (Egypt); Amr, M.A. [Central Lab. for Elemental and Isotopic Analysis, N.R.C. Atomic Energy Authority, Cairo (Egypt); Nuclear Physics Dept., N.R.C., Atomic Energy Authority, Cairo (Egypt); Bashter, I.I. [Physics Dept., Faculty of Science, Zagazig Univ. (Egypt); Abbas, Y. [Physics Dept., Faculty of Science, Suez Canal Univ., Ismailia (Egypt)

    2004-07-01

    Extensive work is under way using high resolution-ICP-MS for {sup 90}Sr, {sup 234}U, {sup 235}U, {sup 238}U, {sup 239}Pu, {sup 240}Pu, and {sup 241}Am detection. Sample preparation procedures based on liquid-liquid extraction and ion exchange chromatography were developed. Sr, U, Pu, and Am were separated from their matrix and concentrated to improve the power of detection in the mass spectrometer. A microconcentric nebulizer with a desolvation introduction system (Ardius) is used. Instrumental limits of detection using Sr and U standard solutions are 0.01 ppt and 0.006 ppt for Sr and U, respectively. A study is presented on the mass interferences for the specified radionuclides. In the environmental samples investigated the {sup 90}Sr/{sup 86}Sr isotope ratio is 6.02 x 10{sup -9} and for {sup 240}Pu/{sup 239}Pu the isotope ratio is 0.17. (orig.)

  8. Late Miocene evolution of the Black Sea: insights from palynology and strontium isotope ratios

    Science.gov (United States)

    Grothe, Arjen; van Baak, Christiaan; Vasiliev, Iuliana; Sangiorgi, Francesca; Reichart, Gert-Jan; Stoica, Marius; Krijgsman, Wout

    2016-04-01

    During the late Miocene, the connection(s) between the Mediterranean Basin and the Atlantic Ocean deteriorated, which ultimately culminated in thick evaporite deposits and a water level drop in the Mediterranean Basin during the so-called Messinian Salinity Crisis (MSC, 5.97 - 5.33 Ma). It has been claimed that Black Sea, in response to the MSC, also desiccated but these claims have been proven incorrectly. Here we present palynological (dinoflagellate cysts and pollen) and strontium isotope ratios from two Black Sea records: the Zheleznyi Rog outcrop section and Deep Sea Drilling Project Hole 380A. Organic walled cyst-producing dinoflagellates are highly sensitive to even small changes in surface waters and strontium isotope ratios are excellent recorders of changing connectivity. Our records provide therefore more insights in the sensitivity of the Black Sea to Messinian Salinity Crisis and the general evolution of the late Miocene Black Sea.

  9. Determination of tin isotope ratios in cassiterite by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    Science.gov (United States)

    Schulze, Marie; Ziegerick, Marco; Horn, Ingo; Weyer, Stefan; Vogt, Carla

    2017-04-01

    In comparison to isotope analysis of dissolved samples femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS) enables precise isotope ratio analyses consuming much less sample material and with a minimum effort in sample preparation. This is especially important for the investigation of valuable historical objects for which visual traces of sampling are unwanted. The present study provides a basis for tin isotope ratio measurements using LA-MC-ICP-MS technique. For this, in house isotope standards had to be defined. Investigations on interferences and matrix effects illustrate that beside Sb only high Te contents (with values above those to be expected in cassiterite) result in a significant shift of the measured tin isotope ratios. This effect can partly be corrected for using natural isotope abundances. However, a natural isotope fractionation of Te cannot be excluded. Tin beads reduced from cassiterite were analysed by laser ablation and after dissolution. It was shown that tin isotope ratios can be determined accurately by using fs-LA-MC-ICP-MS. Furthermore the homogeneity of tin isotope ratios in cassiterite was proven.

  10. On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion–isotope ratio mass spectrometry

    NARCIS (Netherlands)

    Schmitt, J.; Seth, B.; Bock, M; van der Veen, C.; Möller, L.; Sapart, C.J.; Prokopiou, M.; Sowers, T.; Röckmann, T.; Fischer, H

    2013-01-01

    Stable carbon isotope analysis of methane ( 13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentra

  11. Decorporation of cesium-137; Decorporation du cesium-137

    Energy Technology Data Exchange (ETDEWEB)

    Le Fleche, Ph.; Destombe, C.; Grasseau, A.; Mathieu, J.; Chancerelle, Y.; Mestries, J.C. [GMR, Direction des Recherches, Etudes et Techniques, 94 - Arcueil (France)

    1997-12-31

    Cesium radio-isotopes, especially cesium-137 ({sup 137}Cs) are among the radionuclides of main importance produced by a fission reaction in reactor or a nuclear weapon explosion. In the environment, {sup 137}Cs is a major contaminant which can cause severe {beta}, {gamma}irradiations and contaminations. {sup 137}Cs is distributed widely and relatively uniformly throughout the body with the highest concentration in skeletal muscles. A treatment becomes difficult afterwards. The purposes of this report are Firstly to compare the Prussian blue verses cobalt and potassium ferrocyanide (D.I. blue) efficiency for the {sup 137}Cs decorporation and secondly to assess a chronological treatment with D.I. blue. (author)

  12. Assessment of Non-Traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities

    Science.gov (United States)

    2016-03-01

    Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities Distribution Statement A. Approved for pubic...12. DISTRIBUTION / AVAILABILITY STATEMENT 13. SUPPLEMENTARY NOTES 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF...Fahrenheit ( o F) [T( o F) + 459.67]/1.8 kelvin (K) Radiation curie (Ci) [ activity of radionuclides] 3.7 × 10 10 per second (s –1 ) [becquerel (Bq

  13. Methodological Study on AMS Measurement of Ultra-trace Pu Isotope Ratios at CIAE

    Institute of Scientific and Technical Information of China (English)

    DONG; Ke-jun; ZHAO; Qing-zhang; WANG; Chen; HE; Ming; JIANG; Shan; ZHANG; Hui; PANG; Yi-jun; SHEN; Hong-tao; WANG; Xiao-ming; XU; Yong-ning; WU; Shao-yong; YANG; Xu-ran; WANG; Xiang-gao

    2015-01-01

    The determination of ultra-trace plutonium is very important in different fields.A new measurement method of plutonium isotopic ratios with accelerator mass spectrometry(AMS)was developed at China Institute of Atomic Energy(CIAE).Two laboratory reference standards of 239Pu/240 Pu(ST1)and 239Pu/242 Pu(ST2)are17.241and 10.059,a flow blank,a commercial blank and three real samples were respectively

  14. Method for determination of stable carbon isotope ratio of methylnitrophenols in atmospheric particulate matter

    Directory of Open Access Journals (Sweden)

    S. Moukhtar

    2011-11-01

    Full Text Available A technique for the measurement of the stable isotope ratio of methylnitrophenols in atmospheric particulate matter is presented. Atmospheric samples from rural and suburban areas were collected for evaluation of the procedure. Particulate matter was collected on quartz fibre filters using dichotomous high volume air samplers. Methylnitrophenols were extracted from the filters using acetonitrile. The sample was then purified using a combination of high-performance liquid chromatography and solid phase extraction. The final solution was then divided into two aliquots. To one aliquot, a derivatising agent, Bis(trimethylsilyltrifluoroacetamide, was added for Gas Chromatography-Mass Spectrometry analysis. The second half of the sample was stored in a refrigerator. For samples with concentrations exceeding 1 ng μl−1, the second half of the sample was used for measurement of stable carbon isotope ratios by Gas Chromatography-Isotope Ratio Mass Spectrometry.

    The procedure described in this paper provides a method for the analysis of methylnitrophenols in atmospheric particulate matter at concentrations as low as 0.3 pg m−3 and for stable isotope ratios with an accuracy of better than ±0.5‰ for concentrations exceeding 100 pg m−3.

    In all atmospheric particulate matter samples analysed, 2-methyl-4-nitrophenol was found to be the most abundant methylnitrophenol, with concentrations ranging from the low pg m−3 range in rural areas to more than 200 pg m−3 in some samples from a suburban location.

  15. Traceability of synthetic drugs by position-specific deuterium isotope ratio analysis

    Energy Technology Data Exchange (ETDEWEB)

    Brenna, Elisabetta [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: elisabetta.brenna@polimi.it; Fronza, Giovanni [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Instituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)], E-mail: giovanni.fronza@polimi.it; Fuganti, Claudio [Dipartimento di Chimica, Materiali e di Ingegneria Chimica del Politecnico di Milano (Italy) and Istituto CNR per la Chimica del Riconoscimento Molecolare, Via Mancinelli 7, Milan I-20131 (Italy)

    2007-10-10

    Samples of fluoxetine of different origin were submitted to natural abundance {sup 2}H NMR spectroscopy. The deuterium content at the various sites of the molecule was found to depend on its synthetic history. Hints on the synthetic procedure can be obtained by comparison with standard compounds, whose synthesis is known. These preliminary results give an idea of the potential of site-specific isotope ratio analysis in the fight against patent infringement and drug counterfeiting.

  16. Carbon isotope ratio (delta13C) values of urinary steroids for doping control in sport.

    Science.gov (United States)

    Cawley, Adam T; Trout, Graham J; Kazlauskas, Rymantas; Howe, Christopher J; George, Adrian V

    2009-03-01

    The detection of steroids originating from synthetic precursors in relation to their chemically identical natural analogues has proven to be a significant challenge for doping control laboratories accredited by the World Anti-Doping Agency (WADA). Endogenous steroid abuse may be confirmed by utilising the atomic specificity of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) that enables the precise measurement of differences in stable isotope ratios that arise as a result of fractionation patterns inherent in the source of steroids. A comprehensive carbon isotope ratio (delta(13)C) profiling study (n=1262) of urinary ketosteroids is reported that demonstrates the inter-individual variation that can be expected from factors such as diet, ethnicity, gender and age within and between different populations (13 countries). This delta(13)C distribution is shown by principal component analysis (PCA) to provide a statistical comparison to delta(13)C values observed following administration of testosterone enanthate. A limited collection of steroid diol data (n=100; consisting of three countries) is also presented with comparison to delta(13)C values of excreted testosterone to validate criteria for WADA accredited laboratories to prove doping offences.

  17. DoE optimization of a mercury isotope ratio determination method for environmental studies.

    Science.gov (United States)

    Berni, Alex; Baschieri, Carlo; Covelli, Stefano; Emili, Andrea; Marchetti, Andrea; Manzini, Daniela; Berto, Daniela; Rampazzo, Federico

    2016-05-15

    By using the experimental design (DoE) technique, we optimized an analytical method for the determination of mercury isotope ratios by means of cold-vapor multicollector ICP-MS (CV-MC-ICP-MS) to provide absolute Hg isotopic ratio measurements with a suitable internal precision. By running 32 experiments, the influence of mercury and thallium internal standard concentrations, total measuring time and sample flow rate was evaluated. Method was optimized varying Hg concentration between 2 and 20 ng g(-1). The model finds out some correlations within the parameters affect the measurements precision and predicts suitable sample measurement precisions for Hg concentrations from 5 ng g(-1) Hg upwards. The method was successfully applied to samples of Manila clams (Ruditapes philippinarum) coming from the Marano and Grado lagoon (NE Italy), a coastal environment affected by long term mercury contamination mainly due to mining activity. Results show different extents of both mass dependent fractionation (MDF) and mass independent fractionation (MIF) phenomena in clams according to their size and sampling sites in the lagoon. The method is fit for determinations on real samples, allowing for the use of Hg isotopic ratios to study mercury biogeochemical cycles in complex ecosystems.

  18. Mg isotope ratios in giant stars of the globular clusters M 13 and M 71

    CERN Document Server

    Yong, D; Lambert, D L; Yong, David; Aoki, Wako; Lambert, David L.

    2006-01-01

    We present Mg isotope ratios in 4 red giants of the globular cluster M 13 and 1 red giant of the globular cluster M 71 based on spectra obtained with HDS on the Subaru Telescope. We confirm earlier results by Shetrone that for M 13, the ratio varies from (25+26)Mg/24Mg = 1 in stars with the highest Al abundance to (25+26)Mg/24Mg = 0.2 in stars with the lowest Al abundance. However, we separate the contributions of all three isotopes and find a spread in the ratio 24Mg:25Mg:26Mg with values ranging from 48:13:39 to 78:11:11. As in NGC 6752, we find a positive correlation between 26Mg and Al, an anticorrelation between 24Mg and Al, and no correlation between 25Mg and Al. In M 71, our one star has a ratio 70:13:17. For both clusters, the lowest ratios of 25Mg/24Mg and 26Mg/24Mg exceed those observed in field stars at the same metallicity, a result also found in NGC 6752. The contribution of 25Mg to the total Mg abundance is constant within a given cluster and between clusters with 25Mg/(24+25+26)Mg = 0.13. For M...

  19. Tunable Diode Laser Measurements of Leaf-scale Carbon Isotope Discrimination and Ecosystem Respired Carbon and Oxygen Isotope Ratios in a Semi-arid Woodland

    Science.gov (United States)

    McDowell, N.; Chris, B.; Hanson, D.; Kern, S.; Meyer, C.; Pockman, W.; Powers, H.

    2005-12-01

    We present results and speculative interpretation of leaf-level carbon isotope discrimination and ecosystem respired carbon and oxygen isotope ratios from a semi-arid, C3/C4 woodland located in northern New Mexico, USA. Overstory leaf area index (LAI) is dominated by live juniper (Juniperus monosperma) trees with an LAI value of approximately 1.0 m2 per m2 ground area, and has a seasonally dynamic understory of mixed C3 forbs and C4 grasses and cacti, with a maximum LAI of 0.30 m2 per m2 ground area. Ecosystem respired carbon isotope ratios showed values characteristic of C3 dominated photosynthesis (Keeling plot intercepts of -35 to -22 per mil). Seasonal variation was typical of that found in wetter, C3 dominated forests, as was the dependence on climate (e.g. relationships with vapor pressure deficit, soil water content, and canopy conductance). Leaf-level carbon isotope discrimination of the junipers, measured by coupling a Li-Cor 6400 photosynthesis system to the TDL, provided discrimination-Ci and discrimination-vpd relationships consistent with measured ecosystem respired carbon isotope ratios. The oxygen isotope ratio of ecosystem respiration was dependent on rain water isotope composition, but was correlated with soil water content during rain-free periods. The cumulative effect of vapor pressure deficit after a rain event was tightly correlated with the oxygen isotope ratio of ecosystem respiration, suggesting the primary drivers are evaporative enrichment of soil water and perhaps nocturnal leaf enrichment. Instrument precision for carbon and oxygen isotope ratios of carbon dioxide is 0.06 to 0.18 per mil; however, overall precision is somewhat lower due to pressure and sampling effects.

  20. Environmental and biosynthetic influences on carbon and hydrogen isotope ratios of leaf wax n-alkanes

    Science.gov (United States)

    McInerney, F. A.; Freeman, K. H.; Polissar, P. J.; Feakins, S. J.

    2013-12-01

    Both carbon and hydrogen isotope ratios of leaf-wax n-alkanes are influenced by the availability of water in a plant's growth environment. Carbon isotope ratios of bulk tissues in C3 plants demonstrate a strong inverse relationship with measures of available moisture (e.g. mean annual precipitation and precipitation/evaporation). Similarly, hydrogen isotope ratios of leaf wax n-alkanes (δDl) can be enriched relative to precipitation (δDw) by transpiration, which is related to relative humidity and the leaf-to-air vapor pressure deficit. Thus, D-enrichment of leaf-wax n-alkanes relative to precipitation, termed the apparent fractionation (2ɛl/w), becomes more positive with increasing aridity. In theory, more positive values of leaf-wax δ13C (δ13Cl) and 2ɛl/w of leaf-wax n-alkanes should both correspond to more arid conditions in C3 plants. Here we review published and unpublished data on over 100 plants to examine this relationship. Contrary to expectations, C3 dicots show no clear relationship between δ13Cl and 2ɛl/w. This global lack of correlation is surprising given our understanding of aridity related isotopic effects in C3 plants. One possibility is that the implicit assumption of constant fractionation between lipid and bulk tissue is flawed due to the effects of different biosynthetic carriers and reaction pathways. We explore this possibility by examining the offset of leaf-wax carbon isotopes from the bulk leaf tissue (13ɛl/bulk). Different offsets would indicate additional biosynthetic processes are affecting δ13Cl in addition to any direct effects from aridity. We find that 13ɛl/bulk is highly variable, ranging from -1 to -16‰, which could explain the lack of correlation between δ13Cl and 2ɛl/w. In addition, 13ɛl/bulk values for C3 and C4 monocots (averages of -10.6 and -11.4‰ respectively) represent significantly greater offset between leaf wax and bulk tissue than in C3 dicots (average of -4.3‰), which is consistent with previous

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

    Science.gov (United States)

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

    2016-08-01

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

  2. Zn/Cd ratios and cadmium isotope evidence for the classification of lead-zinc deposits.

    Science.gov (United States)

    Wen, Hanjie; Zhu, Chuanwei; Zhang, Yuxu; Cloquet, Christophe; Fan, Haifeng; Fu, Shaohong

    2016-04-28

    Lead-zinc deposits are often difficult to classify because clear criteria are lacking. In recent years, new tools, such as Cd and Zn isotopes, have been used to better understand the ore-formation processes and to classify Pb-Zn deposits. Herein, we investigate Cd concentrations, Cd isotope systematics and Zn/Cd ratios in sphalerite from nine Pb-Zn deposits divided into high-temperature systems (e.g., porphyry), low-temperature systems (e.g., Mississippi Valley type [MVT]) and exhalative systems (e.g., sedimentary exhalative [SEDEX]). Our results showed little evidence of fractionation in the high-temperature systems. In the low-temperature systems, Cd concentrations were the highest, but were also highly variable, a result consistent with the higher fractionation of Cd at low temperatures. The δ(114/110)Cd values in low-temperature systems were enriched in heavier isotopes (mean of 0.32 ± 0.31‰). Exhalative systems had the lowest Cd concentrations, with a mean δ(114/110)Cd value of 0.12 ± 0.50‰. We thus conclude that different ore-formation systems result in different characteristic Cd concentrations and fraction levels and that low-temperature processes lead to the most significant fractionation of Cd. Therefore, Cd distribution and isotopic studies can support better understanding of the geochemistry of ore-formation processes and the classification of Pb-Zn deposits.

  3. An analytical approach to Sr isotope ratio determination in Lambrusco wines for geographical traceability purposes.

    Science.gov (United States)

    Durante, Caterina; Baschieri, Carlo; Bertacchini, Lucia; Bertelli, Davide; Cocchi, Marina; Marchetti, Andrea; Manzini, Daniela; Papotti, Giulia; Sighinolfi, Simona

    2015-04-15

    Geographical origin and authenticity of food are topics of interest for both consumers and producers. Among the different indicators used for traceability studies, (87)Sr/(86)Sr isotopic ratio has provided excellent results. In this study, two analytical approaches for wine sample pre-treatment, microwave and low temperature mineralisation, were investigated to develop accurate and precise analytical method for (87)Sr/(86)Sr determination. The two procedures led to comparable results (paired t-test, with twine sample), processed during each sample batch (calculated Relative Standard Deviation, RSD%, equal to 0.002%. Lambrusco PDO (Protected Designation of Origin) wines coming from four different vintages (2009, 2010, 2011 and 2012) were pre-treated according to the best procedure and their isotopic values were compared with isotopic data coming from (i) soils of their territory of origin and (ii) wines obtained by same grape varieties cultivated in different districts. The obtained results have shown no significant variability among the different vintages of wines and a perfect agreement between the isotopic range of the soils and wines has been observed. Nevertheless, the investigated indicator was not enough powerful to discriminate between similar products. To this regard, it is worth to note that more soil samples as well as wines coming from different districts will be considered to obtain more trustworthy results.

  4. Identifying the Presence of AMD-Derived Soil CO2 in Field Investigations Using Isotope Ratios

    Directory of Open Access Journals (Sweden)

    Kwame Awuah-Offei

    2016-03-01

    Full Text Available Recent incidents of hazardous accumulations of CO2 in homes on or adjacent to reclaimed mine land have been shown to be linked to neutralization reactions between acidic mine drainage and carbonate material. An efficient and economic method is necessary to identify the presence of acid mine drainage- (AMD- derived CO2 on reclaimed mine land, prior to construction. One approach to identify the presence of AMD-derived CO2 is to characterize stable carbon isotope ratios of soil CO2. To do so, a viable method is necessary to acquire soil gas samples for isotope ratio analysis. This paper presents preliminary investigations of the effectiveness of two methods of acquiring gas samples (sampling during soil flux measurements and using slam bar for isotope analysis. The results indicate that direct soil gas sampling is cheaper and provides better results. Neither method is adequate without accounting for temporal effects due to changing gas transport mechanisms. These results have significant implications for safe post-mining land uses and future investigations of leakages from geologic carbon sequestration sites.

  5. Development and Airborne Operation of a Compact Water Isotope Ratio Infrared Spectrometer

    Science.gov (United States)

    Iannone, Rosario Q.; Kassi, Samir; Jost, Hans-Juerg; Chenevier, Marc; Romanini, Daniele; Meijer, Harro A. J.; Dhaniyala, Suresh; Snels, Marcel; Kerstel, Erik R. T.

    2009-01-01

    A sensitive laser spectrometer, named IRIS (water isotope ratio infrared spectrometer), was developed for the in situ detection of the isotopic composition of water vapour in the upper troposphere and the lower stratosphere. Isotope ratio measurements can be used to quantify troposphere stratosphere exchange, and to study the water chemistry in the stratosphere. IRIS is based on the technique of optical feedback cavity-enhanced absorption spectroscopy. It uses a room temperature near-infrared laser, and does not require cryogenic cooling of laser or detectors. The instrument weighs 51 kg including its support structure. Airborne operation was demonstrated during three flights aboard the European M55-Geophysica stratospheric research aircraft, as part of the AMMA/SCOUT-03 (African Monsoon Multidisciplinary Analysis/Stratospheric Climate links with emphasis on the Upper Troposphere and lower stratosphere) campaign in Burkina Faso in August 2006. The data are discussed with reference to a Rayleigh distillation model. As expected, there is no indication of non-mass-dependent fractionation (also known as mass-independent fractionation) in the troposphere. Furthermore, improvements to the thermal management system and a move to a (cryogen-free) longer-wavelength laser source are discussed, which together should result in approximately two orders of magnitude improvement of the sensitivity

  6. Isotopic 32S/33S ratio as a diagnostic of presolar grains from novae

    Directory of Open Access Journals (Sweden)

    A. Parikh

    2014-10-01

    Full Text Available Measurements of sulphur isotopes in presolar grains can help to identify the astrophysical sites in which these grains were formed. A more precise thermonuclear rate of the 33S(p,γ34Cl reaction is required, however, to assess the diagnostic ability of sulphur isotopic ratios. We have studied the 33S(3He,d34Cl proton-transfer reaction at 25 MeV using a high-resolution quadrupole–dipole–dipole–dipole magnetic spectrograph. Deuteron spectra were measured at ten scattering angles between 10° and 55°. Twenty-four levels in 34Cl over Ex=4.6–5.9 MeV were observed, including three levels for the first time. Proton spectroscopic factors were extracted for the first time for levels above the 33S + p threshold, spanning the energy range required for calculations of the thermonuclear 33S(p,γ34Cl rate in classical nova explosions. We have determined a new 33S(p,γ34Cl rate using a Monte Carlo method and have performed new hydrodynamic nova simulations to determine the impact on nova nucleosynthesis of remaining nuclear physics uncertainties in the reaction rate. We find that these uncertainties lead to a factor of ≤5 variation in the 33S(p,γ34Cl rate over typical nova peak temperatures, and variation in the ejected nova yields of SCa isotopes by ≤20%. In particular, the predicted 32S/33S ratio is 110–130 for the nova model considered, compared to 110–440 with previous rate uncertainties. As recent type II supernova models predict ratios of 130–200, the 32S/33S ratio may be used to distinguish between grains of nova and supernova origin.

  7. Identification of Marchfeld asparagus using Sr isotope ratio measurements by MC-ICP-MS

    Energy Technology Data Exchange (ETDEWEB)

    Swoboda, S.; Brunner, M.; Boulyga, S.F.; Galler, P.; Prohaska, T. [University of Natural Resources and Applied Life Sciences, Department of Chemistry-VIRIS Project, Vienna (Austria); Horacek, M. [Austrian Research Centers GmbH, Seibersdorf (Austria)

    2008-01-15

    This work focuses on testing and application of Sr isotope signatures for the fast and reliable authentication and traceability of Asparagus officinalis originating from Marchfeld, Austria, using multicollector inductively coupled plasma mass spectrometry after optimised Rb/Sr separation. The major sample pool comprises freeze-dried and microwave-digested asparagus samples from Hungary and Slovakia which are compared with Austrian asparagus originating from the Marchfeld region, which is a protected geographical indication. Additional samples from Peru, the Netherlands and Germany were limited in number and allowed therefore only restricted statistical evaluation. Asparagus samples from Marchfeld were harvested within two subsequent years in order to investigate the annual variation. The results show that the Sr isotope ratio is consistent within these 2 years of investigation. Moreover, the Sr isotope ratio of total Sr in soil was found to be significantly higher than in an NH{sub 4}NO{sub 3} extract, reflecting the mobile (bioavailable) phase. The isotope composition in the latter extract corresponds well to the range found in the asparagus samples in Marchfeld, even though the concentration of Sr in asparagus shows no direct correlation to the concentration of Sr in the mobile phase of the soil. The major question was whether the 'Marchfelder Spargel' can be distinguished from samples from the neighbouring countries of Hungary and Slovakia. According to our findings, they can be clearly (100%) singled out from the Hungarian samples and can be distinguished from the Slovakian asparagus samples with a probability of more than 80%. (orig.)

  8. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere

    NARCIS (Netherlands)

    Webster, C.R.; Mahaffy, P.R.; Flesch, G.J.; Niles, P.B.; Jones, J.H.; Leshin, L.A.; Atreya, S.K.; Stern, J.C.; Christensen, L.E.; Owen, T.; Franz, H.; Pepin, R.O.; Steele, A.; MSL Science Team, the

    2013-01-01

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ra

  9. Stable carbon isotope ratios of intact GDGTs indicate heterogeneous sources to marine sediments

    Science.gov (United States)

    Pearson, Ann; Hurley, Sarah J.; Walter, Sunita R. Shah; Kusch, Stephanie; Lichtin, Samantha; Zhang, Yi Ge

    2016-05-01

    Thaumarchaeota, the major sources of marine glycerol dibiphytanyl glycerol tetraether lipids (GDGTs), are believed to fix the majority of their carbon directly from dissolved inorganic carbon (DIC). The δ13C values of GDGTs (δ13CGDGT) may be powerful tools for reconstructing variations in the ocean carbon cycle, including paleoproductivity and water mass circulation, if they can be related to values of δ13CDIC. To date, isotope measurements primarily are made on the C40 biphytane skeletons of GDGTs, rather than on complete tetraether structures. This approach erases information revealed by the isotopic heterogeneity of GDGTs within a sample and may impart an isotopic fractionation associated with the ether cleavage. To circumvent these issues, we present δ13C values for GDGTs from twelve recent sediments representing ten continental margin locations. Samples are purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values by Spooling Wire Microcombustion (SWiM)-isotope ratio mass spectrometry (IRMS) with 1σ precision and accuracy of ±0.25‰. Using this approach, we confirm that GDGTs, generally around -19‰, are isotopically "heavy" compared to other marine lipids. However, measured δ13CGDGT values are inconsistent with predicted values based on the 13C content of DIC in the overlying water column and the previously-published biosynthetic isotope fractionation for a pure culture of an autotrophic marine thaumarchaeon. In some sediments, the isotopic composition of individual GDGTs differs, indicating multiple source inputs. The data appear to confirm that crenarchaeol primarily is a biomarker for Thaumarchaeota, but its δ13C values still cannot be explained solely by autotrophic carbon fixation. Overall the complexity of the results suggests that both organic carbon assimilation (ca. 25% of total carbon) and multiple source(s) of exogenous GDGTs (contributing generally <30% of input to sediments) are necessary to explain the observed

  10. He and Ne isotopic ratios along the Terceira Rift: implications for the Azores mantle source

    Science.gov (United States)

    Madureira, P.; Moreira, M. A.; Nunes, J.; Lourenco, N.; Carvalho, M.; Mata, J.; Pinto de Abreu, M.

    2010-12-01

    Noble gas data (He and Ne) on olivine phenocrysts obtained from Azores’ lavas sampled along the Terceira Rift will be presented in this work. The Terceira Rift is considered as one of the slowest spreading system in the world (Vogt & Jung, 2004). Lava samples were collected inland at S. Miguel, Terceira, Graciosa, Pico and Faial Islands as well at sea at D. João de Castro Bank and south Hirondelle basin, the latter being sampled by the ROV cruises in 2008 and 2009. Noble gas data were analyzed in the Noblesse mass spectrometer housed at the IPGP. The most primitive He isotopic ratios were obtained from Pico, Terceira and Hirondelle olivines. Most Ne isotopic ratios are similar to the present-day atmosphere, but distinct 20Ne/22Ne ratios were found for the majority of submarine samples and also Pico and Faial Islands, defining mixing lines with the atmospheric end-member with slopes greater than that defined from MORB lavas. The He-Ne systematics shows that most of the new noble gas data fit in a mixing model between a dominant MORB-type mantle source and a relatively primitive mantle source related with the regional Azores component. However, data from the D. João de Castro Bank argue for the presence of a radiogenic He end-member distinct from MORB. References: Vogt, P. & Jung W. (2004). Earth Planet. Sci. Lett., 218: 77 90.

  11. Investigation of two technical toxaphene products by using isotope ratio mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Vetter, W.; Armbruster, W. [Hohenheim Univ., Stuttgart (Germany). Inst. fuer Lebensmittelchemie; Gleixner, G. [Max-Planck-Institut fuer Biogeochemie, Jena (Germany)

    2004-09-15

    Organochlorine compounds have been used in high quantities throughout the past 60 years. Being long-lived in the environment and toxic to humans and wildlife, some of them were classified as persistent organic pollutants (POPs). One of the POPs of special concern is toxaphene which is produced by the chlorination of the natural product camphene (or {alpha}-pinene). The technical products consist of several hundred compounds, mainly of chlorobornanes with an average number of eight chlorine substituents. Toxaphene has been produced in high quantities in different parts of the world. Even though the use has been discontinued during the last two decades, there are still several ecosystems which are heavily contaminated with this chloropesticide. Due to the huge variety of the technical products accompanied with a severe change of composition in the environment, analytical tracing back of toxaphene residues to a specific product has not yet been achieved. One of the potential analytical tools for distinguishing substances that differ only in their way of production is the determination of ratios of stable isotopes ({sup 13}C/{sup 12}C; {sup 2}H/{sup 1}H; {sup 15}N/{sup 14}N). Since the synthesis of toxaphene is starting from natural compounds obtained from different continents, the technical products could have different ratios of stable isotopes. In this study, we investigated the {sup 13}C/{sup 12}C ratio of two former major toxaphene products.

  12. New manuscript guidelines for the reporting of stable hydrogen, carbon, and oxygen isotope-ratio data

    Energy Technology Data Exchange (ETDEWEB)

    Anon.

    1995-10-01

    To eliminate possible confusion in the reporting of isotopic abundances on non-corresponding scales, the Commission on Atomic Weights and Isotopic Abundances recommended at the 37{sup th} General Assembly at Lisbon, Portugal that (i) {sup 2}H/{sup 1}H relative ratios of all substances be expressed relative to VSMOW (Vienna Standard Mean Ocean Water) on a scale such that {sup 2}H/{sup 1}H of SLAP (Standard Light Antartic Precipitation) is 0.572 times that of VSMOW, (ii) {sup 13}C/{sup 12}C relative ratios of all substances be expressed relative to VPDB (Vienna Peedee belemnite) on a scale such that {sup 13}C/{sup 12}C of NBS 19 carbonate is 1.00195 times that of VPDB, and (iii) {sup 18}O/{sup 16}O ratios of all substances be expressed relative to either VSMOW or VPDB on scales such that {sup 18}O/{sup 16}O of SLAP is 0.9445 times that of VSMOW. (Author)

  13. Direct isotope ratio analysis of individual uranium-plutonium mixed particles with various U/Pu ratios by thermal ionization mass spectrometry.

    Science.gov (United States)

    Suzuki, Daisuke; Esaka, Fumitaka; Miyamoto, Yutaka; Magara, Masaaki

    2015-02-01

    Uranium and plutonium isotope ratios in individual uranium-plutonium (U-Pu) mixed particles with various U/Pu atomic ratios were analyzed without prior chemical separation by thermal ionization mass spectrometry (TIMS). Prior to measurement, micron-sized particles with U/Pu ratios of 1, 5, 10, 18, and 70 were produced from uranium and plutonium certified reference materials. In the TIMS analysis, the peaks of americium, plutonium, and uranium ion signals were successfully separated by continuously increasing the evaporation filament current. Consequently, the uranium and plutonium isotope ratios, except the (238)Pu/(239)Pu ratio, were successfully determined for the particles at all U/Pu ratios. This indicates that TIMS direct analysis allows for the measurement of individual U-Pu mixed particles without prior chemical separation.

  14. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    Energy Technology Data Exchange (ETDEWEB)

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  15. A novel role for methyl cysteinate, a cysteine derivative, in cesium accumulation in Arabidopsis thaliana

    Science.gov (United States)

    Adams, Eri; Miyazaki, Takae; Hayaishi-Satoh, Aya; Han, Minwoo; Kusano, Miyako; Khandelia, Himanshu; Saito, Kazuki; Shin, Ryoung

    2017-01-01

    Phytoaccumulation is a technique to extract metals from soil utilising ability of plants. Cesium is a valuable metal while radioactive isotopes of cesium can be hazardous. In order to establish a more efficient phytoaccumulation system, small molecules which promote plants to accumulate cesium were investigated. Through chemical library screening, 14 chemicals were isolated as ‘cesium accumulators’ in Arabidopsis thaliana. Of those, methyl cysteinate, a derivative of cysteine, was found to function within the plant to accumulate externally supplemented cesium. Moreover, metabolite profiling demonstrated that cesium treatment increased cysteine levels in Arabidopsis. The cesium accumulation effect was not observed for other cysteine derivatives or amino acids on the cysteine metabolic pathway tested. Our results suggest that methyl cysteinate, potentially metabolised from cysteine, binds with cesium on the surface of the roots or inside plant cells and improve phytoaccumulation. PMID:28230101

  16. Discrimination of geographical origin of lentils (Lens culinaris Medik.) using isotope ratio mass spectrometry combined with chemometrics.

    Science.gov (United States)

    Longobardi, F; Casiello, G; Cortese, M; Perini, M; Camin, F; Catucci, L; Agostiano, A

    2015-12-01

    The aim of this study was to predict the geographic origin of lentils by using isotope ratio mass spectrometry (IRMS) in combination with chemometrics. Lentil samples from two origins, i.e. Italy and Canada, were analysed obtaining the stable isotope ratios of δ(13)C, δ(15)N, δ(2)H, δ(18)O, and δ(34)S. A comparison between median values (U-test) highlighted statistically significant differences (pprotein and starch fractions and the relevant results are reported.

  17. High-Sensitivity Measurement of 3He-4He Isotopic Ratios for Ultracold Neutron Experiments

    CERN Document Server

    Mumm, H P; Bauder, W; Abrams, N; Deibel, C M; Huffer, C R; Huffman, P R; Schelhammer, K W; Swank, C M; Janssens, R; Jiang, C L; Scott, R H; Pardo, R C; Rehm, K E; Vondrasek, R; O'Shaughnessy, C M; Paul, M; Yang, L

    2016-01-01

    Research efforts ranging from studies of solid helium to searches for a neutron electric dipole moment require isotopically purified helium with a ratio of 3He to 4He at levels below that which can be measured using traditional mass spectroscopy techniques. We demonstrate an approach to such a measurement using accelerator mass spectroscopy, reaching the 10e-14 level of sensitivity, several orders of magnitude more sensitive than other techniques. Measurements of 3He/4He in samples relevant to the measurement of the neutron lifetime indicate the need for substantial corrections. We also argue that there is a clear path forward to sensitivity increases of at least another order of magnitude.

  18. Unusual stable isotope ratios in amino acid and carboxylic acid extracts from the Murchison meteorite

    Science.gov (United States)

    Epstein, S.; Krishnamurthy, R. V.; Cronin, J. R.; Pizzarello, S.; Yuen, G. U.

    1987-01-01

    The isotopic composition of hydrogen, nitrogen, and carbon in amino acid and monocarboxylic acid extracts from the Murchison meteorite has been determined. The unusually high D/H and N-15/N-14 ratios in the amino acid fraction are uniquely characteristic of known interstellar organic materials. The delta D value of the monocarboxylic acid fraction is lower but still consistent with an interstellar origin. These results confirm the extraterrestrial origin of both classes of compound and provide the first evidence suggesting a direct relationship between the massive organosynthesis occurring in interstellar clouds and the presence of prebiotic compounds in primitive planetary bodies.

  19. Carbon isotope ratios of C4 plants in loess areas of North China

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Carbon isotope ratios (δ13C) of 89 C4 plant samples were determined from the loess area in North China. δ13C values vary between -10.5‰ and -14.6‰ with a mean of -12.6‰. Along a precipitation gradient from the semi-moist area to the semiarid area, then to the arid area, the δ13C values of C4 plants show a slight decreasing trend. The δ13C values of C4 plants in the dry season are found lower than those in the wet season. These trends are opposite to those observed for C3 species.

  20. Source Attribution of Cyanides using Anionic Impurity Profiling, Stable Isotope Ratios, Trace Elemental Analysis and Chemometrics

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-01-08

    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 stable 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

  1. Effects of several variable factors on the isotope ratio by HRGC-MS.

    Science.gov (United States)

    Sawamura, Masayoshi; Satake, Atsushi; Ueno, Takao; Une, Akitoshi; Ukeda, Hiroyuki

    2004-01-01

    In the isotope ratio (Ir) analysis using GC-MS, several variable factors in sampling incidental to any food analysis were investigated for yuzu fruit. The Irs of ten monoterpene hydrocarbons in yuzu essential oils from each of six fruiting positions of three trees were measured. The sign test following t-test of all the Ir values demonstrated that there was no significant difference between both sampling years of 2001 and 2002. There was also no significant variation in the Ir values among the three trees and six fruiting positions in the individual two years.

  2. Recent measurements of 234U/238U isotope ratio in spring waters from the Hadzici area.

    Science.gov (United States)

    Vidic, Alfred; Ilić, Zorana; Benedik, Ljudmila

    2013-06-01

    The Hadzici area has become interesting for investigation since depleted uranium ammunition had been employed in 1995 during the NATO air strike campaign in Bosnia and Herzegovina. The purpose of this study is to determine uranium concentration and (234)U/(238)U activity ratio in the spring waters of this area and to investigate their relationship, as well as spatial variations. The spring water samples were taken at 18 sites in total. For the determination of uranium radioisotopes, radiochemical separation procedure followed by alpha-particle spectrometry was applied. Uranium concentration in analyzed waters range from 0.15 to 1.12 μg/L. Spring waters from carbonate based sediments have a lower uranium concentration of between 0.15 and 0.43 μg/L, in comparison to waters sampled within sandstone-based sediments ranging from 0.53 to 1.12 μg/L. Dissolved uranium shows significant spatial variability and correlation with bedrock type confirmed by Principal Component Analysis and Hierarchical Cluster Analysis. The majority of the analyzed waters have a (234)U/(238)U activity ratio ranging from 1.02 to 1.90, of which half of the results range between 1.02 and 1.16. No apparent depleted uranium (DU) contamination was observed, as (234)U/(238)U activity ratio is dependent on geochemical conditions in the environment. Even though the tested spring waters demonstrate significant variability in uranium concentration, (234)U/(238)U activity ratio and (234)U excess, waters with similar uranium isotopic signatures are observable within the region. The guidelines on the spatial redistribution of dissolved uranium (corresponding to (238)U mass concentration), along with (234)U/(238)U activity ratios were provided by the Inverse Distance Weighting (IDW) method. Waters having similar isotopic signature have been delineated.

  3. Gas chromatographic separation for the H and C stable isotope ratio determination of coal compounds

    Energy Technology Data Exchange (ETDEWEB)

    Antenucci, D.; Jacquemin, C. [Institut Scientifique de Service Public, Liege (Belgium); Bouquegneau, J.M.; Brasseur, A.; Dauby, P.; Pirard, J.P. [Universite de Liege (Belgium); Letolle, R. [Universite Pierre et Marie Curie, Paris (France)

    1997-06-01

    A new, completely automated gas chromatography technique has been developed to separate the different gaseous compounds produced during underground coal gasification for their {sup 13}C/{sup 12}C and D/H isotope ratio measurements. The technique was designed for separation and collection of H{sub 2}, CO, CO{sub 2}, H{sub 2}O, H{sub 2}S, CH{sub 4}, and heavier hydrocarbons. These gaseous compounds are perfectly separated by the gas-phase chromatograph and quantitatively sent to seven combustion and collection lines. H{sub 2}, CO, CH{sub 4}, and heavier hydrocarbons are quantitatively oxidized to CO{sub 2} and/or H{sub 2}O. The isotopic analyses are performed by the sealed-tube method. The zinc method is used for reduction of both water and H{sub 2}S to hydrogen for D/H analysis. Including all preparation steps, the reproducibility of isotope abundance values, for a quantity higher than or equal to 0.1 mL of individual components in a mixture (5 mL of gases being initially injected in the gas chromatograph), is {+-}0.1 per mil for {delta}{sup 13}C{sub PDB} and {+-}6 per mil for {delta}D{sub SMOW}. 20 refs., 3 figs., 4 tabs.

  4. Historical variations of mercury stable isotope ratios in Arctic glacier firn and ice cores

    Science.gov (United States)

    Zdanowicz, C. M.; Krümmel, E. M.; Poulain, A. J.; Yumvihoze, E.; Chen, J.; Å trok, M.; Scheer, M.; Hintelmann, H.

    2016-09-01

    The concentration and isotopic composition of mercury (Hg) were determined in glacier core samples from Canadian Arctic ice caps dating from preindustrial to recent time (early 21st century). Mean Hg levels increased from ≤ 0.2 ng L-1 in preindustrial time to ~0.8-1.2 ng L-1 in the modern industrial era (last ~200 years). Hg accumulated on Arctic ice caps has Δ199Hg and Δ201Hg that are higher (~ -1 to 2.9‰) than previously reported for Arctic snow impacted by atmospheric Hg depletion events (mostly < -1‰), suggesting that these events contribute little to Hg accumulation on ice caps. The range of δ202Hg, Δ199Hg, and Δ201Hg in glacier cores overlaps with that of Arctic Hg0(g) and of seawater in Baffin Bay and also with that of midlatitude precipitation and industrial Hg sources, including coal and Hg ores. A core from Agassiz ice cap (80.7°N) shows a ~ +1‰ shift in δ202Hg over the nineteenth to twentieth centuries that could reflect changes in the isotopic composition of the atmospheric Hg pool in the High Arctic in response to growing industrial emissions at lower latitudes. This study is the first ever to report on historical variations of Hg stable isotope ratios in Arctic ice cores. Results could help constrain future modeling efforts of the global Hg biogeochemical cycle and the atmosphere's response to changing Hg emissions, past and future.

  5. Intra-Shell boron isotope ratios in benthic foraminifera: Implications for paleo-pH reconstructions

    Science.gov (United States)

    Rollion-Bard, C.; Erez, J.

    2009-12-01

    The boron isotope composition of marine carbonates is considered to be a seawater pH proxy. Nevertheless, the use of δ11B has some limitations: 1) the knowledge of fractionation factor (α4-3) between the two boron dissolved species (boric acid and borate ion), 2) the δ11B of seawater may have varied with time and 3) the amplitude of the "vital effects" of this proxy. Using secondary ion mass spectrometry (SIMS), we looked at the internal variability in the boron isotope ratio of the shallow water, symbionts bearing foraminiferan Amphistegina lobifera. Specimens were cultured at constant temperature (24±0.1 °C) in seawater with pH ranging between 7.90 and 8.45. We performed 6 to 8 measurements of δ11B in each foraminifera. Intra-shell boron isotopes show large variability with an upper threshold value of pH ~ 9. The ranges of the skeletal calculated pH values in different cultured foraminifera, show strong correlation with the culture pH values and may thus serve as proxy for pH in the past ocean.

  6. A fast switching electrostatic deflector system for actinide isotopic ratio measurements

    Science.gov (United States)

    Zorko, Benjamin; Child, D. P.; Hotchkis, M. A. C.

    2010-04-01

    We have implemented a fast switching electrostatic system on the actinides beamline on the ANTARES accelerator at ANSTO, to improve the precision of analyses by accelerator mass spectrometry. This high-energy bouncing system is based on a pair of deflector plates, deflecting in the orbit plane, set at the entrance and exit of the analysing magnet. The design of deflector plates is unique, and it was modelled by SIMION in order to minimize field inhomogenity and fringe field effects. The pair of deflector plates are supplied by a high-voltage amplifier driven by an EPICS-enabled control unit, with two 4 W power supplies providing up to ±10 kV modulation. The high-energy bouncing system is synchronized with the existing low-energy bouncing system. To measure the isotopic ratio with the new system, the magnetic fields of the injector and analysing magnets are set to transmit selected isotopes along the beam line with zero voltage applied. The other isotopes of interest are transmitted by keeping the magnetic fields constant and modulating the voltages on the injector magnet chamber and on the high-energy deflector plates.

  7. Gas Compositions and He-C Isotopic Ratios of Fumarolic Samples from Negros Island, Central Philippines

    Science.gov (United States)

    Lee, Hsiao-Fen; Yang, Tsanyao Frank; Faith Lan, Tefang; Chen, Yue-Gau; Sincioco, Jaime S.; Solidum, Renato U., Jr.

    2010-05-01

    Four volcanoes that are distributed in the Negros Island, Central Philippines, include Kanlaon Volcano which is considered as one of the most active volcanoes in Philippines. All of these volcanoes are related to subduction system of Negros trench and form the Negros volcanic arc. Besides Kanlaon, from north to south, the volcanoes in Negros Island are Silay Volcano, Mandalagan Volcano and Cuernos de Negros Volcano. Although there is no eruption record of these three volcanoes in last 10,000 years, due to the ongoing solfataric/fumarolic activities, the Philippine Institute of Volcanology and Seismology (PHIVOLCS) classifies these as 'potentially active' volcanoes. It means that there is still a considerable threat and risk of eruption. Fumarolic gas samples and bubbling gas samples of hot spring were collected in February 2007 and April 2008 to compare the compositions with others in the world. We analyzed the gas composition, carbon isotopes of CO2, and helium isotopes of these samples. The results of these samples show a similar composition as those of low-temperature fumaroles in other parts of the world, i.e., temperature 1. H2O is the major species of these gas samples, and CO2 is the dominant component after de-watering. Minor components include H2S, N2 and CH4. The gas composition of most of these samples falls in the range of affinity with convergent plate gases associated with groundwater based on the plot of N2-He-Ar diagram. The high 3He/4He ratios indicate a mantle-derived degassing source in origin, i.e., magma chambers could still exist beneath these volcanoes. Helium isotopes ratios show a decreasing trend from north to south, such distribution could be due to more crustal contamination caused by the collision event which happened in the northern part of the island. The carbon isotopic values of CO2 are far less negative than the values from a magma source. There are other carbon sources of CO2, most likely a thick sequence of limestone formation in

  8. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    Science.gov (United States)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  9. Evaluation of Affinity-Tagged Protein Expression Strategies using Local and Global Isotope Ratio Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Hervey, IV, William Judson [ORNL; Khalsa-Moyers, Gurusahai K [ORNL; Lankford, Patricia K [ORNL; Owens, Elizabeth T [ORNL; McKeown, Catherine K [ORNL; Lu, Tse-Yuan S [ORNL; Foote, Linda J [ORNL; Morrell-Falvey, Jennifer L [ORNL; McDonald, W Hayes [ORNL; Pelletier, Dale A [ORNL; Hurst, Gregory {Greg} B [ORNL

    2009-01-01

    Protein enrichments of engineered, affinity-tagged (or bait ) fusion proteins with interaction partners are often laden with background, non-specific proteins, due to interactions that occur in vitro as an artifact of the technique. Furthermore, the in vivo expression of the bait protein may itself affect physiology or metabolism. In this study, intrinsic affinity purification challenges were investigated in a model protein complex, DNA-dependent RNA polymerase (RNAP), encompassing chromosome- and plasmid-encoding strategies for bait proteins in two different microbial species: Escherichia coli and Rhodopseudomonas palustris. Isotope ratio measurements of bait protein expression strains relative to native, wild-type strains were performed by liquid chromatography tandem mass spectrometry (LC-MS-MS) to assess bait protein expression strategies in each species. Authentic interacting proteins of RNAP were successfully discerned from artifactual co-isolating proteins by the isotopic differentiation of interactions as random or targeted (I-DIRT) method (A. J. Tackett et al. J. Proteome Res. 2005, 4 (5), 1752-1756). To investigate broader effects of bait protein production in the bacteria, we compared proteomes from strains harboring a plasmid that encodes an affinity-tagged subunit (RpoA) of the RNAP complex with the corresponding wild-type strains using stable isotope metabolic labeling. The ratio of RpoA abundance in plasmid strains versus wild type was 0.8 for R. palustris and 1.7 for E. coli. While most other proteins showed no appreciable difference, proteins significantly increased in abundance in plasmid-encoded bait-expressing strains of both species included the plasmid encoded antibiotic resistance protein, GenR and proteins involved in amino acid biosynthesis. Together, these local, complex-specific and more global, whole proteome isotopic abundance ratio measurements provided a tool for evaluating both in vivo and in vitro effects of plasmid

  10. Chemometrical exploration of an isotopic ratio data set of acetylsalicylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Stanimirova, I. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Daszykowski, M. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Van Gyseghem, E. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Bensaid, F.F. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Lees, M. [Eurofins Scientific Analytics, Rue Pierre Adolphe Bobierre, 44323 Nantes Cedex 3 (France); Smeyers-Verbeke, J. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Massart, D.L. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium); Vander Heyden, Y. [ChemoAC, FABI, Analytical Chemistry and Pharmaceutical Technology, Vrije Universiteit Brussel-VUB, Laarbeeklaan 103, B-1090 Brussels (Belgium)]. E-mail: yvanvdh@vub.ac.be

    2005-11-03

    A data set consisting of fourteen isotopic ratios or quantities derived from such ratios for samples of acetylsalicylic acid (aspirin), commercialized by various pharmaceutical companies from different countries, was analyzed. The goal of the data analysis was to explore whether results can be linked to geographical origin or other features such as different manufacturing processes, of the samples. The methods of data analysis used were principal component analysis (PCA), robust principal component analysis (RPCA), projection pursuit (PP) and multiple factor analysis (MFA). The results do not seem to depend on geographic origin, except for some samples from India. They do depend on the pharmaceutical companies. Moreover, it seems that the samples from certain pharmaceutical companies form clusters of similar samples, suggesting that there is some common feature between those pharmaceutical companies. Variable selection performed by means of MFA showed that the number of variables can be reduced to five without loss of information.

  11. Fractionation in position-specific isotope composition during vaporization of environmental pollutants measured with isotope ratio monitoring by ¹³C nuclear magnetic resonance spectrometry.

    Science.gov (United States)

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

    2015-10-01

    Isotopic fractionation of pollutants in terrestrial or aqueous environments is a well-recognized means by which to track different processes during remediation. As a complement to the common practice of measuring the change in isotope ratio for the whole molecule using isotope ratio monitoring by mass spectrometry (irm-MS), position-specific isotope analysis (PSIA) can provide further information that can be exploited to investigate source and remediation of soil and water pollutants. Position-specific fractionation originates from either degradative or partitioning processes. We show that isotope ratio monitoring by (13)C NMR (irm-(13)C NMR) spectrometry can be effectively applied to methyl tert-butylether, toluene, ethanol and trichloroethene to obtain this position-specific data for partitioning. It is found that each compound exhibits characteristic position-specific isotope fractionation patterns, and that these are modulated by the type of evaporative process occurring. Such data should help refine models of how remediation is taking place, hence back-tracking to identify pollutant sources.

  12. Effects of shock and Martian alteration on Tissint hydrogen isotope ratios and water content

    Science.gov (United States)

    Hallis, L. J.; Huss, G. R.; Nagashima, K.; Taylor, G. J.; Stöffler, D.; Smith, C. L.; Lee, M. R.

    2017-03-01

    The Tissint meteorite, a picritic shergottite, fell to Earth in Morocco on the 18th of July 2011, and is only the fifth Martian meteorite witnessed to fall. Hydrogen isotope ratios and water contents are variable within different minerals in Tissint. Ringwoodite and shock melt pockets contain elevated D/H ratios relative to terrestrial values (δD = 761-4224‰). These high ratios in recrystallized phases indicate significant implantation of hydrogen from the D-rich Martian atmosphere during shock. In contrast, although olivine has detectable water abundances (230-485 ppm), it exhibits much lower D/H ratios (δD = +88 to -150‰), suggesting this water was not implanted from the Martian atmosphere. The minimal terrestrial weathering experienced by Tissint gives confidence that the olivine-hosted water has a Martian origin, but its high concentration indicates direct inheritance from the parental melt is improbable, especially given the low pressure of olivine crystallisation. Incorporation of a low δD crustal fluid, or deuteric alteration during crystallisation, could explain the relatively high water contents and low D/H ratios in Tissint olivine.

  13. Authenticity of carbon dioxide bubbles in French ciders through multiflow-isotope ratio mass spectrometry measurements.

    Science.gov (United States)

    Gaillard, Laetitia; Guyon, Francois; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-01

    A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (δ(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a δ(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas δ(13)C value in the expected range. Nevertheless, some ciders have δ(13)C values outside the 3σ limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label.

  14. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses

    Science.gov (United States)

    BONG, Y.; Shin, W.; Gautam, M. K.; Jeong, Y.; Lee, A.; Jang, C.; Lim, Y.; Chung, G.; Lee, K.

    2012-12-01

    Recently, the Korean market has seen many cases of Chinese cabbage (Brassica rapa ssp. pekinensis) that have been imported from China, yet are sold as a Korean product to illegally benefit from the price difference between the two products. This study aims to establish a method of distinguishing the geographical origin of Chinese cabbage. One hundred Chinese cabbage heads from Korea and 60 cabbage heads from China were subjected to multielement composition and strontium isotope ratio (87Sr/86Sr) analyses. The 87Sr/86Sr ratio differed, based on the geological characteristics of their district of production. In addition, the content of many elements differed between cabbages from Korea and China. In particular, the difference in the content of Sr and Ti alone and the combination of Sr, Ca, and Mg allowed us to distinguish relatively well between Korea and China as the country of origin. The present study demonstrates that the chemical and Sr isotopic analyses exactly reflect the geology of the production areas of Chinese cabbage. Also, multivariate statistical analyses of multiple elements were found to be very effective in distinguishing the geographical origin of Chinese cabbages.

  15. Determining the geographical origin of Chinese cabbages using multielement composition and strontium isotope ratio analyses.

    Science.gov (United States)

    Bong, Yeon-Sik; Shin, Woo-Jin; Gautam, Mukesh Kumar; Jeong, Youn-Joong; Lee, A-Reum; Jang, Chang-Soon; Lim, Yong-Pyo; Chung, Gong-Soo; Lee, Kwang-Sik

    2012-12-15

    Recently, the Korean market has seen many cases of Chinese cabbage (Brassica rapa ssp. pekinensis) that have been imported from China, yet are sold as a Korean product to illegally benefit from the price difference between the two products. This study aims to establish a method of distinguishing the geographical origin of Chinese cabbage. One hundred Chinese cabbage heads from Korea and 60 cabbage heads from China were subjected to multielement composition and strontium isotope ratio ((87)Sr/(86)Sr) analyses. The (87)Sr/(86)Sr ratio differed, based on the geological characteristics of their district of production. In addition, the content of many elements differed between cabbages from Korea and China. In particular, the difference in the content of Sr and Ti alone and the combination of Sr, Ca, and Mg allowed us to distinguish relatively well between Korea and China as the country of origin. The present study demonstrates that the chemical and Sr isotopic analyses exactly reflect the geology of the production areas of Chinese cabbage.

  16. Line shift, line asymmetry, and the 6Li/7Li isotopic ratio determination

    CERN Document Server

    Cayrel, Roger; Chand, Hum; Bonifacio, Piercarlo; Spite, Monique; Spite, François; Petitjean, Patrick; Ludwig, Hans-Günter; Caffau, Elisabetta

    2007-01-01

    Context: Line asymmetries are generated by convective Doppler shifts in stellar atmospheres, especially in metal-poor stars, where convective motions penetrate to higher atmospheric levels. Such asymmetries are usually neglected in abundance analyses. The determination of the 6Li/7Li isotopic ratio is prone to suffering from such asymmetries, as the contribution of 6Li is a slight blending reinforcement of the red wing of each component of the corresponding 7Li line, with respect to its blue wing. Aims: The present paper studies the halo star HD 74000 and estimates the impact of convection-related asymmetries on the Li isotopic ratio determination. Method: Two methods are used to meet this aim. The first, which is purely empirical, consists in deriving a template profile from another element that can be assumed to originate in the same stellar atmospheric layers as Li I, producing absorption lines of approximately the same equivalent width as individual components of the 7Li I resonance line. The second metho...

  17. What climate information is recorded in stable isotope ratios of wood lignin methoxyl groups?

    Science.gov (United States)

    Greule, Markus; Keppler, Frank

    2010-05-01

    The stable isotope composition of the bioelements C, O, H and N in plant organic matter is known to be a very powerful for various environmental impacts. Particularly tree rings are suitable for this analysis because they exhibit a "climate archive" with a yearly or even biannual resolution. One of the most determined wood compounds is cellulose which amongst others is used to reconstruct the temperature due to measurement of stable hydrogen and oxygen isotopes. Therefore cellulose is converted into cellulose nitrate to eliminate the exchangeable hydroxyl hydrogen or equilibration methods are used. However, a general problem associated with the determination of the stable hydrogen values of marker compounds for the study of climate and environmental conditions is the isolation of the pure compound for analysis by isotope ratio mass spectrometry. Exploitation of components of wood as markers, in particular, has been restricted by the very labour intensive and time consuming preparation of samples (e.g. cellulose nitrate). An alternative way to record climate information from tree rings was recently proposed by Keppler et al. (2007) who measured the stable hydrogen values of methoxyl groups in wood. Lignin methoxyl groups are considered to be stable, i.e. the hydrogen atoms of the methoxyl moiety do not exchange with those of plant water during ongoing metabolic reactions in the plant. Thus the initial deuterium content of the methoxyl groups of lignin in woody tissue at formation is retained throughout the lifetime of the tree and in preserved tissue. The methoxyl content of lignin in wood is usually determined by the Zeisel method (Zeisel, 1885) - the reaction between methyl ethers and hydroiodic acid to form methyl iodide. Exploiting this reaction for the measurement of stable hydrogen values of lignin methoxyl groups ensures that during the entire analytical procedure the isotope signal is preserved since no isotopic exchange occurs between the methyl groups and

  18. Recycling and Mantle Stirring Determined by 142Nd/144Nd Isotopic Ratios

    Science.gov (United States)

    Jacobsen, S. B.; Ranen, M. C.

    2004-12-01

    It is now well established that 146Sm was live in the early solar system with an initial uniform 146Sm/144Sm ratio of ~0.008. Harper and Jacobsen (1992) discovered that a sample from Isua (~3.8 Ga old) had a positive 142Nd/144Nd anomaly of 33 ppm when compared to normal terrestrial and chondritic Nd. Furthermore, Jacobsen and Harper (1996) reported results from other Isua as well as Acasta (~4 Ga old) samples. Three other Isua samples had a possible small range (about -15 to +15), while two Acasta samples had no anomalies (normal to within 5 ppm). The presence of 142Nd anomalies at Isua has recently been confirmed by two other groups (Boyet et al. 2003; Caro et al. 2003). The available data demonstrate both the existence of early depleted mantle and that the early mantle was isotopically heterogeneous. As discussed by Jacobsen and Harper (1996), the recycling rate can be determined by tracing the decay of the average 142Nd/144Nd value of the depleted mantle. In addition, by using the 142Nd/144Nd heterogeneity in the depleted mantle through time we can determine the stirring rate of the mantle (Kellogg, Jacobsen and O'Connell, 2002) as a function of time. For this project our goal is to obtain a resolution in 142Nd/144Nd measurements of ~1 ppm. We have thus compared results obtained for the Nd isotope composition and 142Nd enriched standards for three different TIMS instruments: The Finnigan MAT 262 at Harvard, the Isoprobe-T and Finnigan TRITON mass spectrometers in GV Instrument's and Thermo Electron's demo laboratories in Manchester and Bremen, respectively. The Finnigan TRITON was designed in response to a request from the senior author for such an instrument. The results obtained so far demonstrate that all three instruments yield the same 142Nd/144Nd, 143Nd/144Nd and 145Nd/144Nd isotopic ratios to within a few ppm, while 148Nd/144Nd and 150Nd/144Nd ratios agree to within 10-20 ppm, when all ratios are normalized to 146Nd/144Nd using the exponential law. Due to

  19. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    Science.gov (United States)

    Sturchio, N. C.; Keith, T. E. C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface ( in situ temperatures ranging from 81 to 199°C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The δ 18O values of the thirty-two analyzed silica samples (quartz, chalcedony, α-cristobalite, and β-cristobalite) range from -7.5 to +2.8‰ . About one third of the silica 7samples have δ 18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7‰) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have δ 18O values higher (by 3.5 to 7.9‰) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with

  20. Estimating the distribution of strontium isotope ratios (87Sr/86Sr in the Precambrian of Finland

    Directory of Open Access Journals (Sweden)

    Lars Kaislaniemi

    2011-12-01

    Full Text Available A method to estimate the 87Sr/86Sr ratio of a rock based on its age and Rb/Sr ratio is presented. This method, together with data from the Rock Geochemical Database of Finland (n=6544 is used to estimate the 87Sr/86Sr ratios in the Precambrian of Finland and in its different major units. A generalization to cover the whole area of Finland is achieved by smoothing of estimation points. The estimation method is evaluated by comparing its results to published Rb-Sr isotope analyses (n=138 obtained on the Finnish Precambrian. The results show correspondence to different geological units of Finland,but no systematic difference between Archaean and younger areas is evident. Evaluation of the method shows that most of the estimates are reliable and accurate to be used as background material for provenance studies in archaeology, paleontology and sedimentology. However, some granitic rocks may have large (>1.0 % relative errors.Strontium concentration weighted average of the estimates differs only by 0.001 from the average 87Sr/86Sr ratio (0.730 of the rivers on the Fennoscandian shield.

  1. Isotope systematics of a juvenile intraplate volcano: Pb, Nd, and srisotope ratios of basalts from Loihi Seamount, Hawaii

    Energy Technology Data Exchange (ETDEWEB)

    Staudigel, H. (Columbia Univ., Palisades, NY (USA). Lamont-Doherty Geological Observatory; Scripps Institution of Oceanography, La Jolla, CA (USA)); Zindler, A.; Leslie, T. (Columbia Univ., Palisades, NY (USA). Lamont-Doherty Geological Observatory); Hart, S.R.; Chen, C.Y. (Massachusetts Inst. of Tech., Cambridge (USA). Dept. of Earth and Planetary Sciences); Clague, D. (Geological Survey, Menlo Park, CA (USA))

    1984-07-01

    Sr, Nd, and Pb isotope ratios for a representative suite of 15 basanites, alkali basalts, transitional basalts and tholeiites from Loihi Seamount, Hawaii, display unusually large variations for a single volcano, but lie within known ranges for Hawaiian basalts. Nd isotope ratios in alkali basalts show the largest relative variation (0.51291 - 0.51305), and include the nearly constant tholeiite value (approx.= 0.51297). Pb isotope ratios show similarly large ranges for tholeiites and alkali basalts and continue Tatsumoto's (31) 'Loa' trend towards higher /sup 206/Pb//sup 204/Pb, ratios, resulting in a substantial overlap with the 'Kea' trend. /sup 206/Pb//sup 204/Pb ratios for Loihi and other volcanoes along the Loa and Kea trends (31) are observed to correlate with the age of the underlying lithosphere suggesting lithosphere involvement in the formation of Hawaiian tholeiites. Loihi lavas display no correlation of Nd, Sr, or Pb isotope ratios with major element compositions or eruptive age, in contrast with observations of some other Hawaiian volcanoes. Isotope data for Loihi, as well as average values for Hawaiian volcanoes, are not adequately explained by previously proposed two-end-member models; new models for the origin and the development of Hawaiian volcanoes must include mixing of at least three geochemically distinct source regions and allow for the involvement of heterogeneous oceanic lithosphere.

  2. Quantifying Uranium Isotope Ratios Using Resonance Ionization Mass Spectrometry: The Influence of Laser Parameters on Relative Ionization Probability

    Energy Technology Data Exchange (ETDEWEB)

    Isselhardt, Brett H. [Univ. of California, Berkeley, CA (United States)

    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 in 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.

  3. Fidelity of Stable Oxygen Isotope Ratios as Environmental Recorders Using Multiple Coral Cores From Coastal Kenya

    Science.gov (United States)

    Naish, T.; Carter, B.; Abbott, S.; Field, B.; Zhu, H.; Wilson, G.; Alloway, B.; Edwards, S.; Pillans, B.; Barker, A.; Niessen, F.; Maslen, G.; Beu, A.; Fleitmann, D.; Dunbar, R. B.; Mucciarone, D. A.

    2004-12-01

    Climate variability in the western equatorial Indian Ocean reflects the combined influence of seasonally changing sea surface temperature (SST), ocean currents, and monsoon circulation, as well as inter-annual to -decadal variability associated with ENSO in the Pacific. However, the Indian Ocean also exhibits variability that appears unrelated to ENSO in the Pacific. The nature of interactions between air-sea variability in the Indian and Pacific oceans is not yet fully resolved, in part because of the lack of long-term, high-resolution SST records from key localities in the Indian Ocean. Such records are now being obtained using oxygen isotope profiles measured on corals from East Africa, Indonesia, Australia, and Indian Oceania (Maldives, Seychelles), with the longest coral-based time series from Malindi, Kenya, covering the last 300 years at near-monthly resolution. The value of these developing coral records depends on the fidelity with which they record regional climate variability. In order to assess the fidelity of oxygen isotope ratios (\\delta18O) in Indian Ocean corals as a proxy for sea surface temperature, we have generated stable isotopic time series from multiple Porites lutea coral heads collected along the coast of Kenya. Coral-based isotopic paleoclimatology is labor and time-intensive so detailed analyses using multiple coral heads from different sites within a region are extremely rare. Most published records are produced from a single coral head, yet questions have been raised about the accuracy of such records. To address such concerns, near-monthly resolution isotopic profiles, spanning 10 to 50 years prior to 1997, were measured on a total of 8 cores from five sites along a north-south transect between 2° and 4° S (Kiwayu: 2° 2'S, 41° 2'E, Malindi: 3° 14'S, 40° 8'E, Watamu: 3° 23'S, 39° 52'E, Mombasa: 3° 59'S, 39° 5'E, and Kisite: 4° 43'S, 39° 23'E. Correlations among individual \\delta18O time series (r values range from 0.65 to

  4. ANALYSIS OF RICIN TOXIN PREPARATIONS FOR CARBOHYDRATE AND FATTY ACID ABUNDANCE AND ISOTOPE RATIO INFORMATION

    Energy Technology Data Exchange (ETDEWEB)

    Wunschel, David S.; Kreuzer-Martin, Helen W.; Antolick, Kathryn C.; Colburn, Heather A.; Moran, James J.; Melville, Angela M.

    2009-12-01

    employing a quadrupole MS system for compound identification and an isotope ratio MS for measuring the stable isotope ratios of deuterium and hydrogen (D/H) in fatty acids. Finally, the method for analyzing the compound abundance data is included. This study indicates that removal of ricinoleic acid is a conserved consequence of each processing step we tested. Furthermore, the stable isotope D/H ratio of ricinoleic acid distinguished between two of the three castor seed sources. Concentrations of arabinose, xylose, mannose, glucosamine and myo-inositol differentiated between crude or acetone extracted samples and samples produced by protein precipitation. Taken together these data illustrate the ability to distinguish between processes used to purify a ricin sample as well as potentially the source seeds.

  5. Heavy with child? Pregnancy status and stable isotope ratios as determined from biopsies of humpback whales

    Science.gov (United States)

    Clark, Casey T.; Fleming, Alyson H.; Calambokidis, John; Kellar, Nicholas M.; Allen, Camryn D.; Catelani, Krista N.; Robbins, Michelle; Beaulieu, Nicole E.; Steel, Debbie; Harvey, James T.

    2016-01-01

    Understanding reproductive rates of wild animal populations is crucially important for management and conservation. Assessing pregnancy status of free-ranging cetaceans has historically been difficult; however, recent advances in analytical techniques have allowed the diagnosis of pregnancy from small samples of blubber tissue. The primary objectives of this study were as follows: (i) to test the efficacy of blubber progesterone assays as a tool for diagnosing pregnancy in humpback whales (Megaptera novaeangliae); (ii) to estimate the pregnancy rate of humpback whales in Monterey Bay, California; and (iii) to investigate the relationship between stable isotopes and reproductive status of these whales. Progesterone concentrations of female whales fell into two distinct groups, allowing for diagnostic separation of pregnant and non-pregnant individuals. Pregnancy rate varied between years of the study (48.4%% in 2011 and 18.5% in 2012), but fell within the range of other estimates of reproductive success for this population. Stable carbon and nitrogen isotope ratios were examined to investigate the impacts of pregnancy on these values. Neither δ15N nor δ13C varied in a consistent way among animals of different sex or reproductive status. The relationship between δ15N and δ13C was strongly positive for male and non-pregnant female humpbacks; however, no relationship existed for pregnant whales. This difference may be indicative of the effects of pregnancy on δ15N, resulting from tissue synthesis and reduced excretion of nitrogenous waste, as well as on δ13C through increased mobilization of lipid stores to meet the energetic demands of pregnancy. Ultimately, our results support the use of blubber progesterone assays for diagnosing pregnancy in humpback whales and indicate that, when paired with other approaches (e.g. stable isotope analysis), pregnancy status can be an informative tool for addressing questions about animal physiology, ecology and population

  6. Stable isotope ratio analysis for verifying the authenticity of balsamic and wine vinegar.

    Science.gov (United States)

    Perini, M; Paolini, M; Simoni, M; Bontempo, L; Vrhovsek, U; Sacco, M; Thomas, F; Jamin, E; Hermann, A; Camin, F

    2014-08-13

    In this paper, we investigate whether the analysis of stable isotope ratios D/H and ¹³C/¹²C in ethanol and acetic acid and of ¹⁸O/¹⁶O in water can be applied to the ingredients of "aceto balsamico di Modena IGP" (ABM) to evaluate their authenticity. We found that impurities in the extraction solution do not affect the ¹³C/¹²C of acetic acid and the D/H values of acetic acid are not affected under a composite NMR experiment. The standard deviation of repeatability and standard deviation of reproducibility are comparable in wine vinegar and ABM and generally lower than those quoted in the official methods. This means that the validation parameters quoted in the official methods can also be applied to the ingredients of ABM. In addition, we found no changes in the isotopic values from wine to vinegar and to ABM, and from the original must to the ABM must, providing experimental evidence that reference data from wine databanks can also be used to evaluate the authenticity of vinegar and ABM.

  7. Use of isotope ratios to identify sources contributing to pediatric lead poisoning in Peru.

    Science.gov (United States)

    Naeher, Luke P; Rubin, Carol S; Hernandez-Avila, Mauricio; Noonan, Gary P; Paschal, Dan; Narciso, Juan; Lain, Rocio Espinoza; Gastanaga, Carmen; Almeyda, Rosa; Jarrett, Jeff; Caldwell, Kathleen L; McGeehin, Michael

    2003-09-01

    In 1998, a school-based blood lead level (BLL) survey of 2,510 children, conducted in Lima and Callao, Peru, revealed elevated BLLs in children from 2 Callao schools (mean BLL = 25.6 microg/dl; n = 314) and in children from Callao overall (mean BLL = 15.2 microg/dl; n = 898), compared with children from Lima (mean BLL = 7.1 microg/dl; n = 1,612). Public health officials at Peru's Direccion General de Salud Ambiental (DIGESA) hypothesized that a possible source of the elevated pediatric BLLs observed in Callao was a large depository near the port where mineral concentrates are stored prior to shipment. The U.S. Centers for Disease Control and Prevention worked with DIGESA to identify source(s) that contributed to the pediatric lead poisonings by comparing isotopic profiles of lead in blood, mineral, gasoline, and air filter samples. The lead isotope ratio (IR) observed in mineral samples from the depository in Callao differed from those in gasoline samples from Lima and Callao. The blood lead IRs of children living near the depository were similar to the IRs of the mineral samples and different from the IRs of the gasoline samples, suggesting that lead from the depository-and not gasoline-was the primary source of lead in these children. Lead IR analysis of regional air filter samples supported these findings.

  8. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    Energy Technology Data Exchange (ETDEWEB)

    Magdas, D. A., E-mail: gabriela.cristea@itim-cj.ro; Cristea, G., E-mail: gabriela.cristea@itim-cj.ro; Bot, A.; Puscas, R.; Radu, S.; Mirel, V. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath Str., 400293 Cluj-Napoca (Romania); Cordea, D. V.; Mihaiu, M. [University of Agricultural Science and Veterinary Medicine, 3-5 Calea Manastur, 400372 Cluj-Napoca (Romania)

    2013-11-13

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ{sup 18}O and δ{sup 2}H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ{sup 18}O and δ{sup 2}H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  9. Measurements of stable isotope ratios in milk samples from a farm placed in the mountains of Transylvania

    Science.gov (United States)

    Magdas, D. A.; Cristea, G.; Cordea, D. V.; Bot, A.; Puscas, R.; Radu, S.; Mirel, V.; Mihaiu, M.

    2013-11-01

    Product origin is of great importance for consumers especially because its association in consumer's perception with food quality, freedom from disease or pollution. Stable isotope ratio analysis is a powerful technique in food authenticity and traceability control which has been introduced within the European wine industry to ensure authenticity of wine provenance and to detect adulteration. Isotopic ratios measurements have also been successfully to other food commodities like: fruit juices, honey and dairy foods. The δ18O and δ2H content in milk water reflects the isotope composition of the ground water drunk by animals. Seasonal effects are also very important: in summer, milk water contains higher δ18O and δ2H values due to the fresh plants that are ate by animals. Relative carbon stable isotope abundances in total milk reflect the isotopic composition of the diet fed to the dairy cows. In this study the hydrogen, oxygen and carbon isotopic composition of 15 milk samples coming from a unit placed in the mountains of Transylvania was investigated. The distribution of the obtained isotopic values was than discussed taking into account that all the animals were feed with the same type of forage and consumed water was taken from the same source.

  10. Biomedical and Forensic Applications of Combined Catalytic Hydrogenation-Stable Isotope Ratio Analysis

    Directory of Open Access Journals (Sweden)

    Mark A. Sephton

    2007-01-01

    Full Text Available Studies of biological molecules such as fatty acids and the steroid hormones have the potential to benefit enormously from stable carbon isotope ratio measurements of individual molecules. In their natural form, however, the body’s molecules interact too readily with laboratory equipment designed to separate them for accurate measurements to be made.Some methods overcome this problem by adding carbon to the target molecule, but this can irreversibly overprint the carbon source ‘signal’. Hydropyrolysis is a newly-applied catalytic technique that delicately strips molecules of their functional groups but retains their carbon skeletons and stereochemistries intact, allowing precise determination of the carbon source. By solving analytical problems, the new technique is increasing the ability of scientists to pinpoint molecular indicators of disease, elucidate metabolic pathways and recognise administered substances in forensic investigations.

  11. Complementary stable carbon isotope ratio and amount of substance measurements in sports anti-doping.

    Science.gov (United States)

    Cawley, Adam T; George, Adrian V

    2012-12-01

    The detection of steroids originating from synthetic precursors against a background of their chemically identical natural analogues has proven to be a significant challenge for doping control laboratories accredited by the World Anti-Doping Agency (WADA). The complementary application of gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) has been demonstrated to provide specific detection of endogenous steroid misuse for improved anti-doping analysis. Markers of synthetically derived steroids are reviewed on the basis of abnormal urinary excretions and low (13)C content. A combinatorial approach is presented for the interpretation of GC-MS and GC-C-IRMS data in the anti-doping context. This methodology can allow all relevant information concerning an individual's metabolism to be assessed in order to make an informed decision with respect to a doping violation.

  12. Development and Deployment of Retrofit PolarisQ Ion Trap Mass Spectrometer for Isotope Ratio Measurements

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, Cyril V. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Whitten, William B. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-11-01

    This report describes Oak Ridge National Laboratory’s (ORNL) FY15 progress in support of National Nuclear Security Administration’s (NNSA) Portable Mass Spectrometer project. A retrofit PolarisQ ion trap mass spectrometer (RPMS) has been assembled from components of two PolarisQ ion trap mass spectrometers used in previous isotope ratio programs. The retrofit mass spectrometer includes a custom Hastelloy vacuum chamber which is about ¼ the size of the standard aluminum vacuum chamber and reduces the instrument weight from the original by nine pounds. In addition, the new vacuum chamber can be independently heated to reduce impurities such as water, which reacts with UF6 to produce HF in the vacuum chamber. The analyzer and all components requiring service are mounted on the chamber lid, facilitating quick and easy replacement of consumable components such as the filament and electron multiplier.

  13. Carbon isotope ratio mass spectrometry for detection of endogenous steroid use: a testing strategy.

    Science.gov (United States)

    Ahrens, Brian D; Butch, Anthony W

    2013-07-01

    Isotope ratio mass spectrometry (IRMS) testing is performed to determine if an atypical steroid profile is due to administration of an endogenous steroid. Androsterone (Andro) and etiocholanolone (Etio), and/or the androstanediols (5α- and 5β-androstane-3α,17β-diol) are typically analyzed by IRMS to determine the (13) C/(12) C ratio. The ratios of these target compounds are compared to the (13) C/(12) C ratio of an endogenous reference compound (ERC) such as 5β-pregnane-3α,20α-diol (Pdiol). Concentrations of Andro and Etio are high so (13) C/(12) C ratios can easily be measured in most urine samples. Despite the potentially improved sensitivity of the androstanediols for detecting the use of some testosterone formulations, additional processing steps are often required that increase labour costs and turnaround times. Since this can be problematic when performing large numbers of IRMS measurements, we established thresholds for Andro and Etio that can be used to determine the need for additional androstanediol testing. Using these criteria, 105 out of 2639 urine samples exceeded the Andro and/or Etio thresholds, with 52 of these samples being positive based on Andro and Etio IRMS testing alone. The remaining 53 urine samples had androstanediol IRMS testing performed and 3 samples were positive based on the androstanediol results. A similar strategy was used to establish a threshold for Pdiol to identify athletes with relatively (13) C-depleted values so that an alternative ERC can be used to confirm or establish a true endogenous reference value. Adoption of a similar strategy by other laboratories can significantly reduce IRMS sample processing and analysis times, thereby increasing testing capacity.

  14. Seaweed against strontium and preussian blue against cesium

    Directory of Open Access Journals (Sweden)

    G Michanek

    1988-06-01

    Full Text Available The fact that alginates bind strontium and cyanates bind cesium and are capable of removing these elements from living organisms is scientifically verified. Zeolites offer another possibility for exchange of these ions. Practical research should be initiated to find the right doses and procedure to decrease the body burden of radioactive isotopes in reindeer.Alger mot strontium och berlinerblått mot cesium.Abstract in Swedish / Sammanfattning: Mitt budskap år kort: Alger binder strontium, Berlinerblått binder cesium, Sätt fart på forskning och forsök!

  15. Long-term stability of hydrogen isotope ratios in hydrated volcanic glass

    Science.gov (United States)

    Cassel, Elizabeth J.; Breecker, Daniel O.

    2017-03-01

    The advancement of conceptual and numerical geodynamic models necessitates quantitative, orogen-scale paleoelevation data. Felsic volcanic glasses, which record the hydrogen isotope compositions (δD) of meteoric water shortly after deposition, provide several advantages as a paleoelevation proxy. Questions remain, however, about the reliability of this relatively new proxy, including the effect of hydrofluoric (HF) acid abrasion in the preparation of glass shards for hydrogen isotope analysis and the stability of hydrogen isotope ratios in hydrated glass shards over geologic time (106-107 years). HF acid abrasion of natural ancient glass shards results in systematic shifts in glass δD values away from modern water δD values. To evaluate the effectiveness of HF acid abrasion, we treated 70-150 μm glass shards separated from various natural tephras with deuterium-labeled water (DLW; δD = +18,205‰) for up to 400 days. For all glasses, this treatment resulted in elevated δD values in comparison to untreated samples. HF acid abrasion after DLW exposure, however, removed this effect and restored glass shards to their original untreated δD values in samples older than 104 years. HF acid abrasion removes hydrous alteration precipitates at the glass surface without measurably changing the δD values of the underlying hydrated glass, regardless of abrasion duration or glass composition. Additionally, 45-34 Ma glasses record δD values that directly reflect their depositional environments as determined by stratigraphy: glasses from tuffs deposited in demonstrably evaporative lacustrine environments have relatively high δD values compared to glasses from contemporaneous tuffs deposited in nearby fluvial environments, which have much lower δD values. The preservation of δD values that systematically vary with original depositional environment, despite >30 Myr of post-hydration exposure to the same meteoric water, indicates that these volcanic glasses resisted

  16. Using Lead Concentrations and Stable Lead Isotope Ratios to Identify Contamination Events in Alluvial Soils

    Directory of Open Access Journals (Sweden)

    Diane Saint-Laurent

    2010-01-01

    Full Text Available Soils contaminated with hydrocarbons (C10–C50, polycyclic aromatic hydrocarbons (PAHs, and other contaminants (e.g., As, Cd, Cu, Pb were recently discovered on the banks of the Saint-François and Massawippi rivers. Alluvial soils are contaminated over a distance of 100 kilometers, and the level of the contaminated-hydrocarbon layer in the soil profiles is among the highest at the Windsor and Richmond sites. Concentrations of lead and stable lead isotope ratios (204Pb/206Pb, 207Pb/206Pb, 208Pb/206Pb are also used to identify contamination events. The maximum and minimum values detected in soil profiles for arsenic, cadmium, and lead vary from 3.01 to 37.88 mg kg-1 (As, 0.11 to 0.81 mg kg-1 (Cd 12.32 to 149.13 mg kg-1 (Pb, respectively, while the 207Pb/206Pb isotopic ratio values are between 0.8545 and 0.8724 for all the profiles. The highest values of trace elements (As, Pb and Zn were detected in the hydrocarbon layer (C10–C50, most often located at the bottom of the profiles (160, 200, and 220 cm in depth. The various peaks recorded in the soils and the position of the profiles suggest that various contaminants were transported by the river on several occasions and infiltrated the soil matrix or deposited on floodplains during successive floods. Atmospheric particles which entered the river or deposited on riverbanks must also be considered as another source of pollution recorded in soils.

  17. Influences of β-HCG administration on carbon isotope ratios of endogenous urinary steroids.

    Science.gov (United States)

    Piper, Thomas; Baume, Norbert; Strahm, Emanuel; Emery, Caroline; Saugy, Martial

    2012-05-01

    Several factors influencing the carbon isotope ratios (CIR) of endogenous urinary steroids have been identified in recent years. One of these should be the metabolism of steroids inside the body involving numerous different enzymes. A detailed look at this metabolism taking into account differences found between steroids excreted as glucuronides or as sulphates and hydrogen isotope ratios of different steroids pointed out possibility of unequal CIR at the main production sites inside the male body - the testes and the adrenal glands. By administration of β-HCG it is possible to strongly stimulate the steroid production within the testes without influencing the production at the adrenal glands. Therefore, this treatment should result in changed CIR of urinary androgens in contrast to the undisturbed pre-treatment values. Four male volunteers received three injections of β-HCG over a time course of 5 days and collected their urine samples at defined intervals after the last administration. Those samples showing the largest response in contrast to the pre-administration urines were identified by steroid profile measurements and subsequent analysed by GC/C/IRMS. CIR of androsterone, etiocholanolone, testosterone, 5α- and 5β-androstanediol and pregnanediol were compared. While pregnanediol was not influenced, most of the investigated androgens showed depleted values after treatment. The majority of differences were found to be statistically significant and nearly all showed the expected trend towards more depleted δ(13)C-values. These results support the hypothesis of different CIR at different production sites inside the human body. The impact of these findings on doping control analysis will be discussed.

  18. Zinc isotope ratios of bones and teeth as new dietary indicators: results from a modern food web (Koobi Fora, Kenya)

    Science.gov (United States)

    Jaouen, Klervia; Beasley, Melanie; Schoeninger, Margaret; Hublin, Jean-Jacques; Richards, Michael P.

    2016-05-01

    In order to explore the possibilities of using zinc (Zn) stable isotope ratios as dietary indicators, we report here on the measurements of the ratio of stable isotopes of zinc (66Zn/64Zn, expressed here as δ66Zn) in bioapatite (bone and dental enamel) of animals from a modern food web in the Koobi Fora region of the Turkana Basin in Kenya. We demonstrate that δ66Zn values in both bone and enamel allow a clear distinction between carnivores and herbivores from this food web. Differences were also observed between browsers and grazers as well as between carnivores that consumed bone (i.e. hyenas) compared to those that largely consume flesh (i.e. lions). We conclude that Zn isotope ratio measurements of bone and teeth are a new and promising dietary indicator.

  19. Online technique for isotope and mixing ratios of CH4, N2O, Xe and mixing ratios of organic trace gases on a single ice core sample

    Directory of Open Access Journals (Sweden)

    J. Schmitt

    2014-03-01

    Full Text Available Polar ice cores enclosing trace gas species offer a unique archive to study changes in the past atmosphere and in terrestrial/marine source regions. Here we present a new online technique for ice core and air samples to measure a suite of isotope ratios and mixing ratios of trace gas species on a single small sample. Isotope ratios are determined on methane, nitrous oxide and xenon with reproducibilities for ice core samples of 0.15‰ for δ13C-CH4, 0.22‰ for δ15N-N2O, 0.34 ‰ for δ18O-N2O, and 0.05‰ for δ136Xe. Mixing ratios are determined on methane, nitrous oxide, xenon, ethane, propane, methyl chloride and dichloro-difluoromethane with reproducibilities of 7 ppb for CH4, 3 ppb for N2O, 50 ppt for 136Xe, 70 ppt for C2H6, 70 ppt for C3H8, 20 ppt for CH3Cl, and 2 ppt for CCl2F2. The system consists of a vacuum extraction device, a preconcentration unit and a gas chromatograph coupled to an isotope ratio mass spectrometer. CH4 is combusted to CO2 prior to detection while we bypassed the oven for all other species. The highly automated system uses only ~160 g ice, equivalent to ~16 mL air, which is less than previous methods. This large suite of parameters on a single ice sample is new and helpful to study phase relationships of parameters which are usually not measured together. A multi-parameter dataset is also key to understand in situ production processes of organic species in the ice, a critical issue observable in many organic trace gases. Novel is the determination of xenon isotope ratios using doubly charged Xe ions. The attained precision for δ136Xe is suitable to correct the isotopic ratios and mixing ratios for gravitational firn effects, with the benefit that this information is derived from the same sample. Lastly, anomalies in the Xe mixing ratio, δXe/air, can be used to detect melt layers.

  20. Study on strontium isotope abundance-ratio measurements by using a 13-MeV proton beam

    Science.gov (United States)

    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.

  1. The identification of lead ammunition as a source of lead exposure in First Nations: The use of lead isotope ratios

    Energy Technology Data Exchange (ETDEWEB)

    Tsuji, Leonard J.S. [Department of Environment and Resource Studies, University of Waterloo, Waterloo, Ontario, N2L 3G1 (Canada)], E-mail: ljtsuji@fes.uwaterloo.ca; Wainman, Bruce C. [Faculty of Health Sciences, McMaster University, Hamilton, Ontario, L8N 3Z5 (Canada); Martin, Ian D. [Department of Environment and Resource Studies, University of Waterloo, Waterloo, Ontario, N2L 3G1 (Canada); Sutherland, Celine [Attawapiskat First Nation Health Services, Attawapiskat, Ontario, P0L 1A0 (Canada); Weber, Jean-Philippe; Dumas, Pierre [Centre de toxicologie, Institut national de sante publique du Quebec, Quebec City, Quebec, G1V 5B3 (Canada); Nieboer, Evert [Faculty of Health Sciences, McMaster University, Hamilton, Ontario, L8N 3Z5 (Canada); Institute of Community Medicine, University of Tromso, Tromso N-9037 (Norway)

    2008-04-15

    The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of {sup 206}Pb/{sup 204}Pb and {sup 206}Pb/{sup 207}Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (p < 0.05) positive correlations for {sup 206}Pb/{sup 204}Pb and {sup 206}Pb/{sup 207}Pb, and a significant negative correlation for {sup 208}Pb/{sup 206}Pb, as predicted if leaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.

  2. The identification of lead ammunition as a source of lead exposure in First Nations: the use of lead isotope ratios.

    Science.gov (United States)

    Tsuji, Leonard J S; Wainman, Bruce C; Martin, Ian D; Sutherland, Celine; Weber, Jean-Philippe; Dumas, Pierre; Nieboer, Evert

    2008-04-15

    The use of lead shotshell to hunt water birds has been associated with lead-contamination in game meat. However, evidence illustrating that lead shotshell is a source of lead exposure in subsistence hunting groups cannot be deemed definitive. This study seeks to determine whether lead shotshell constitutes a source of lead exposure using lead isotope ratios. We examined stable lead isotope ratios for lichens, lead shotshell and bullets, and blood from residents of Fort Albany and Kashechewan First Nations, and the City of Hamilton, Ontario, Canada. Data were analyzed using ANOVA and regression analyses. ANOVA of isotope ratios for blood revealed significant differences with respect to location, but not sex. Hamilton differed from both Kashechewan and Fort Albany; however, the First Nations did not differ from each other. ANOVA of the isotope ratios for lead ammunition and lichens revealed no significant differences between lichen groups (north and south) and for the lead ammunition sources (pellets and bullets). A plot of (206)Pb/(204)Pb and (206)Pb/(207)Pb values illustrated that lichens and lead ammunition were distinct groupings and only the 95% confidence ellipse of the First Nations group overlapped that of lead ammunition. In addition, partial correlations between blood-lead levels (adjusted for age) and isotope ratios revealed significant (pleaded ammunition were the source of lead exposure. In conclusion, lead ammunition was identified as a source of lead exposure for First Nations people; however, the isotope ratios for lead shotshell pellets and bullets were indistinguishable. Thus, lead-contaminated meat from game harvested with lead bullets may also be contributing to the lead body burden.

  3. Gas Chromatography-Mass Spectrometry Based Isotopic Abundance Ratio Analysis of Biofield Energy Treated Methyl-2-napthylether (Nerolin)

    OpenAIRE

    2016-01-01

    Methyl-2-napthylether (nerolin) is an organic compound and has the applications in pharmaceutical, and perfume industry. The stable isotope ratio analysis is increasing importance in various field of scientific research. The objective of the current study was to evaluate the effect of the biofield energy treatment on the isotopic abundance ratios of PM+1/PM(2H/1H or 13C/12C or 17O/16O) and PM+2/PM (18O/16O) in nerolin using the gas chromatography-mass spectrometry (GC-MS). The compound neroli...

  4. Isotopic Ratios of Carbon and Oxygen in Titan's CO using ALMA

    CERN Document Server

    Serigano, Joseph; Cordiner, Martin A; Irwin, Patrick G J; Teanby, Nicholas A; Charnley, Steven B; Lindberg, Johan E

    2016-01-01

    We report interferometric observations of carbon monoxide (CO) and its isotopologues in Titan's atmosphere using the Atacama Large Millimeter/submillimeter Array (ALMA). The following transitions were detected: CO (J = 1-0, 2-1, 3-2, 6-5), $^{13}$CO (J = 2-1, 3-2, 6-5), C$^{18}$O (J = 2-1, 3-2), and C$^{17}$O (J = 3-2). Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code. We present the first spectroscopic detection of $^{17}$O in the outer solar system with C$^{17}$O detected at > 8$\\sigma$ confidence. The abundance of CO was determined to be 49.6 ${\\pm}$ 1.8 ppm, assumed to be constant with altitude, with isotopic ratios $^{12}$C/$^{13}$C = 89.9 ${\\pm}$ 3.4, $^{16}$O/$^{18}$O = 486 ${\\pm}$ 22, and $^{16}$O/$^{17}$O = 2917${\\pm}$359. The measurements of $^{12}$C/$^{13}$C and $^{16}$O/$^{18}$O ratios are the most precise values obtained in Titan's atmospheric CO to date. Our res...

  5. Probing the metabolic water contribution to intracellular water using oxygen isotope ratios of PO4

    Science.gov (United States)

    Li, Hui; Yu, Chan; Wang, Fei; Chang, Sae Jung; Yao, Jun; Blake, Ruth E.

    2016-05-01

    Knowledge of the relative contributions of different water sources to intracellular fluids and body water is important for many fields of study, ranging from animal physiology to paleoclimate. The intracellular fluid environment of cells is challenging to study due to the difficulties of accessing and sampling the contents of intact cells. Previous studies of multicelled organisms, mostly mammals, have estimated body water composition—including metabolic water produced as a byproduct of metabolism—based on indirect measurements of fluids averaged over the whole organism (e.g., blood) combined with modeling calculations. In microbial cells and aquatic organisms, metabolic water is not generally considered to be a significant component of intracellular water, due to the assumed unimpeded diffusion of water across cell membranes. Here we show that the 18O/16O ratio of PO4 in intracellular biomolecules (e.g., DNA) directly reflects the O isotopic composition of intracellular water and thus may serve as a probe allowing direct sampling of the intracellular environment. We present two independent lines of evidence showing a significant contribution of metabolic water to the intracellular water of three environmentally diverse strains of bacteria. Our results indicate that ˜30-40% of O in PO4 comprising DNA/biomass in early stationary phase cells is derived from metabolic water, which bolsters previous results and also further suggests a constant metabolic water value for cells grown under similar conditions. These results suggest that previous studies assuming identical isotopic compositions for intracellular/extracellular water may need to be reconsidered.

  6. Carbon isotope evidence implying high O2/CO2 ratios in the Permo-Carboniferous atmosphere

    Science.gov (United States)

    Beerling, D. J.; Lake, J. A.; Berner, R. A.; Hickey, L. J.; Taylor, D. W.; Royer, D. L.

    2002-11-01

    Theoretical models predict a marked increase in atmospheric O2 to ∼35% during the Permo-Carboniferous (∼300 Ma) occurring against a low (∼0.03%) CO2 level. An upper O2 value of 35%, however, remains disputed because ignition data indicate that excessive global forest fires would have ensued. This uncertainty limits interpretation of the role played by atmospheric oxygen in Late Paleozoic biotic evolution. Here, we describe new results from laboratory experiments with vascular land plants that establish that a rise in O2 to 35% increases isotopic fractionation (Δ13C) during growth relative to control plants grown at 21% O2. Despite some effect of the background atmospheric CO2 level on the magnitude of the increase, we hypothesize that a substantial Permo-Carboniferous rise in O2 could have imprinted a detectable geochemical signature in the plant fossil record. Over 50 carbon isotope measurements on intact carbon from four fossil plant clades with differing physiological ecologies and ranging in age from Devonian to Cretaceous reveal a substantial Δ13C anomaly (5‰) occurring between 300 and 250 Ma. The timing and direction of the Δ13C excursion is consistent with the effects of a high O2 atmosphere on plants, as predicted from photosynthetic theory and observed in our experiments. Preliminary calibration of the fossil Δ13C record against experimental data yields a predicted O2/CO2 mixing ratio of the ancient atmosphere consistent with that calculated from long-term models of the global carbon and oxygen cycles. We conclude that further work on the effects of O2 in the combustion of plant materials and the spread of wildfire is necessary before existing data can be used to reliably set the upper limit for paleo-O2 levels.

  7. Estimation of food composition of Hodotermes mossambicus (Isoptera: Hodotermitidae) based on observations and stable carbon isotope ratios

    Institute of Scientific and Technical Information of China (English)

    Craig T. Symes; Stephan Woodborne

    2011-01-01

    The diet of the harvester termite Hodotermes mossambicus was investigated at two sites with distinct dietary components: C4 grasses (δ13 C isotope values, -13.8‰to -14.0‰) and C3 plants (δ13C isotope values, -25.6‰ to -27.1‰). By comparing observations of food items carried into the colony by the termites and carbon isotope ratios of whole termites (that determined assimilated carbon), the relative proportion of the C3 and C4 plant food components of the termite diet was estimated. There was agreement between the observational data and stable carbon isotopic data, with grass representing approximately 93% of the diet of H, mossambicus at two study sites (urban and rural) on the South African highveld. However, when correcting for mass of food items, that is, C3 and C4, carried by termites, the proportion of grass (C4) in the diet may be underestimated.

  8. Pliocene diatom and sponge spicule oxygen isotope ratios from the Bering Sea: isotopic offsets and future directions

    Directory of Open Access Journals (Sweden)

    A. M. Snelling

    2014-05-01

    Full Text Available Oxygen isotope analyses of different size fractions of Pliocene diatoms (δ18Odiatom from the Bering Sea show no evidence of an isotope offset and support the use of bulk diatom species samples for palaeoceanographic reconstructions. Additional samples containing concentrations of sponge spicules produce δ18O values several per mille lower than δ18Odiatom with a calculated mean offset of 3.6‰ ± 0.7. This difference is significantly greater than modern day variations in water δ18O through the regional water column. Despite the potential for oxygen isotope disequilibrium within δ18Osponge, there appears to be some similarity between δ18Osponge and a global stacked benthic δ18Oforam record. This highlights the potential for δ18Osponge in palaeoenvironmental research at sites where carbonates are not readily preserved.

  9. Addressing the current bottlenecks of metabolomics: Isotopic Ratio Outlier Analysis™, an isotopic-labeling technique for accurate biochemical profiling.

    Science.gov (United States)

    de Jong, Felice A; Beecher, Chris

    2012-09-01

    Metabolomics or biochemical profiling is a fast emerging science; however, there are still many associated bottlenecks to overcome before measurements will be considered robust. Advances in MS resolution and sensitivity, ultra pressure LC-MS, ESI, and isotopic approaches such as flux analysis and stable-isotope dilution, have made it easier to quantitate biochemicals. The digitization of mass spectrometers has simplified informatic aspects. However, issues of analytical variability, ion suppression and metabolite identification still plague metabolomics investigators. These hurdles need to be overcome for accurate metabolite quantitation not only for in vitro systems, but for complex matrices such as biofluids and tissues, before it is possible to routinely identify biomarkers that are associated with the early prediction and diagnosis of diseases. In this report, we describe a novel isotopic-labeling method that uses the creation of distinct biochemical signatures to eliminate current bottlenecks and enable accurate metabolic profiling.

  10. Stable isotope ratios of carbon and hydrogen to distinguish olive oil from shark squalene-squalane.

    Science.gov (United States)

    Camin, Federica; Bontempo, Luana; Ziller, Luca; Piangiolino, Cristiana; Morchio, Gianni

    2010-06-30

    Squalene and its hydrogenated derivate squalane are widely used in the pharmaceutical and cosmetic fields. The two compounds are mainly produced from the liver oil of deep sea sharks and from olive oil distillates. Squalene and squalane from shark cost less than the same compounds derived from olive oil, and the use of these shark-derived compounds is unethical in cosmetic formulations. In this work we investigate whether (13)C/(12)C and (2)H/(1)H ratios can distinguish olive oil from shark squalene/squalane and can detect the presence of shark derivates in olive oil based products. The (13)C/(12)C ratios (expressed as delta(13)C values) of bulk samples and of pure compounds measured using isotope ratio mass spectrometry (IRMS) were significantly lower in authentic olive oil squalene/squalane (N: 13; -28.4 +/- 0.5 per thousand; -28.3 +/- 0.8 per thousand) than in shark squalene/squalane samples (N: 15; -20.5 +/- 0.7 per thousand; -20.4 +/- 0.6 per thousand). By defining delta(13)C threshold values of -27.4 per thousand and -26.6 per thousand for olive oil bulk and pure squalene/squalane, respectively, illegal addition of shark products can be identified starting from a minimum of 10%. (2)H/(1)H analysis is not useful for distinguishing the two different origins. Delta(13)C analysis is proposed as a suitable tool for detecting the authenticity of commercial olive oil squalene and squalane samples, using IRMS interfaced to an elemental analyser if the purity is higher than 80% and IRMS interfaced to a gas chromatography/combustion system for samples with lower purity, including solutions of squalane extracted from cosmetic products.

  11. The quality control of fruit juices by using the stable isotope ratios and trace metal elements concentrations

    Science.gov (United States)

    Magdas, D. A.; Dehelean, A.; Puscas, R.; Cristea, G.; Tusa, F.; Voica, C.

    2012-02-01

    In the last years, a growing number of research articles detailing the use of natural abundance light stable isotopes variations and trace metal elements concentration as geographic "tracers" to determine the provenance of food have been published. These investigations exploit the systematic global variations of stable hydrogen, oxygen and carbon isotope ratios in (combination) relation with trace metal element concentrations. The trace metal elements content of plants and also their light stable isotopic ratios are mainly related to the geological and pedoclimatic characteristics of the site of growth. The interpretation of such analysis requires an important number of data for authentic natural juices regarding the same seasonal and regional origin, because the isotopic analysis parameters of fruit juices show remarkable variability depending on climatologically factors. In this work was mesured H, C, O stable isotope ratios and the concentrations of 16 elements (P, K, Mg, Na, Ca, Cu, Cr, Ni, Zn, Pb, Co, As, Cd, Mn, Fe and Hg) from 12 single strength juices. The natural variations that appear due to different environmental and climatic conditions are presented and discussed.

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

    Science.gov (United States)

    Godin, Jean-Philippe; McCullagh, James S O

    2011-10-30

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

  13. Silicon isotope ratio measurements by inductively coupled plasma tandem mass spectrometry for alteration studies of nuclear waste glasses.

    Science.gov (United States)

    Gourgiotis, Alkiviadis; Ducasse, Thomas; Barker, Evelyne; Jollivet, Patrick; Gin, Stéphane; Bassot, Sylvain; Cazala, Charlotte

    2017-02-15

    High-level, long-lived nuclear waste arising from spent fuel reprocessing is vitrified in silicate glasses for final disposal in deep geologic formations. In order to better understand the mechanisms driving glass dissolution, glass alteration studies, based on silicon isotope ratio monitoring of (29)Si-doped aqueous solutions, were carried out in laboratories. This work explores the capabilities of the new type of quadrupole-based ICP-MS, the Agilent 8800 tandem quadrupole ICP-MS/MS, for accurate silicon isotope ratio determination for alteration studies of nuclear waste glasses. In order to avoid silicon polyatomic interferences, a new analytical method was developed using O2 as the reaction gas in the Octopole Reaction System (ORS), and silicon isotopes were measured in mass-shift mode. A careful analysis of the potential polyatomic interferences on SiO(+) and SiO2(+) ion species was performed, and we found that SiO(+) ion species suffer from important polyatomic interferences coming from the matrix of sample and standard solutions (0.5M HNO3). For SiO2(+), no interferences were detected, and thus, these ion species were chosen for silicon isotope ratio determination. A number of key settings for accurate isotope ratio analysis like, detector dead time, integration time, number of sweeps, wait time offset, memory blank and instrumental mass fractionation, were considered and optimized. Particular attention was paid to the optimization of abundance sensitivity of the quadrupole mass filter before the ORS. We showed that poor abundance sensitivity leads to a significant shift of the data away from the Exponential Mass Fractionation Law (EMFL) due to the spectral overlaps of silicon isotopes combined with different oxygen isotopes (i.e. (28)Si(16)O(18)O(+), (30)Si(16)O(16)O(+)). The developed method was validated by measuring a series of reference solutions with different (29)Si enrichment. Isotope ratio trueness, uncertainty and repeatability were found to be <0

  14. Amino acid δ13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry

    DEFF Research Database (Denmark)

    Raghavan, Maanasa; McCullagh, James S. O.; Lynnerup, Niels

    2010-01-01

    We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS......). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context...... as a proxy for bone collagen at the amino acid level, this validates compound-specific isotope studies using hair as a model for palaeodietary reconstruction. Our results suggest that a small offset observed in the bulk delta(13)C values of the hair and bone samples may be attributed to two factors: (i...

  15. Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

    Science.gov (United States)

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

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant.

  16. USE OF STABLE CARBON ISOTOPE RATIOS OF FATTY ACIDS TO EVALUATE MICROBIAL CARBON SOURCES IN TERRESTRIAL ENVIRONMENTS

    Science.gov (United States)

    We use measurements of the concentration and stable carbon isotopic ratio (D 13C) of individual microbial phospholipid fatty acids (PLFAs) in soils as indicators of live microbial biomass levels and microbial carbon source. We found that intensive sugar cane cultivation leads to ...

  17. Lead isotope ratios in tree bark pockets: An indicator of past air pollution in the Czech Republic

    Energy Technology Data Exchange (ETDEWEB)

    Conkova, M. [Charles University, Faculty of Natural Sciences, Benatska 8, Prague 1 (Czech Republic)], E-mail: conkova@chmi.cz; Kubiznakova, J. [Czech Hydrometeorogical Institute, Na Sabatce 17, Prague 4 (Czech Republic)], E-mail: kubiznakova@chmi.cz

    2008-10-15

    Tree bark pockets were collected at four sites in the Czech Republic with differing levels of lead (Pb) pollution. The samples, spanning 1923-2005, were separated from beech (Fagus sylvatica) and spruce (Picea abies). Elevated Pb content (0.1-42.4 {mu}g g{sup -1}) reflected air pollution in the city of Prague. The lowest Pb content (0.3-2.6 {mu}g g{sup -1}) was found at the Kosetice EMEP 'background pollution' site. Changes in {sup 206}Pb/{sup 207}Pb and {sup 208}Pb/{sup 206}Pb isotope ratios were in agreement with operation times of the Czech main anthropogenic Pb sources. Shortly after the Second World War, the {sup 206}Pb/{sup 207}Pb isotope ratio in bark pockets decreased from 1.17 to 1.14 and the {sup 208}Pb/{sup 206}Pb isotope ratio increased from 2.12 to 2.16. Two dominant emission sources responsible for these changes, lignite and leaded petrol combustion, contributed to the shifts in Pb isotope ratios. Low-radiogenic petrol Pb ({sup 206}Pb/{sup 207}Pb of 1.11) lead to lower {sup 206}Pb/{sup 207}Pb in bark pockets over time. High-radiogenic lignite-derived Pb ({sup 206}Pb/{sup 207}Pb of 1.18 to 1.19) was detected in areas affected by coal combustion rather than by traffic.

  18. Strontium concentrations and isotope ratios in a forest-river system in the South Qinling Mts., China.

    Science.gov (United States)

    Bu, Hongmei; Song, Xianfang; Zhang, Quanfa; Burford, Michele A

    2016-04-15

    The concentrations of dissolved strontium (Sr) and isotope ratios ((87)Sr/(86)Sr) in rainwater, river water, and water from forest soil are measured to investigate the contributions of these sources to a river during base flow conditions in the relatively pristine South Qinling Mountains, China. Dissolved Sr concentrations and (87)Sr/(86)Sr ratios vary significantly between different water types (p system in a mountainous catchment.

  19. Hydrologic control of the oxygen isotope ratio of ecosystem respiration in a semi-arid woodland

    Directory of Open Access Journals (Sweden)

    J. H. Shim

    2013-07-01

    Full Text Available We conducted high frequency measurements of the δ18O value of atmospheric CO2 from a juniper (Juniperus monosperma woodland in New Mexico, USA, over a four-year period to investigate climatic and physiological regulation of the δ18O value of ecosystem respiration (δR. Rain pulses reset δR with the dominant water source isotope composition, followed by progressive enrichment of δR. Transpiration (ET was significantly related to post-pulse δR enrichment because the leaf water δ18O value showed strong enrichment with increasing vapor pressure deficit that occurs following rain. Post-pulse δR enrichment was correlated with both ET and the ratio of ET to soil evaporation (ET/ES. In contrast, the soil water δ18O value was relatively stable and δR enrichment was not correlated with ES. Model simulations captured the large post-pulse δR enrichments only when the offset between xylem and leaf water δ18O value was modeled explicitly and when a gross flux model for CO2 retro-diffusion was included. Drought impacts δR through the balance between evaporative demand, which enriches δR, and low soil moisture availability, which attenuates δR enrichment through reduced ET. The net result, observed throughout all four years of our study, was a negative correlation of post-precipitation δR enrichment with increasing drought.

  20. Sulfur chemistry and isotopic ratios in the starburst galaxy NGC 253

    CERN Document Server

    Martín, S; Mauersberger, R; Henkel, C; García-Burillo, S

    2004-01-01

    Based on observations of the most abundant sulfur-bearing molecules (H2S, CS, NS, SO, H2CS, OCS, and SO2) carried out with the IRAM 30m telescope and SEST, we present the first analysis of the sulfur chemistry of an extragalactic source, the nuclear region of the starburst galaxy NGC 253. This is the first time that H2S and, tentatively, H2CS are detected towards the nucleus of a starburst galaxy. Source averaged fractional abundances of these molecules are a few 10^-9, except for CS and OCS which are more abundant (10^-8). Sulfur isotopic ratios, 32S/34S~8+-2 and 34S/33S>9, are measured through observations of 13CS, C34S, and C33S. A comparison with the observed relative abundances towards different prototypical Galactic sources suggests that the chemical composition of NGC 253 is similar to that found towards the molecular clouds complexes like Sgr B2 in the nuclear region of the Milky Way. The large overabundance of OCS compared to the predictions of time-dependent sulfur chemistry models supports the idea...

  1. Cu Purification Using an Extraction Resin for Determination of Isotope Ratios by Multicollector ICP-MS

    Directory of Open Access Journals (Sweden)

    Akio Makishima

    2014-06-01

    Full Text Available A new simple and quick method has been established for separation of Cu from solutions using an extraction chromatographic resin utilizing Aliquat® 336 (commercially available as TEVA™ resin and Cu(I. This method involves the use of a one milliliter column containing 0.33 mL TEVA™ resin on 0.67 mL Amberchrom® CG-71C acrylic resin. Copper was adsorbed on the column by forming Cu(I with 0.15% ascorbic acid in 0.05 mol·L−1 HBr, while other major elements except Zn showed no adsorption. After removal of the major elements (Na, Mg, Al, P, K, Ca, Cr, Mn, Fe, Co and Ni, Cu was recovered using 2 mol·L−1 HNO3. The recovery yield and total blank were 102% ± 2% and 0.25 ng, respectively. To evaluate the separation method, Cu isotope ratios were determined by a standard-sample-standard bracketing method using multicollector inductively coupled plasma-mass spectrometry (ICP-MS, with a repeatability of 0.04‰ and 0.25‰ (SD, for the standard solution and the solutions from low S (<0.1% S silicate standards, respectively.

  2. Authenticity and quality of animal origin food investigated by stable-isotope ratio analysis.

    Science.gov (United States)

    Vinci, Giuliana; Preti, Raffaella; Tieri, Alessandra; Vieri, Simone

    2013-02-01

    Authentication of a food product is the procedure by which it is verified that the product matches the statements on the label, and that it conforms to what is established by regulations. This testing process includes analysis of the ingredients, determination of the geographical origin, and examination of the production methods. In particular, the use of rapid, effective and reliable analytical methods, when correctly applied to verify the authenticity and the traceability of the product, represents a valuable and irreplaceable tool for the authorities to carry out control functions. Tools and methodologies from scientific innovation and technological evolution can help to quickly locate particularly sophisticated frauds and adulterations. The feeding regime of livestock is a fundamental issue for the properties and safety of animal origin food, but this regime is often hidden from the consumer, making the zootechnical sector more prone to fraudulent practices. This review reports the results recently obtained in authentication of animal origin food by the application of stable-isotope ratio analysis, the most promising analytical technique in this field.

  3. Origins of invasive piscivores determined from the strontium isotope ratio (87Sr/86Sr) of otoliths

    Science.gov (United States)

    Wolff, Brian A.; Johnson, Brett M.; Breton, Andre R.; Martinez, Patrick J.; Winkelman, Dana L.; Gillanders, Bronwyn

    2012-01-01

    We examined strontium isotope ratios (87Sr/86Sr) in fish otoliths to determine the origins of invasive piscivores in the Upper Colorado River Basin (UCRB, western USA). We examined 87Sr/86Sr from fishes in different reservoirs, as well as the temporal stability and interspecies variability of 87Sr/86Sr of fishes within reservoirs, determined if 87Sr/86Sr would be useful for "fingerprinting" reservoirs where invasive piscivores may have been escaping into riverine habitat of endangered fishes in the UCRB, and looked for evidence that such movement was occurring. Our results showed that in most cases 87Sr/86Sr was unique among reservoirs, overlapped among species in a given reservoir, and was temporally stable across years. We identified the likely reservoir of origin of river-caught fish in some cases, and we were also able to determine the year of possible escapement. The approach allowed us to precisely describe the 87Sr/86Sr fingerprint of reservoir fishes, trace likely origins of immigrant river fish, and exclude potential sources, enabling managers to focus control efforts more efficiently. Our results demonstrate the potential utility of 87Sr/86Sr as a site-specific and temporally stable marker for reservoir fish and its promise for tracking fish movements of invasive fishes in river-reservoir systems.

  4. Determination of the origin of urinary norandrosterone traces by gas chromatography combustion isotope ratio mass spectrometry.

    Science.gov (United States)

    Hebestreit, Moritz; Flenker, Ulrich; Fusshöller, Gregor; Geyer, Hans; Güntner, Ute; Mareck, Ute; Piper, Thomas; Thevis, Mario; Ayotte, Christiane; Schänzer, Wilhelm

    2006-09-01

    On the one hand, 19-norandrosterone (NA) is the most abundant metabolite of the synthetic anabolic steroid 19-nortestosterone and related prohormones. On the other hand, small amounts are biosynthesized by pregnant women and further evidence exists for physiological origin of this compound. The World Anti-Doping Agency (WADA) formerly introduced threshold concentrations of 2 or 5 ng of NA per ml of urine to discriminate 19-nortestosterone abuse from biosynthetic origin. Recent findings showed however, that formation of NA resulting in concentrations in the range of the threshold levels might be due to demethylation of androsterone in urine, and the WADA 2006 Prohibited List has defined NA as endogenous steroid. To elucidate the endogenous or exogenous origin of NA, (13)C/(12)C-analysis is the method of choice since synthetic 19-nortestosterone is derived from C(3)-plants by partial synthesis and shows delta(13)C(VPDB)-values of around -28 per thousand. Endogenous steroids are less depleted in (13)C due to a dietary mixture of C(3)- and C(4)-plants. An extensive cleanup based on two high performance liquid chromatography cleanup steps was applied to quality control and doping control samples, which contained NA in concentrations down to 2 ng per ml of urine. (13)C/(12)C-ratios of NA, androsterone and etiocholanolone were measured by gas chromatography/combustion/isotope ratio mass spectrometry. By comparing delta(13)C(VPDB)-values of androsterone as endogenous reference compound with NA, the origin of NA in doping control samples was determined as either endogenous or exogenous.

  5. Understanding continental-scale variation in plant hydrogen and oxygen isotope ratios - Pseudotsuga menziesii across a 1500 km transect

    Science.gov (United States)

    West, J. B.; Wilson, E.; Hyodo, A.

    2013-12-01

    The isotopic composition of plant tissues provides an important recorder of vegetation response to climate. Hydrogen and oxygen isotope ratios have been used to infer precipitation isotope ratios and therefore variability in temperature. While this is the case, important questions remain about the primary drivers of plant tissue hydrogen and oxygen isotope ratio variation, including fundamental questions about the role of plant physiology. Relatively recent work suggests, in some species, an important role of physiology in organic matter d2H, in particular stomatal conductance, while other work suggests a distinct lack of influence of physiology. It is critical that mechanistic models of plant tissue variation in δ2H and δ18O can encompass landscape and larger-scale variability in plant isotope ratios. In particular existing models need to be compared to large-scale observations in order to assess their ability to describe variation in climate and plant physiology driven by such geographic variables as continentality and elevation. We report on ongoing work to better understand the role of climate and other drivers in plant tissue isotopic composition across relatively large spatial scales. An approximately 1500 km-long transect was established from the Continental Divide in North America (at approximately 39° N latitude) to the Coast Range. Leaf, branch, and tree core samples of Pseudotsuga menziesii were collected, along with surface waters. At each location, samples were collected from at least three elevations and on the western and eastern slopes of the target mountain range. Xylem water broadly reflected local precipitation as inferred from a global precipitation isoscape model and local surface water measurements. There was also a clear difference across the transect in apparent access to surface water, with the drier interior showing greater source water evaporative enrichment. In addition, the relationships between leaf water and stem water changed

  6. Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)

    Science.gov (United States)

    Brand, Willi A.; Coplen, Tyler B.; Vogl, Jochen; Rosner, Martin; Prohaska, Thomas

    2014-01-01

    Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.

  7. Cesium chloride: preventive medicine for radioactive cesium exposure?

    Science.gov (United States)

    Braverman, E R; Sohler, A; Pfeiffer, C C

    1988-06-01

    Cesium is produced in high yield fission of uranium and plutonium. Radioactive cesium needles are a radiation hazard for radiotherapists. In this age of nuclear reactors, i.e. Chernobyl, radioactive cesium exposure may be a growing problem. Furthermore, there are numerous therapeutic potentials for cesium therapy, i.e. cancer, depression and schizophrenia. We explored the clearance of cesium in man and found that an oral dose of 50 mg maintains elevated blood cesium levels for 80 days. Cesium is accumulated mainly in the red blood cell fraction. Larger doses (6-9 grams) produce no observed harmful effects and maintain elevated blood levels of cesium for more than a year. Our data suggests there is a threshold of maximum cesium saturation in blood; if maintained, any additional cesium exposure, i.e. radioactive cesium, would be excreted at a more rapid rate. It is probable that large cesium doses can protect against radiation toxicity by blocking sites on red blood cells and thereby result in increased excretion and clearance of the radioactive forms of cesium. This hypothesis should be easily testable in laboratory animals.

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

    Science.gov (United States)

    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

  9. Spatial Distribution of Lead Isotope Ratios and Inorganic Element Concentrations in Epiphytic Lichens from the Athabasca Oil Sands Region

    Science.gov (United States)

    Graney, J. R.; Landis, M. S.; Puckett, K.; Edgerton, E.; Krupa, S.; Percy, K.

    2013-12-01

    Coupled studies of inorganic element concentrations and lead (Pb) isotope ratios have been conducted on Hypogymnia physodes samples collected in the Athabasca Oil Sands Region (AOSR) in Alberta, Canada in 2002, 2008, and 2011. To investigate the spatial extent of air emissions, the lichens were collected from sites as far as 160 km from the mining and processing operations. 30 milligram sub-samples of the lichens were microwave digested, and the extracts were analyzed using DRC-ICPMS to determine elemental concentrations, and sector field ICPMS to measure Pb isotope ratios. Concentrations of elements in the lichens were found to reflect proximity to mining and oil processing sites as well as topography, ecosystem differences, and the metabolic biogeochemistry of the lichens. An exponential decrease in concentration of metals associated with fugitive dust (aluminum and others) versus distance from the mining sites, suggests elevated coarse particle emissions associated with mining operations. Near source concentrations of metals with an oil signature (vanadium and others) are less enhanced and more homogeneous than the metals in the fugitive dust, reflecting emission and deposition of smaller diameter particles at greater distances from oil processing sources. The mining and oil processing signatures are superimposed over elemental concentrations that reflect the nutrient needs of the lichens. These findings are being confirmed through ongoing studies using dichot samplers to collect coarse and fine particulate aerosol samples. The lichen samples collected beyond 50 km from the mining and processing sites cluster into a Pb isotope grouping with a 207Pb / 206Pb ratio of 0.8650 and a 208Pb / 206Pb ratio near 2.095. This grouping likely reflects the regional background Pb isotope ratio signature. 207Pb / 206Pb and 208Pb / 206Pb ratios decrease as one nears the mining and processing operations. This indicates that other Pb source(s), (e.g. Pb in the bitumen from the oil

  10. Application of multi-isotope ratios to study the source and quality of urban groundwater in Metro Manila, Philippines

    Energy Technology Data Exchange (ETDEWEB)

    Hosono, Takahiro, E-mail: hosono@kumamoto-u.ac.jp [Priority Organization for Innovation and Excellence, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Siringan, Fernando [Marine Science Institute, University of the Philippines, Diliman, Quezon City 1101 (Philippines); Yamanaka, Tsutomu [Terrestrial Environment Research Center, University of Tsukuba, Tsukuba, Ibaraki 305-8577 (Japan); Umezawa, Yu [Faculty of Fisheries, Nagasaki University, 1-14 Bunkyo-machi Nagasaki, 852-8521 (Japan); Onodera, Shin-ichi [Graduate School of Integrated Arts and Sciences, Hiroshima University, 1-7-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8521 (Japan); Nakano, Takanori; Taniguchi, Makoto [Research Institute for Humanity and Nature, 457-4 Motoyama Kamigamo, Kita-ku, Kyoto 603-8047 (Japan)

    2010-06-15

    To characterize water quality in terms of dissolved elements and to investigate both the origin of the water and the source and behavior of groundwater contaminants in Metro Manila, 33 water (groundwater and surface water) samples were analyzed for ion and element concentrations, H and O isotope ratios ({delta}D-H{sub 2}O and {delta}{sup 18}O-H{sub 2}O), SO{sub 4}{sup 2-} isotope ratios ({delta}{sup 34}S-SO{sub 4}{sup 2-} and {delta}{sup 18}O-SO{sub 4}{sup 2-}), and Sr isotope ratio ({sup 87}Sr/{sup 86}Sr). The chemical measurements showed that the primary important environmental concerns within Metro Manila are groundwater salinization for both shallow and deep aquifers, and As concentrations (up to 22.5 {mu}g/L) in shallow groundwaters. Comparison of SO{sub 4}{sup 2-} and Sr isotope values with possible source materials revealed that contamination by man-made materials such as fertilizers and detergents are present in some shallow groundwaters. Shallow groundwater having higher {delta}D-H{sub 2}O and {delta}{sup 18}O-H{sub 2}O values (av. -44 per mille {+-} 5.6 per mille and -6.8 per mille {+-} 0.6 per mille, respectively, n = 15) than deep groundwater (av. -48 per mille {+-} 4.4 per mille and -7.4 per mille {+-} 0.7 per mille, respectively, n = 7) suggests that the origins of H{sub 2}O in both groundwaters are different from each other. Since the mixing of shallow and deep groundwater does not commonly occur under Metro Manila, the contaminants in the shallow aquifers are unlikely to be transported into the deep aquifers. Sulfate reduction by bacterial activity was observed for some groundwaters, resulting in a maximum elevation in {delta}{sup 34}S-SO{sub 4}{sup 2-} values of around 10 per mille. By using SO{sub 4}{sup 2-} isotope ratios as an indicator of changes in redox conditions and Sr isotope ratio as a source indicator, it was shown that As was dissolved from unconsolidated sedimentary deposits of volcanic origin which enclose shallow unconfined aquifers

  11. {sup 15}N/{sup 14}N isotopic ratio and statistical analysis: an efficient way of linking seized Ecstasy tablets

    Energy Technology Data Exchange (ETDEWEB)

    Palhol, Fabien; Lamoureux, Catherine; Chabrillat, Martine; Naulet, Norbert

    2004-05-10

    In this study, the {sup 15}N/{sup 14}N isotopic ratios of 106 samples of 3,4-methylenedioxymethamphetamine (MDMA) extracted from Ecstasy tablets are presented. These ratios, measured using gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS), show a large discrimination between samples with a range of {delta}{sup 15}N values between -17 and +19%o, depending on the precursors and the method used in clandestine laboratories. Thus, {delta}{sup 15}N values can be used in a statistical analysis carried out in order to link Ecstasy tablets prepared with the same precursors and synthetic pathway. The similarity index obtained after principal component analysis and hierarchical cluster analysis appears to be an efficient way to group tablets seized in different places.

  12. Congener-specific carbon isotopic analysis of technical PCB and PCN mixtures using two-dimensional gas chromatography-isotope ratio mass spectrometry.

    Science.gov (United States)

    Horii, Yuichi; Kannan, Kurunthachalam; Petrick, Gert; Gamo, Toshitaka; Falandysz, Jerzy; Yamashita, Nobuyoshi

    2005-06-01

    Analysis of stable carbon isotope fractionation is a useful method to study the sources and fate of anthropogenic organic contaminants such as polychlorinated biphenyls (PCBs) in the environment. To evaluate the utility of carbon isotopes, determination of isotopic ratios of 13C/12C in source materials, for example, technical PCB preparations, is needed. In this study, we determined delta13C values of 31 chlorobiphenyl (CB) congeners in 18 technical PCB preparations and 15 chloronaphthalene (CN) congeners in 6 polychlorinated naphthalene preparations using two-dimensional gas chromatography-combustion furnace-isotope ratio mass spectrometry (2DGC-C-IRMS). Development of 2DGC-IRMS enabled improved resolution and sensitivity of compound-specific carbon isotope analysis (CSIA) of CB or CN congeners. Delta13C values of PCB congeners ranged from -34.4 (Delors) to -22.0/1000 (Sovol). Analogous PCB preparations with similar chlorine content, but different geographical origin, had different delta13C values. PCB preparations from Eastern European countries--Delors, Sovol, Trichlorodiphenyl, and Chlorofen--had distinct delta13C values. PCB mixtures showed increased 13C depletion with increasing chlorine content. Delta13C values for individual CB congeners varied depending on the degree of chlorination in technical mixtures. Delta13C values of CN congeners in Halowaxes ranged from -26.3 to -21.7/1000 and these values are within the ranges observed for PCBs. This study establishes the range of delta13C values in technical PCB and PCN preparations, which may prove to be useful in the determination of sources of these compounds in the environment. This is the first study to employ 2DGC-IRMS analysis of delta13C values in technical PCB and PCN preparations.

  13. Emerging techniques in vegetable oil analysis using stable isotope ratio mass spectrometry

    Directory of Open Access Journals (Sweden)

    Rhodes, Christopher

    2002-03-01

    Full Text Available As the practice of vegetable oil adulteration becomes more sophisticated, the possibility to subvert detection using established techniques such as capillary gas chromatography is increasing. One of the most powerful techniques to be used in food authenticity studies is stable isotope ratio mass spectrometry (SIRMS which utilises differences in the natural abundance of the stable isotopes of the ‘light’ bio-elements hydrogen, nitrogen, carbon, oxygen and sulfur to detect food fraud. SIRMS has found application in the authentication of a wide range of foodstuffs, including fruit juices, wines, spirits, honey and to detect the adulteration of flavour compounds with synthetic analogues. This papers reviews the current state-of-the-art for the authentication of vegetable oils using SIRMS and highlights emergent techniques such as compound- and position specific-isotope mass spectrometry. These latter developments offer the potential to provide more rapid and improved detection of the economic adulteration of vegetable oils.A medida que la práctica de la adulteración de aceites vegetales se hace más sofisticada, las posibilidades de evitar la detección utilizando técnicas tradicionales como la cromatografía de gases en columna capilar aumentan. Una de las técnicas más poderosas que más se utilizan en los estudios de autentificación de alimentos es la espectrometría de masas de relaciones isotópicas, que utiliza diferencias en la abundancia natural de isótopos estables de elementos ligeros biológicos hidrógeno, nitrógeno, carbón, oxigeno y azufre para detectar fraude en los alimentos. La espectrometría de masas de relaciones isotópicas ha encontrado aplicación en la autentificación de una amplia gama de alimentos, incluyendo zumos de frutas, vinos, bebidas alcohólicas de alta graduación, miel, y en la detección de la adulteración de los compuestos aromáticos con sus análogos de origen sintético. Este trabajo

  14. Protein Stable Isotope Fingerprinting (P-SIF): Multidimensional Protein Chromatography Coupled to Stable Isotope-Ratio Mass Spectrometry

    Science.gov (United States)

    Pearson, A.; Bovee, R. J.; Mohr, W.; Tang, T.

    2012-12-01

    As metagenomics increases our insight into microbial community diversity and metabolic potential, new approaches are required to determine the biogeochemical expression of this potential within ecosystems. Because stable isotopic analysis of the major bioactive elements (C, N) has been used historically to map flows of substrates and energy among macroscopic food webs, similar principles may apply to microbes. To address this challenge, we have developed a new analytical approach called Protein Stable Isotope Fingerprinting (P-SIF). P-SIF generates natural stable isotopic fingerprints of microbial individual or community proteomes. The main advantage of P-SIF is the potential to bridge the gap between diversity and function, thereby providing a window into the "black box" of environmental microbiology and helping to decipher the roles of uncultivated species. Our method implements a three-way, orthogonal scheme to separate mixtures of whole proteins into subfractions dominated by single or closely-related proteins. Protein extracts first are isoelectrically focused in a gel-free technique that yields 12 fractions separated over a gradient of pH 3-10. Each fraction then is separated by size-exclusion chromatography into 20 pools, ranging from >100kD to ~10kD. Finally, each of these pools is subjected to HPLC and collected in 40 time-slices based on protein hydrophobicity. Theoretical calculation reveals that the true chromatographic resolution of the total scheme is 5000, somewhat less than the 9600 resulting fractions. High-yielding fractions are subjected to δ13C analysis by spooling-wire microcombustion irMS (SWiM-irMS) optimized for samples containing 1-5 nmol carbon. Here we will present the method, results for a variety of pure cultures, and preliminary data for a sample of mixed environmental proteins. The data show the promise of this method for unraveling the metabolic complexity hidden within microbial communities.

  15. Poster 9: Isotopic Ratios of Carbon and Oxygen in Titan's CO using ALMA

    Science.gov (United States)

    Serigano, Joseph; Nixion, Conor A.; Cordiner, Martin A.; Irwin, Patrick G. J.; Teanby, Nick A.; Charnley, Steven B.; Lindberg, Johan E.

    2016-06-01

    The advent of the Atacama Large Millimeter/Submillimeter Array (ALMA) has provided a new and powerful facility for probing the atmospheres of solar system targets at long wavelengths (84-720 GHz) where the rotational lines of small, polar molecules are prominent. In the complex atmosphere of Titan, photochemical processes dissociate and ionize molecular nitrogen and methane in the upper atmosphere, creating a complex inventory of trace hydrocarbons and nitriles. Additionally, the existence of oxygen on Titan facilitates the synthesis of molecules of potential astrobiological importance. Utilization of ground-based submillimeter observations of Titan has proven to be a powerful tool to complement results from spacecraft observations. ALMA provides the ability to probe this region in greater detail with unprecedented spectral and spatial resolution at high sensitivity, allowing for the derivation of vertical mixing profiles, molecular detections, and observations of latitudinal and seasonal variations. Recent ALMA studies of Titan have presented spectrally and spatially-resolved maps of HNC and HC3N emission (Cordiner et al. 2014), as well as the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan's atmosphere (Cordiner et al. 2015). This poster will focus on ALMA observations of carbon monoxide (CO) and its isotopologues 13CO, C18O, and C 17O in Titan's atmosphere. Molecular abundances and the vertical atmospheric temperature profile were derived by modeling the observed emission line profiles using NEMESIS, a line-by-line radiative transfer code (Irwin et al. 2008). This study reports the first spectroscopic detection of 17O in the outer solar system with C17O detected at >8σ confidence. The abundances of these molecules and isotopic ratios of 12C/13C, 16O/18O, and 16O/17O will be presented. General implications for the history of Titan from these measurements will be discussed.

  16. Relations between oxygen stable isotopic ratios in precipitation and relevant meteorological factors in southwest China

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    The correlations of isotopic ratios in precipitation with temperature, air pressure and humidity at dif- ferent altitudes, in southwest China, are analyzed. There appear marked negative correlations for the δ 18O in precipitation with precipitation amount, vapor pressure and atmospheric precipitable water (PW) at Mengzi, Simao and Tengchong stations on synoptic timescale; the marked negative correlations between the δ 18O in precipitation and the diurnal mean temperature at 400 hPa, 500 hPa, 700 hPa and 850 hPa are different from the temperature effect in middle-high-latitude inland. Moreover, the notable positive correlation between the δ 18O in precipitation and the dew-point deficit △Td at different altitudes is found at the three stations. On annual timescale, the annual precipitation amount weighted mean δ 18O display the negative correlations not only with annual precipitation but also with annual mean temperature at 500 hPa. It can be deduced that, in the years with abnormally strong summer monsoon, more warm and wet air from low-latitude oceans is transported northward along the vapor channel located in southwest China and generates abnormally strong rainfall on the way. Meanwhile, the ab- normally strong condensation process will release more condensed latent heat into atmosphere, and lead to the rise of atmospheric temperature during rainfall, but decline of the δ 18O in precipitation. On the contrary, in the years with abnormally weak summer monsoon, the abnormally weak condensation process will release less condensed latent heat into atmosphere, and lead to the decline of atmos- pheric temperature during rainfall, but increase of the δ 18O in precipitation.

  17. Relations between oxygen stable isotopic ratios in precipitation and relevant meteorological factors in southwest China

    Institute of Scientific and Technical Information of China (English)

    ZHANG XinPing; LIU JingMiao; SUN WeiZheng; HUANG YiMin; ZHANG JianMing

    2007-01-01

    The correlations of isotopic ratios in precipitation with temperature, air pressure and humidity at different altitudes, in southwest China, are analyzed. There appear marked negative correlations for the δ18O in precipitation with precipitation amount, vapor pressure and atmospheric precipitable water(PW) at Mengzi, Simao and Tengchong stations on synoptic timescale; the marked negative correlations between the δ18O in precipitation and the diurnal mean temperature at 400 hPa,500 hPa,700 hPa and 85O hPa are different from the temperature effect in middle-high-latitude inland. Moreover, the notable positive correlation between the δ18O in precipitation and the dew-point deficit △Td at different altitudes is found at the three stations. On annual timescale, the annual precipitation amount weighted mean δ18O display the negative correlations not only with annual precipitation but also with annual mean temperature at 500 hPa. It can be deduced that, in the years with abnormally strong summer monsoon, more warm and wet air from low-latitude oceans is transported northward along the vapor channel located in southwest China and generates abnormally strong rainfall on the way. Meanwhile, the abnormally strong condensation process will release more condensed latent heat into atmosphere, and lead to the rise of atmospheric temperature during rainfall. But decline of the δ18O in precipitation. On the contrary, in the years with abnormally weak summer monsoon, the abnormally weak condensation process will release less condensed latent heat into atmosphere, and lead to the decline of atmospheric temperature during rainfall, but increase of the δ18O in precipitation.

  18. Potential of using stable nitrogen isotope ratio measurements to resolve fuel and thermal NOx in coal combustion

    Energy Technology Data Exchange (ETDEWEB)

    Chenggong Sun; Janos Lakatos; Colin E. Snape; Tony Fallick [University of Nottingham, Nottingham (United Kingdom). School of Chemical, Environmental and Mining Engineering (SChEME)

    2003-07-01

    In order to examine the potential of applying isotopic analysis to apportion NOx formation from different mechanisms, stable nitrogen isotope ratio measurements have been conducted on a number of thermal/prompt (diesel) and actual (coal) PF NO samples generated from a 1MW test facility at Powergen (UK), together with measurements on a range of pyrolysis and combustion chars obtained from a drop-tube reactor. A highly effective nitrogen-free sorbent, derived from white sugar with Mn as promoter, has been developed using an innovative procedure. This adsorbent has facilitated, for the first time, the determination of {delta}{sup 15}N values without background corrections. The isotopic data indicate that the thermal/prompt NOx collected during start-up with diesel as fuel has a {delta}{sup 15}N of close to 6.5(per thousand) compared to +15(per thousand) for the actual PF sample analysed. Thus, differences of up to ca. 20(per thousand) have been found to exist between thermal and PF fuel (char) NOx isotopic values. This augurs very well for the further development of the approach in order to help quantify the extent of thermal/prompt NOx formation in PF combustion. Measurements on chars have indicated that the extent of isotopic fractionation that occurs between coal-N and NOx from char is related to the reactivity of coals. Further, it would appear that much of the isotopic fractionation that occurs between coal nitrogen and fuel NO arises in the formation of char, although further fractionation can be inferred to occur during char combustion. In contrast, a lesser degree of isotopic fractionation is associated with the formation of thermal NO (ca. 6(per thousand)), atmospheric nitrogen having a value of 0(per thousand). 4 refs., 6 tabs.

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

    Science.gov (United States)

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

    2009-01-01

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

  20. Stable isotope ratio mass spectrometry and physical comparison for the forensic examination of grip-seal plastic bags.

    Science.gov (United States)

    Taylor, Erica; Carter, James F; Hill, Jenny C; Morton, Carolyn; Daeid, Niamh Nic; Sleeman, Richard

    2008-05-20

    Plastic bags are frequently used to package drugs, explosives and other contraband. There exists, therefore, a requirement in forensic casework to compare bags found at different locations. This is currently achieved almost exclusively by the use of physical comparisons such as birefringence patterns. This paper discusses some of the advantages and shortcomings of this approach, and presents stable isotope ratio mass spectrometry (IRMS) as a supplementary tool for effecting comparisons of this nature. Carbon and hydrogen isotopic data are presented for sixteen grip-seal plastic bags from a wide range of sources, in order to demonstrate the range of values which is likely to be encountered. Both isotopic and physical comparison (specifically birefringence) techniques are then applied to the analysis of rolls of bags from different manufacturing lots from a leading manufacturer. Both approaches are able to associate bags from a common production batch. IRMS can be applied to small fragments which are not amenable to physical comparisons, and is able to discriminate bags which could be confused using birefringence patterns alone. Similarly, in certain cases birefringence patterns discriminate bags with similar isotopic compositions. The two approaches are therefore complementary. When more than one isotopically distinct region exists within a bag (e.g. the grip-seal is distinct from the body) the ability to discriminate and associate bags is greatly increased.

  1. Isotope ratio measurement of uranium in safeguards environmental samples by inductively-coupled plasma mass spectrometry (ICP-MS)

    Energy Technology Data Exchange (ETDEWEB)

    Magara, Masaaki; Sakakibara, Takaaki; Kurosawa, Setsumi; Takahashi, Masato; Sakurai, Satoshi; Hanzawa, Yukiko; Esaka, Fumitaka; Watanabe, Kazuo; Usuda, Shigekazu [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2002-04-01

    In order to measure isotope ratio of uranium in safeguards environmental samples with ICP-MS precisely, production of polyatomic ions of IrAr, PtAr and AuAr was measured and mass bias of ICP-MS is investigated by using isotopic standards of uranium and lead. The intensities of IrAr, PtAr and AuAr relative to the atomic ions were found to be 1.8 x 10{sup -6}, 1.6 x 10{sup -5} and 4.1 x 10{sup -5}, respectively. The production of {sup 193}Ir{sup 40}Ar is too small to interfere with the measurement of {sup 233}U, if the concentration of Ir is the same level as that of {sup 233}U. However, there is possibility that the presence of Pt and Au interferes with the measurement of minor isotopes of uranium and {sup 237}Np. On the other hand, the mass biases of {sup 235}U/{sup 238}U and {sup 208}Pb/{sup 206}Pb were measured with the parameter of {sup 238}U{sup 16}O/{sup 238}U. Since unexpected change of the mass bias during measurements causes frequently erroneous results, the monitoring of {sup 238}U{sup 16}O/{sup 238}U is effective for the precise isotope ratio measurement. (author)

  2. Using Gas Chromatography/Isotope Ratio Mass Spectrometry to Determine the Fractionation Factor for H2 Production by Hydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hui; Ghandi, H.; Shi, Liang; Kreuzer, Helen W.; Ostrom, Nathaniel; Hegg, Eric L.

    2012-01-15

    Hydrogenases catalyze the reversible formation of H2, and they are key enzymes in the biological cycling of H2. H isotopes should be a very useful tool in quantifying proton trafficking in biological H2 production processes, but there are several obstacles that have thus far limited the use of this tool. In this manuscript, we describe a new method that overcomes some of these barriers and is specifically designed to measure isotopic fractionation during enzyme-catalyzed H2 evolution. A key feature of this technique is that purified hydrogenases are employed, allowing precise control over the reaction conditions and therefore a high level of precision. A custom-designed high-throughput gas chromatography-isotope ratio mass spectrometer is employed to measure the isotope ratio of the H2. Using this method, we determined that the fractionation factor of H2 production by the [NiFe]-hydrogenase from Desulfivibrio fructosovran is 0.27. This result indicates that, as expected, protons are highly favored over deuterons during H2 evolution. Potential applications of this new method are discussed.

  3. Assessing diet in savanna herbivores using stable carbon isotope ratios of faeces

    Directory of Open Access Journals (Sweden)

    D. Codron

    2005-06-01

    Full Text Available In African savannas, browse-based resources (@3 plants are isotopically distinct from grasses (@4 plants. The carbon isotopic composition of the basic plant diet is recorded in animal tissues. Mammal faeces are a readily accessible, non-invasive, sample material for temporally resolved dietary reconstructions. Faeces, however, include both undigested plant matter and waste, hence accuracy of dietary calculations could potentially be compromised by shifts in plant isotopic values related to seasonal or spatial differences, or by variability in the isotopic differences between faeces and diet. A controlled feeding study of four ungulate species showed a small, consistent difference between diet and faeces of-0.9 o, irrespective of whether the diet was @3 or C4-based. Results from faeces oftaxa known to be pure grazers, pure browsers, and mixed-feeders from the Kruger National Park were entirely consistent with their diets, but the accuracy of dietary reconstructions is enhanced with data from local plant communities.

  4. The application of inductively coupled plasma dynamic reaction cell mass spectrometry for measurement of selenium isotopes, isotope ratios and chromatographic detection of selenoamino acids

    DEFF Research Database (Denmark)

    Sloth, Jens Jørgen; Larsen, Erik Huusfeldt

    2000-01-01

    orders of magnitude by using methane as reactive cell gas in the DRC. By using 3% v/v methanol in water for carbon-enhanced ionisation of selenium, the sensitivity of Se-80 was 10(4) counts s(-1) per ng ml(-1) of selenium, and the estimated limit of detection was 6 pg ml(-1). The precision of the isotope...... ratios. Deuterated methane used as the DRC gas showed that hydrogen transfer from methane was not involved in the formation of SeH as SeD was absent in the mass spectrum. The almost interference-free detection of selenium by ICP-DRC-MS made the detection of the Se-80 isotope possible for detection...

  5. Stable isotope ratios in meteoric recharge and groundwater at Mt. Vulture volcano, southern Italy

    Science.gov (United States)

    Paternoster, M.; Liotta, M.; Favara, R.

    2008-01-01

    SummaryA rain gauge network consisting of five sites located at different altitudes, ranging from 320 to 1285 m.a.s.l., was installed at Mt. Vulture volcano (southern Italy). Rain water samples were collected monthly over a two-year period and their isotopic composition (δ 18O and δD) was analyzed. During the same period, circulating groundwater was sampled from 24 springs and wells distributed throughout the study area. Monthly isotopic composition values were used to determine the local meteoric water line (LMWL). Its slope is slightly lower than the relationship defined by Longinelli and Selmo (Longinelli, A., Selmo, E., 2003. Isotopic composition of precipitation in Italy: a first overall map. J. Hydrol. 270, 75-88) for southern Italy. The groundwater samples analyzed were distributed essentially along the LMWL. The weighted local meteoric water line (WLMWL), defined through the mean values weighted by the rainfall amount, however, may define in a short range the meteoric end-member in the local hydrological cycle more precisely. Since most of the groundwater sampling locations do not show seasonal variations in their stable isotope values, the flow system appears to be relatively homogeneous. The mean altitude of the recharge by rainfall infiltration was estimated on the basis of the local vertical isotopic gradient δ 18O. A few springs, which show anomalous isotopic values, reveal more regional circulation systems, associated with tectonic structures responsible for the ascent of deeper water.

  6. Investigation of the {sup 236}U/{sup 238}U isotope abundance ratio in uranium ores and yellow cake samples

    Energy Technology Data Exchange (ETDEWEB)

    Srncik, M. [Vienna Univ. (Austria). Dept. of Inorganic Chemistry; European Commission, Joint Research Centre, Karlsruhe (Germany). Institute for Transuranium Elements; Mayer, K.; Hrnecek, E.; Wallenius, M.; Varga, Z. [European Commission, Joint Research Centre, Karlsruhe (Germany). Institute for Transuranium Elements; Steier, P. [Vienna Univ. (Austria). VERA Lab.; Wallner, G. [Vienna Univ. (Austria). Dept. of Inorganic Chemistry

    2011-07-01

    Uranium ores and yellow cake samples of known geographic origin were investigated for their n({sup 236}U)/n({sup 238}U) isotope abundance ratio. Samples from four different uranium mines in Australia, Brazil and Canada were selected. Uranium was separated by UTEVA {sup registered} Resin and was measured by Accelerator Mass Spectrometry (AMS) at the Vienna Environmental Research Accelerator (VERA). The measurement of the isotope abundance ratio n({sup 236}U)/n({sup 238}U) will be used to investigate possible correlations between the original mineral (uranium ore) and the intermediate product (yellow cake). Such correlations are useful indicators for nuclear forensic or for non-proliferation purposes. (orig.)

  7. Determination of the geographic origin of rice by chemometrics with strontium and lead isotope ratios and multielement concentrations.

    Science.gov (United States)

    Ariyama, Kaoru; Shinozaki, Miyuki; Kawasaki, Akira

    2012-02-22

    The objective of this study was to develop a technique for determining the country of origin of rice in the Japanese market. The rice samples included a total of 350 products grown in Japan (n = 200), the United States (n = 50), China (n = 50), and Thailand (n = 50). In this study, (87)Sr/(86)Sr and Pb isotope ((204)Pb, (206)Pb, (207)Pb, and (208)Pb) ratios and multielement concentrations (Al, Fe, Co, Ni, Cu, Rb, Sr, and Ba) were determined by high-resolution inductively coupled plasma mass spectrometry. By combining three chemometric techniques based on different principles and determination criteria, the countries of origin of rice were determined. The predictions made by 10-fold cross-validation were around 97% accurate. The presented method demonstrated the effectiveness of determining the geographic origin of an agricultural product by combining several chemometric techniques using heavy element isotope ratios and multielement concentrations.

  8. Measurement of the isotope ratio of acetic acid in vinegar by HS-SPME-GC-TC/C-IRMS.

    Science.gov (United States)

    Hattori, Ryota; Yamada, Keita; Shibata, Hiroki; Hirano, Satoshi; Tajima, Osamu; Yoshida, Naohiro

    2010-06-23

    Acetic acid is the main ingredient of vinegar, and the worth of vinegar often depends on the fermentation of raw materials. In this study, we have developed a simple and rapid method for discriminating the fermentation of the raw materials of vinegar by measuring the hydrogen and carbon isotope ratio of acetic acid using head space solid-phase microextraction (HS-SPME) combined with gas chromatography-high temperature conversion or combustion-isotope ratio mass spectrometry (GC-TC/C-IRMS). The measurement of acetic acid in vinegar by this method was possible with repeatabilities (1sigma) of +/-5.0 per thousand for hydrogen and +/-0.4 per thousand for carbon, which are sufficient to discriminate the origin of acetic acid. The fermentation of raw materials of several vinegars was evaluated by this method.

  9. Isotope ratios of H, C, and O in CO2 and H2O of the martian atmosphere.

    Science.gov (United States)

    Webster, Chris R; Mahaffy, Paul R; Flesch, Gregory J; Niles, Paul B; Jones, John H; Leshin, Laurie A; Atreya, Sushil K; Stern, Jennifer C; Christensen, Lance E; Owen, Tobias; Franz, Heather; Pepin, Robert O; Steele, Andrew; Achilles, Cherie; Agard, Christophe; Alves Verdasca, José Alexandre; Anderson, Robert; Anderson, Ryan; Archer, Doug; Armiens-Aparicio, Carlos; Arvidson, Ray; Atlaskin, Evgeny; Aubrey, Andrew; Baker, Burt; Baker, Michael; Balic-Zunic, Tonci; Baratoux, David; Baroukh, Julien; Barraclough, Bruce; Bean, Keri; Beegle, Luther; Behar, Alberto; Bell, James; Bender, Steve; Benna, Mehdi; Bentz, Jennifer; Berger, Gilles; Berger, Jeff; Berman, Daniel; Bish, David; Blake, David F; Blanco Avalos, Juan J; Blaney, Diana; Blank, Jen; Blau, Hannah; Bleacher, Lora; Boehm, Eckart; Botta, Oliver; Böttcher, Stephan; Boucher, Thomas; Bower, Hannah; Boyd, Nick; Boynton, Bill; Breves, Elly; Bridges, John; Bridges, Nathan; Brinckerhoff, William; Brinza, David; Bristow, Thomas; Brunet, Claude; Brunner, Anna; Brunner, Will; Buch, Arnaud; Bullock, Mark; Burmeister, Sönke; Cabane, Michel; Calef, Fred; Cameron, James; Campbell, John; Cantor, Bruce; Caplinger, Michael; Caride Rodríguez, Javier; Carmosino, Marco; Carrasco Blázquez, Isaías; Charpentier, Antoine; Chipera, Steve; Choi, David; Clark, Benton; Clegg, Sam; Cleghorn, Timothy; Cloutis, Ed; Cody, George; Coll, Patrice; Conrad, Pamela; Coscia, David; Cousin, Agnès; Cremers, David; Crisp, Joy; Cros, Alain; Cucinotta, Frank; d'Uston, Claude; Davis, Scott; Day, Mackenzie; de la Torre Juarez, Manuel; DeFlores, Lauren; DeLapp, Dorothea; DeMarines, Julia; DesMarais, David; Dietrich, William; Dingler, Robert; Donny, Christophe; Downs, Bob; Drake, Darrell; Dromart, Gilles; Dupont, Audrey; Duston, Brian; Dworkin, Jason; Dyar, M Darby; Edgar, Lauren; Edgett, Kenneth; Edwards, Christopher; Edwards, Laurence; Ehlmann, Bethany; Ehresmann, Bent; Eigenbrode, Jen; Elliott, Beverley; Elliott, Harvey; Ewing, Ryan; Fabre, Cécile; Fairén, Alberto; Farley, Ken; Farmer, Jack; Fassett, Caleb; Favot, Laurent; Fay, Donald; Fedosov, Fedor; Feldman, Jason; Feldman, Sabrina; Fisk, Marty; Fitzgibbon, Mike; Floyd, Melissa; Flückiger, Lorenzo; Forni, Olivier; Fraeman, Abby; Francis, Raymond; François, Pascaline; Freissinet, Caroline; French, Katherine Louise; Frydenvang, Jens; Gaboriaud, Alain; Gailhanou, Marc; Garvin, James; Gasnault, Olivier; Geffroy, Claude; Gellert, Ralf; Genzer, Maria; Glavin, Daniel; Godber, Austin; Goesmann, Fred; Goetz, Walter; Golovin, Dmitry; Gómez Gómez, Felipe; Gómez-Elvira, Javier; Gondet, Brigitte; Gordon, Suzanne; Gorevan, Stephen; Grant, John; Griffes, Jennifer; Grinspoon, David; Grotzinger, John; Guillemot, Philippe; Guo, Jingnan; Gupta, Sanjeev; Guzewich, Scott; Haberle, Robert; Halleaux, Douglas; Hallet, Bernard; Hamilton, Vicky; Hardgrove, Craig; Harker, David; Harpold, Daniel; Harri, Ari-Matti; Harshman, Karl; Hassler, Donald; Haukka, Harri; Hayes, Alex; Herkenhoff, Ken; Herrera, Paul; Hettrich, Sebastian; Heydari, Ezat; Hipkin, Victoria; Hoehler, Tori; Hollingsworth, Jeff; Hudgins, Judy; Huntress, Wesley; Hurowitz, Joel; Hviid, Stubbe; Iagnemma, Karl; Indyk, Steve; Israël, Guy; Jackson, Ryan; Jacob, Samantha; Jakosky, Bruce; Jensen, Elsa; Jensen, Jaqueline Kløvgaard; Johnson, Jeffrey; Johnson, Micah; Johnstone, Steve; Jones, Andrea; Joseph, Jonathan; Jun, Insoo; Kah, Linda; Kahanpää, Henrik; Kahre, Melinda; Karpushkina, Natalya; Kasprzak, Wayne; Kauhanen, Janne; Keely, Leslie; Kemppinen, Osku; Keymeulen, Didier; Kim, Myung-Hee; Kinch, Kjartan; King, Penny; Kirkland, Laurel; Kocurek, Gary; Koefoed, Asmus; Köhler, Jan; Kortmann, Onno; Kozyrev, Alexander; Krezoski, Jill; Krysak, Daniel; Kuzmin, Ruslan; Lacour, Jean Luc; Lafaille, Vivian; Langevin, Yves; Lanza, Nina; Lasue, Jeremie; Le Mouélic, Stéphane; Lee, Ella Mae; Lee, Qiu-Mei; Lees, David; Lefavor, Matthew; Lemmon, Mark; Lepinette Malvitte, Alain; Léveillé, Richard; Lewin-Carpintier, Éric; Lewis, Kevin; Li, Shuai; Lipkaman, Leslie; Little, Cynthia; Litvak, Maxim; Lorigny, Eric; Lugmair, Guenter; Lundberg, Angela; Lyness, Eric; Madsen, Morten; Maki, Justin; Malakhov, Alexey; Malespin, Charles; Malin, Michael; Mangold, Nicolas; Manhes, Gérard; Manning, Heidi; Marchand, Geneviève; Marín Jiménez, Mercedes; Martín García, César; Martin, Dave; Martin, Mildred; Martínez-Frías, Jesús; Martín-Soler, Javier; Martín-Torres, F Javier; Mauchien, Patrick; Maurice, Sylvestre; McAdam, Amy; McCartney, Elaina; McConnochie, Timothy; McCullough, Emily; McEwan, Ian; McKay, Christopher; McLennan, Scott; McNair, Sean; Melikechi, Noureddine; Meslin, Pierre-Yves; Meyer, Michael; Mezzacappa, Alissa; Miller, Hayden; Miller, Kristen; Milliken, Ralph; Ming, Douglas; Minitti, Michelle; Mischna, Michael; Mitrofanov, Igor; Moersch, Jeff; Mokrousov, Maxim; Molina Jurado, Antonio; Moores, John; Mora-Sotomayor, Luis; Morookian, John Michael; Morris, Richard; Morrison, Shaunna; Mueller-Mellin, Reinhold; Muller, Jan-Peter; Muñoz Caro, Guillermo; Nachon, Marion; Navarro López, Sara; Navarro-González, Rafael; Nealson, Kenneth; Nefian, Ara; Nelson, Tony; Newcombe, Megan; Newman, Claire; Newsom, Horton; Nikiforov, Sergey; Nixon, Brian; Noe Dobrea, Eldar; Nolan, Thomas; Oehler, Dorothy; Ollila, Ann; Olson, Timothy; de Pablo Hernández, Miguel Ángel; Paillet, Alexis; Pallier, Etienne; Palucis, Marisa; Parker, Timothy; Parot, Yann; Patel, Kiran; Paton, Mark; Paulsen, Gale; Pavlov, Alex; Pavri, Betina; Peinado-González, Verónica; Peret, Laurent; Perez, Rene; Perrett, Glynis; Peterson, Joe; Pilorget, Cedric; Pinet, Patrick; Pla-García, Jorge; Plante, Ianik; Poitrasson, Franck; Polkko, Jouni; Popa, Radu; Posiolova, Liliya; Posner, Arik; Pradler, Irina; Prats, Benito; Prokhorov, Vasily; Purdy, Sharon Wilson; Raaen, Eric; Radziemski, Leon; Rafkin, Scot; Ramos, Miguel; Rampe, Elizabeth; Raulin, François; Ravine, Michael; Reitz, Günther; Rennó, Nilton; Rice, Melissa; Richardson, Mark; Robert, François; Robertson, Kevin; Rodriguez Manfredi, José Antonio; Romeral-Planelló, Julio J; Rowland, Scott; Rubin, David; Saccoccio, Muriel; Salamon, Andrew; Sandoval, Jennifer; Sanin, Anton; Sans Fuentes, Sara Alejandra; Saper, Lee; Sarrazin, Philippe; Sautter, Violaine; Savijärvi, Hannu; Schieber, Juergen; Schmidt, Mariek; Schmidt, Walter; Scholes, Daniel; Schoppers, Marcel; Schröder, Susanne; Schwenzer, Susanne; Sebastian Martinez, Eduardo; Sengstacken, Aaron; Shterts, Ruslan; Siebach, Kirsten; Siili, Tero; Simmonds, Jeff; Sirven, Jean-Baptiste; Slavney, Susie; Sletten, Ronald; Smith, Michael; Sobrón Sánchez, Pablo; Spanovich, Nicole; Spray, John; Squyres, Steven; Stack, Katie; Stalport, Fabien; Stein, Thomas; Stewart, Noel; Stipp, Susan Louise Svane; Stoiber, Kevin; Stolper, Ed; Sucharski, Bob; Sullivan, Rob; Summons, Roger; Sumner, Dawn; Sun, Vivian; Supulver, Kimberley; Sutter, Brad; Szopa, Cyril; Tan, Florence; Tate, Christopher; Teinturier, Samuel; ten Kate, Inge; Thomas, Peter; Thompson, Lucy; Tokar, Robert; Toplis, Mike; Torres Redondo, Josefina; Trainer, Melissa; Treiman, Allan; Tretyakov, Vladislav; Urqui-O'Callaghan, Roser; Van Beek, Jason; Van Beek, Tessa; VanBommel, Scott; Vaniman, David; Varenikov, Alexey; Vasavada, Ashwin; Vasconcelos, Paulo; Vicenzi, Edward; Vostrukhin, Andrey; Voytek, Mary; Wadhwa, Meenakshi; Ward, Jennifer; Weigle, Eddie; Wellington, Danika; Westall, Frances; Wiens, Roger Craig; Wilhelm, Mary Beth; Williams, Amy; Williams, Joshua; Williams, Rebecca; Williams, Richard B; Wilson, Mike; Wimmer-Schweingruber, Robert; Wolff, Mike; Wong, Mike; Wray, James; Wu, Megan; Yana, Charles; Yen, Albert; Yingst, Aileen; Zeitlin, Cary; Zimdar, Robert; Zorzano Mier, María-Paz

    2013-07-19

    Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.

  10. Carbon isotope ratios of Phanerozoic marine cements: Re-evaluating the global carbon and sulfur systems

    Science.gov (United States)

    Carpenter, Scott J.; Lohmann, Kyger C.

    1997-11-01

    Original δ 13C values of abiotically precipitated marine cements from a variety of stratigraphic intervals have been used to document secular variations in the δ 13C values of Phanerozoic oceans. These, together with the ° 34S values of coeval marine sulfates, are used to examine the global cycling of carbon and sulfur. It is generally accepted that secular variation in δ 13C and δ 34S values of marine carbonates and sulfates is controlled by balanced oxidation-reduction reactions and that their long-term, steady-state variation can be predicted from the present-day isotopic fractionation ratio (Δ c/Δ s) the ratio of the riverine flux of sulfur and carbon ( Fs/ Fc). The predicted slope of the linear relation between δ 13C carb and δ 34S sulfate values is approximately -0.10 to -0.14. However, temporal variation observed in marine cement δ 13C values and the 6345 values of coeval marine sulfates produces a highly significant linear relation ( r2 = 0.80; α > 95%) with a slope of -0.24; approximately twice the predicted value. This discordance suggests that either the Phanerozoic average riverine Fs/ Fc was 1.6-3.3 times greater than today's estimates or that an additional source of 34S-depleted sulfur or 13C-enriched carbon, other than continental reservoirs, was active during the Phanerozoic. This new relation between marine δ 13C and δ 34S values suggests that the flux of reduced sulfur, iron, and manganese from seafloor hydrothermal systems affects oceanic O2 levels which, in turn, control the oxidation or burial of organic matter, and thus the δ 13C value of marine DIC. Therefore, the sulfur system (driven by seafloor hydrothermal systems) controls the carbon system rather than organic carbon burial controlling the response of δ 34S values (via formation of sedimentary pyrite). Secular variation of marine 87Sr/86Sr ratios and δ 13C values argues for a coupling of δ 34S and δ 34S values to variation in the relative contribution of seafloor

  11. Evaluation of Perchlorate Sources in the Rialto-Colton and Chino California Subbasins using Chlorine and Oxygen Isotope Ratio Analysis

    Science.gov (United States)

    2015-03-01

    chlorine-36. gt·mmdwater. forensic . Atacama. nitrate. fettilizeJ·. Chile. Rialto 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF 18. NUMBER 19a. NAME...transport in the study area; (2) water chemistry analyses, including major ion composition, ClO4- concentrations, stable isotope ratios of...Chile. Most significantly for forensic studies in the U.S., indigenous natural ClO4- has been widely detected in the southwestern U.S., as

  12. Tracing the transport of anthropogenic lead in the atmosphere and in soils using isotopic ratios

    Science.gov (United States)

    Erel, Yigal; Veron, Alain; Halicz, Ludwik

    1997-11-01

    The isotopic composition of lead in aerosols and soils in Israel is used to characterize the sources of anthropogenic lead in the region, to ascertain the isotopic composition of natural, rock-derived lead in specific areas, and to determine rates of anthropogenic lead migration in soils. The isotopic composition of lead currently emitted from cars in Israel ( 206Pb /207Pb = 1.115 ± 2 ) is controlled by alkyl-lead produced in France and Germany. In addition to petrol-lead, two more sources of anthropogenic lead can be detected in sampled aerosols: the first one has low concentrations of lead (˜4 ng/m 3) and 206Pb /207Pb ˜ 1.157 , and is most likely lead, emitted in Turkey, that traveled across the eastern Mediterranean basin; the second type of aerosols contains a mixture of lead emitted in several countries including Turkey, Greece, and Ukraine ( 206Pb /207Pb value of 1.155-1.160; [Pb] ˜ 20-30 ng/m 3). Anthropogenic lead is more accessible for acid leaching than natural lead, therefore, it is more labile in the soil. The isotopic composition of lead in the acid-leached fraction of near-road soil profiles record the histor of alkyl-lead emission in the country. Based on changes in the isotopic composition of lead with soil depth, it is estimated that anthropogenic lead migrates into the soil at approximately 0.5 cm/y. A soil profile from a relatively remote area is less contaminated by anthropogenic lead and displays a different distribution of lead isotopic values with depth. The isotopic composition of lead suggests that natural lead in soils developed on carbonate bedrock is derived from clays, either from the rock-esidue (the clay fraction in the carbonate bedrock), or from airborne clay, but not from lead released from the carbonate fraction in the rock.

  13. Stable hydrogen isotope ratios of lignin methoxyl groups as a paleoclimate proxy and constraint of the geographical origin of wood.

    Science.gov (United States)

    Keppler, Frank; Harper, David B; Kalin, Robert M; Meier-Augenstein, Wolfram; Farmer, Nicola; Davis, Simon; Schmidt, Hanns-Ludwig; Brown, David M; Hamilton, John T G

    2007-01-01

    Stable isotope ratios of organic compounds are valuable tools for determining the geographical origin, identity, authenticity or history of samples from a vast range of sources such as sediments, plants and animals, including humans. Hydrogen isotope ratios (delta(2)H values) of methoxyl groups in lignin from wood of trees grown in different geographical areas were measured using compound-specific pyrolysis isotope ratio mass spectrometry analysis. Lignin methoxyl groups were depleted in (2)H relative to both meteoric water and whole wood. A high correlation (r(2) = 0.91) was observed between the delta(2)H values of the methoxyl groups and meteoric water, with a relatively uniform fractionation of -216 +/- 19 per thousand recorded with respect to meteoric water over a range of delta(2)H values from -110 in northern Norway to +20 per thousand in Yemen. Thus, woods from northern latitudes can be clearly distinguished from those from tropical regions. By contrast, the delta(2)H values of bulk wood were only relatively poorly correlated (r(2) = 0.47) with those of meteoric water. Measurement of the delta(2)H values of lignin methoxyl groups is potentially a powerful tool that could be of use not only in the constraint of the geographical origin of lignified material but also in paleoclimate, food authenticity and forensic investigations.

  14. Hydrologic control of the oxygen isotope ratio of ecosystem respiration in a semi-arid woodland

    Directory of Open Access Journals (Sweden)

    J. H. Shim

    2013-01-01

    Full Text Available We conducted high frequency measurements of the δ18O value of atmospheric CO2 from a juniper (Juniperus monosperma woodland in New Mexico, USA, over a four-year period to investigate climatic and physiological regulation of the δ18O value of ecosystem respiration (δR. Rain pulses reset δR with the dominant water source isotope composition, followed by progressive enrichment of δR. Transpiration (ET was significantly related to post-pulse δR enrichment because leaf water δ18O value showed strong enrichment with increasing vapor pressure deficit that occurs following rain. Post-pulse δR enrichment was correlated with both ET and the ratio of ET to soil evaporation (ET / ES. In contrast, soil water δ18O value was relatively stable and δR enrichment was not correlated with ES. Model simulations captured the large post-pulse δR enrichments only when the offset between xylem and leaf water δ18O value was modeled explicitly and when a gross flux model for CO2 retro-diffusion was included. Drought impacts δR through the balance between evaporative demand, which enriches δR, and low soil moisture availability, which attenuates δR enrichment through reduced ET. The net result, observed throughout all four years of our study, was a negative correlation of post-precipitation δR enrichment with increasing drought.

  15. Laser-based measurements of 18O/16O stable isotope ratios (δ18O in wine samples

    Directory of Open Access Journals (Sweden)

    Gupta M

    2013-09-01

    Full Text Available Manish Gupta,1 J Brian Leen,1 Elena Simone Franklin Berman,1 Aldo Ciambotti2 1Los Gatos Research, Mountain View, CA, USA; 2Consiglio per la Ricerca e la Sperimentazione in Agricoltura, Centro di Ricerca per l'Enologia, Asti, Italy Abstract: Wine counterfeiting is an international, multi-billion dollar issue, with some estimates suggesting that up to 5% of wines sold at auctions or secondary markets are fraudulent. Isotope ratio mass spectrometer (IRMS measurements of the 18O/16O stable isotope ratio (δ18O of water-in-wine have been used for wine authentication; however, these analyses are time-consuming and costly. In this preliminary study, off-axis integrated cavity output spectroscopy (OA-ICOS is used to quantify δ18O in wines. This laser-based method has been extensively used to study water isotopes for hydrological and medical applications. Recently, the development of a spectral contaminant identifier (SCI has extended the application of these OA-ICOS analyzers to contaminated water samples (eg, plant, soil, and leaf waters. Here, we utilize OA-ICOS with the SCI to characterize wine samples (9%–15% ethanol, and show that the laser-based instrument provides a δ18O measurement precision of ±0.07‰ (1σ and agrees with IRMS to within ±0.63‰ (1σ. Moreover, by training the SCI on isotopically-characterized wines, the agreement with IRMS improves to within ±0.30‰ (1σ. The utility of the instrument is demonstrated by measuring watered and mixed wines. The method presented here can be readily extended to address other food authentication applications. Keywords: wine isotopes, wine fraud, counterfeit wines, OA-ICOS

  16. delta(13)C and delta(2)H isotope ratios in amphetamine synthesized from benzaldehyde and nitroethane.

    Science.gov (United States)

    Collins, Michael; Salouros, Helen; Cawley, Adam T; Robertson, James; Heagney, Aaron C; Arenas-Queralt, Andrea

    2010-06-15

    Previous work in these laboratories and by Butzenlechner et al. and Culp et al. has demonstrated that the delta(2)H isotope value of industrial benzaldehyde produced by the catalytic oxidation of toluene is profoundly positive, usually in the range +300 per thousand to +500 per thousand. Synthetic routes leading to amphetamine, methylamphetamine or their precursors and commencing with such benzaldehyde may be expected to exhibit unusually positive delta(2)H values. Results are presented for delta(13)C and delta(2)H isotope values of 1-phenyl-2-nitropropene synthesized from an industrial source of benzaldehyde, having a positive delta(2)H isotope value, by a Knoevenagel condensation with nitroethane. Results are also presented for delta(13)C and delta(2)H isotope values for amphetamine prepared from the resulting 1-phenyl-2-nitropropene. The values obtained were compared with delta(13)C and delta(2)H isotope values obtained for an amphetamine sample prepared using a synthetic route that did not involve benzaldehyde. Finally, results are presented for samples of benzaldehyde, 1-phenyl-2-nitropropene and amphetamine that had been seized at a clandestine amphetamine laboratory.

  17. Utility of 5A molecular sieves to measure carbon isotope ratios in lipid biomarkers.

    Science.gov (United States)

    Tolosa, Imma; Ogrinc, Nives

    2007-09-21

    A procedure using 5A zeolite sorption to separate cyclic/branched organic compounds from the linear ones was developed and carbon isotopic fractionation effects were investigated in different families of compounds, e.g. within the hydrocarbon and alcohol compounds. The 5A sieve has a pore size such that only linear components can be incorporated into the pores whereas the cyclic/branched compounds are remaining free in the organic solution. The sorbed compounds were released from the molecular sieve with HF and solvent extracted with hexane. The method enables the isolation of linear saturated classes, such as n-alkanes and n-fatty alcohols from branched/cyclic compounds without isotopic fractionation for compound-specific isotope analysis (CSIA) of delta(13)C. However, alkene hydrocarbons, sterols and some aromatics were completely or partly degraded with the molecular sieve.

  18. Seasonal dynamics of stable isotopes and element ratios in authigenic calcites during their precipitation and dissolution, Sacrower See (northeastern Germany

    Directory of Open Access Journals (Sweden)

    Bernd ZOLITSCHKA

    2009-08-01

    Full Text Available The seasonal evolution of chemical and physical water properties as well as particle fluxes was monitored in Sacrower See (northeastern Germany during two consecutive years (Oct 2003 - Oct 2005. Additonally, we measured δ18O and δ13C as well as Sr:Ca and Mg:Ca ratios of authigenic calcites that were collected in sequencing sediment traps in order to disentangle environmental and climatic factors controlling these parameters. In particular, our aim was to find out if element ratios and the isotopic composition of calcites reflect changes in water and air temperatures. Lake water is highly enriched in 18O (-1.3 to -2.5‰ VSMOW with an evaporative increase of 0.6‰ during summer. Values are 5-6‰ more positive than groundwater values and 4-5‰ more positive than long-term weighted annual means of precipitation. During spring and summer, high amounts of dissolved phosphate cause eutrophic conditions and calcite precipitation in isotopic disequilibrium. Measured values are depleted in 18O by 2 to 10‰ compared to calculated equilibrium values. Resuspension and partial dissolution of calcite in the water column contribute to this isotopic divergence in summer and autumn as δ18Oca and δ13C values increased in the hypolimnion during this time. Mg:Ca and Sr:Ca ratios are altered by dissolution as well. In the hypolimnion these ratios were higher than in the epilimnion. Another reason for the huge deviation between measured and theoretical δ18Oca values during summer is the occurrence of large amounts of Phacotus lenticularis in the carbonate fraction. High amounts of Phacotus lead to more negative δ18Oca and more positive δ13C values. Several characteristics of δ18Oca and δ13C are also reflected by Mg:Ca and Sr:Ca ratios and isotopic composition of oxygen and carbon were influenced by the onset and stability of stratification. Especially the earlier onset of stratification in 2005 caused higher sediment fluxes and more positive carbon and

  19. Stable isotope ratios in Cape gannets around the southern coasts of Africa reveal penetration of biogeographic patterns in oceanic signatures

    Science.gov (United States)

    Jaquemet, Sébastien; McQuaid, Christopher

    2008-11-01

    The southern coasts of Africa are influenced by two major oceanic currents, leading to biogeographic patterns in inshore and offshore species assemblages, and in the stable isotope signatures of suspended particulate matter and filter-feeding mussels. We used the stable isotope ratios of carbon ( 13C/ 12C) and nitrogen ( 15N/ 14N) from the blood and feathers of adult and chick Cape gannets ( Morus capensis) to investigate whether the geographic differences observed at the lower levels in the marine communities are deep penetrating effects that reach top predators. Additionally, we evaluated whether trophic segregation occurs between adult and reared chick gannets, and whether a shift to wintering habitat occurs in adults. The study was conducted during the 2006 breeding season on Bird Island in the Agulhas system, and on Malgas and Ichaboe Islands, in the south and north Benguela respectively. Our results showed significant differences in the isotope ratios of members of different colonies, but no intra-colony differences between tissues or age groups. These results indicate that there is neither age-related nor temporal segregation in the diet of members of the same colony. Feather isotopic values suggest that adults remain all year round in the same habitats, and do not undertake long migration after reproduction. Since all gannets tend to target similar prey, we attributed among-colony differences in isotope signatures mostly to the oceanic conditions experienced by the main prey of birds rather than substantial differences in diet composition. Overall, isotopic signatures segregate the two current systems, with depleted carbon values in the Agulhas and enriched nitrogen values in the upwelled waters of the Benguela. Within the Benguela birds from Ichaboe in the north had higher δ 15N values than those from Malgas in the south, which we attributed to differences in the functioning of the upwelling cells in the vicinity of the two colonies. Finally, slight

  20. Coupling groundwater residence time and 234U/238U isotopic ratios in a granitic catchment (Vosges, Eastern France)

    Science.gov (United States)

    Viville, Daniel; Aquilina, Luc; Ackerer, Julien; Chatton, Eliot; Labasque, Thierry; Pierret, Marie-Claire; Granet, Mathieu; Perrone, Thierry; Chabaux, François

    2016-04-01

    Weathering processes are active in surface waters but groundwater also represents no neglectable chemical fluxes. As residence-time in groundwater are high, silicate weathering might take place and control Si, Ca and C fluxes. Weathering processes can be deduced from U isotopic ratios but the kinetics of these processes remain relatively poorly constrained. In order to better characterize these processes, we have coupled residence-times deduced from anthropogenic gases (CFC and SF6) analysis and 234U/238U isotopic ratios determination. Samples were collected in the Strengbach catchment (Hydro-geochemical Observatory OHGE, Vosges, eastern France). Two campaigns were carried out in May and August 2015 during two highly contrasted hydro-climatic periods. Both springs and boreholes down to 80 m depth have been sampled. A very clear geochemical distinction is observed between groundwater from surface springs and deeper groundwater from boreholes. Springs show much lower residence-time (few years) and specific chemical composition. Deeper groundwater have residence-time of several decades and different geochemical composition. A clear SF6 production is observed with increasing SF6 concentrations with residence-time. The campaign of May is characterized by highly groundwater levels and spring fluxes. All groundwater show very low residence time, except in the boreholes at depth greater than 40 m. Conversely, during low groundwater-level period in August, the residence times are much higher and CFC concentrations indicate a large mixing process between surface groundwater and deeper levels. The 234U/238U isotopic ratios confirm this vertical zonation in the boreholes, with much higher activity ratios in the deep ground-waters from borehole than in the surface and spring waters; Such high U activity ratios are indicative of long water-rock interactions, which is consistent with the long residence times deducted from the CFC and SF6 data.

  1. Carbon isotope ratio monitoring-gas chromatography mass spectrometric measurements in the marine environment: biomarker sources and paleoclimate applications.

    Science.gov (United States)

    Tolosa, I; Lopez, J F; Bentaleb, I; Fontugne, M; Grimalt, J O

    1999-09-30

    Some applications in the use of compound-specific isotopic analyses (CSIA) for biomarker source elucidation in the marine environment and its potential applications to paleoclimatology are evaluated in the present study. The potential use of the carbon isotope ratios of marine biomarkers as recorders of CO2 levels has been considered. A significant correlation between delta 13C cholesterol of suspended particulates and seawater CO2 concentrations from the south Indian Ocean has been found. delta 13C composition in biomarkers of different functionalities from three photosynthetic organisms has been examined. Small variations within and between biosynthetically related compound classes have been observed in cyanobacteria. In algae, e.g. diatoms and dinoflagellates, significant differences between the average delta 13C composition of fatty acids and sterols were observed (7.5/1000 and 2/1000, respectively). These differences can be attributed to diverse isotope effects associated with different biosynthetic reactions. Isotopic variations among homologues of the same lipid class have also been observed. In diatoms, variations were up to 5/1000 within each class of fatty acids and sterols and in the dinoflagellate species, these variations were lower than 3/1000. These differences, and particularly the intra-specific shifts in delta 13C lipid composition, must be considered for the correct interpretation of changes in delta 13C molecular signatures in the marine environment.

  2. Concentrations and activity ratios of uranium isotopes in groundwater from Doñana National Park, South of Spain

    Science.gov (United States)

    Bolívar, J. P.; Olías, M.; González-García, F.; García-Tenorio, R.

    2008-08-01

    The levels and distribution of natural radionuclides in groundwaters from the unconfined Almonte-Marismas aquifer, upon which Doñana National Park is located, have been analysed. Most sampled points were multiple piezometers trying to study the vertical distribution of the hydrogeochemical characteristics in the aquifer. Temperature, pH, electrical conductivity, dissolved oxygen and redox potential were determined in the field. A large number of parameters, physico-chemical properties, major and minor ions, trace elements and natural radionuclides (U-isotopes, Th-isotopes, Ra-isotopes and 210Po), were also analysed. In the southern zone, where aeolian sands crop out, water composition is of the sodium chloride type, and the lower U-isotopes concentrations have been obtained. As water circulates through the aquifer, bicarbonate and calcium concentrations increase slightly, and higher radionuclides concentrations were measured. Finally, we have demonstrated that 234U/238U activity ratios can be used as markers of the type of groundwater and bedrock, as it has been the case for old waters with marine origin confined by a marsh in the south-east part of aquifer.

  3. Intergroup variation in stable isotope ratios reflects anthropogenic impact on the Barbary macaques (Macaca sylvanus) of Gibraltar.

    Science.gov (United States)

    Schurr, Mark R; Fuentes, Agustín; Luecke, Ellen; Cortes, John; Shaw, Eric

    2012-01-01

    Interactions with humans impact many aspects of behavior and ecology in nonhuman primates. Because of the complexities of the human-nonhuman primate interface, methods are needed to quantify the effects of anthropogenic interactions, including their intensity and differential impacts between nonhuman primate groups. Stable isotopes can be used to quickly and economically assess intergroup dietary variation, and provide a framework for the development of specific hypotheses about anthropogenic impact. This study uses stable carbon and nitrogen isotope analysis to examine intraspecific variation in diet between five groups of Barbary macaques, Macaca sylvanus, in the Upper Rock Nature Reserve, Gibraltar. Analysis of hair from 135 macaques showed significant differences in δ(13)C and δ(15)N values between a group with minimal tourist contact and groups that were main tourist attractions. Because we observed no overt physiological or substantial behavioral differences between the groups, feeding ecology is the most likely cause of any differences in stable isotope ratios. Haphazard provisioning by tourists and Gibraltarians is a likely source of dietary variation between groups. Stable isotope analysis and observational data facilitate a deeper understanding of the feeding ecology of the Barbary macaques relevant to the role of an anthropogenic ecology for the species.

  4. Performance of the wet oxidation unit of the HPLC isotope ratio mass spectrometry system for halogenated compounds.

    Science.gov (United States)

    Gilevska, Tetyana; Gehre, Matthias; Richnow, Hans Hermann

    2014-08-05

    The performance of liquid chromatography-isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ(13)C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ(13)C(EA/LC-IRMS) = 8.8‰, TFA Δδ(13)C(EA/LC-IRMS) = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ(13)C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment.

  5. Nuclear Spectroscopy with Copper Isotopes of Extreme N/Z Ratios

    CERN Multimedia

    La commara, M; Roeckl, E; Van duppen, P L E; Schmidt, K A; Lettry, J

    2002-01-01

    The collaboration aims to obtain detailed nuclear spectroscopy information on isotopes close to the magic proton number Z=28 Very neutron-rich and neutron-deficient copper isotopes are ionized with the ISOLDE resonance ionization laser ion source (RILIS) to provide beams with low cross contamination.\\\\ \\\\On the neutron-deficient side the high $Q_\\beta$-values of $^{56}$Cu (15~MeV) and $^{57}$Cu (8.8~MeV) allow to study levels at high excitation energies in the doubly magic nucleus $^{56}$Ni and the neighbouring $^{57}$Ni. On the neutron-rich side the spectroscopy with separated copper isotopes allows presently the closest approach to the doubly magic $^{78}$Ni at an ISOL facility. Up to now no suitable target material with a rapid release was found for nickel itself. A slow release behaviour has to be assumed also for the chemically similar elements iron and cobalt.\\\\ \\\\Using a narrow-bandwidth dye laser and tuning of the laser frequency allows to scan the hyperfine splittings of the copper isotopes and isome...

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

    Science.gov (United States)

    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...

  7. CNO abundances and carbon isotope ratios in evolved stars of the open clusters NGC 2324, NGC 2477, and NGC 3960

    Science.gov (United States)

    Tautvaišienė, Gražina; Drazdauskas, Arnas; Bragaglia, Angela; Randich, Sofia; Ženovienė, Renata

    2016-10-01

    Aims: Our main aim is to determine carbon-to-nitrogen and carbon isotope ratios for evolved giants in the open clusters NGC 2324, NGC 2477, and NGC 3960, which have turn-off masses of about 2 M⊙, and to compare them with predictions of theoretical models. Methods: High-resolution spectra were analysed using a differential synthetic spectrum method. Abundances of carbon were derived using the C2 Swan (0, 1) band heads at 5135 and 5635.5 Å. The wavelength interval 7940-8130 Å with strong CN features was analysed to determine nitrogen abundances and carbon isotope ratios. The oxygen abundances were determined from the [O i] line at 6300 Å. Results: The mean values of the CNO abundances are [C/Fe] = -0.35 ± 0.06 (s.d.), [N/Fe] = 0.28 ± 0.05, and [O/Fe] = -0.02 ± 0.10 in seven stars of NGC 2324; [C/Fe] = -0.26 ± 0.02, [N/Fe] = 0.39 ± 0.04, and [O/Fe] = -0.11 ± 0.06 in six stars of NGC 2477; and [C/Fe] = -0.39 ± 0.04, [N/Fe] = 0.32 ± 0.05, and [O/Fe] = -0.19 ± 0.06 in six stars of NGC 3960. The mean C/N ratio is equal to 0.92 ± 0.12, 0.91 ± 0.09, and 0.80 ± 0.13, respectively. The mean 12C /13C ratio is equal to 21 ± 1, 20 ± 1, and 16 ± 4, respectively. The 12C /13C and C/N ratios of stars in the investigated open clusters were compared with the ratios predicted by stellar evolution models. Conclusions: The mean values of the 12C /13C and C/N ratios in NGC 2324 and NGC 2477 agree well with the first dredge-up and thermohaline-induced extra-mixing models, which are similar for intermediate turn-off mass stars. The 12C /13C ratios in the investigated clump stars of NGC 3960 span from 10 to 20. The mean carbon isotope and C/N ratios in NGC 3960 are close to predictions of the model in which the thermohaline- and rotation-induced (if rotation velocity at the zero-age main sequence was 30% of the critical velocity) extra-mixing act together. Based on observations collected at ESO telescopes under programmes 072.D-0550 and 074.D-0571.

  8. Determination of the natural abundance δ15N of taurine by gas chromatography-isotope ratio measurement mass spectrometry.

    Science.gov (United States)

    Tea, Illa; Antheaume, Ingrid; Besnard, Jorick; Robins, Richard J

    2010-12-15

    The measurement of the nitrogen isotope ratio of taurine (2-aminoethanesulphonic acid) in biological samples has a large number of potential applications. Taurine is a small water-soluble molecule which is notoriously difficult to analyze due to its polarity and functionality. A method is described which allows the determination of the natural abundance δ(15)N values of taurine and structural analogues, such as 3-amino-1-propanesulphonic acid (APSA), by isotope ratio mass spectrometry interfaced to gas chromatography (GC-irm-MS). The one-step protocol exploits the simultaneous derivatization of both functionalities of these aminosulphonic acids by reaction with triethylorthoacetate (TEOA). Conditions have been established which ensure quantitative reaction thus avoiding any nitrogen isotope fractionation during derivatization and workup. The differences in the δ(15)N values of derivatized and non-derivatized taurine and APSA all fall within the working range of 0.4‰ (-0.02 to 0.39‰). When applied to four sources of taurine with various δ(15)N values, the method achieved excellent reproducibility and accuracy. The optimized method enables the determination of the natural abundance δ(15)N values of taurine over the concentration range 1.5-7.84 µmol.mL(-1) in samples of biological origin.

  9. A model composition for Mars derived from the oxygen isotopic ratios of martian/SNC meteorites. [Abstract only

    Science.gov (United States)

    Delaney, J. S.

    1994-01-01

    Oxygen is the most abundant element in most meteorites, yet the ratios of its isotopes are seldom used to constrain the compositional history of achondrites. The two major achondrite groups have O isotope signatures that differ from any plausible chondritic precursors and lie between the ordinary and carbonaceous chondrite domains. If the assumption is made that the present global sampling of chondritic meteorites reflects the variability of O reservoirs at the time of planetessimal/planet aggregation in the early nebula, then the O in these groups must reflect mixing between known chondritic reservoirs. This approach, in combination with constraints based on Fe-Mn-Mg systematics, has been used previously to model the composition of the basaltic achondrite parent body (BAP) and provides a model precursor composition that is generally consistent with previous eucrite parent body (EPB) estimates. The same approach is applied to Mars exploiting the assumption that the SNC and related meteorites sample the martian lithosphere. Model planet and planetesimal compositions can be derived by mixing of known chondritic components using O isotope ratios as the fundamental compositional constraint. The major- and minor-element composition for Mars derived here and that derived previously for the basaltic achondrite parent body are, in many respects, compatible with model compositions generated using completely independent constraints. The role of volatile elements and alkalis in particular remains a major difficulty in applying such models.

  10. Links between purchase location and stable isotope ratios of bottled water, soda, and beer in the United States.

    Science.gov (United States)

    Chesson, Lesley A; Valenzuela, Luciano O; O'Grady, Shannon P; Cerling, Thure E; Ehleringer, James R

    2010-06-23

    This study investigated the impact of purchase location on the stable isotope ratios of beverages by measuring the delta(2)H and delta(18)O values of bottled water, soda, beer, and tap water collected across the contiguous United States. Measured beverage delta(2)H and delta(18)O values generally fit the Global Meteoric Water Line (GMWL), suggesting region-of-origin information is recorded in beverage water. Tap water delta(2)H and delta(18)O values were strongly correlated with the stable isotope ratios of bottled water and soda purchased in the same location. Beer water delta(2)H and delta(18)O values were also correlated with tap water, although not as strongly. Variability in delta(2)H and delta(18)O values among beverages purchased at a single location ranged from 2 to 41 per thousand and from 0.3 to 5.2 per thousand, respectively, but was generally moderate in most locations. It was concluded that the isotopic composition of local tap water is a reasonable proxy for consumers' fluid intake in most U.S. cities.

  11. The use of δ13C isotope ratio mass spectrometry for methamphetamine profiling: comparison of ephedrine and pseudoephedrine-based samples to P2P-based samples.

    Science.gov (United States)

    Toske, Steven G; Morello, David R; Berger, Jennifer M; Vazquez, Etienne R

    2014-01-01

    Differentiating methamphetamine samples produced from ephedrine and pseudoephedrine from phenyl-2-propanone precursors is critical for assigning synthetic route information for methamphetamine profiling. The use of isotope ratio mass spectrometry data is now a key component for tracking precursor information. Recent carbon (δ(13)C) isotope results from the analysis of numerous methamphetamine samples show clear differentiation for ephedrine and pseudoephedrine-produced samples compared to P2P-produced samples. The carbon isotope differences were confirmed from synthetic route precursor studies.

  12. The relationship between needle sugar carbon isotope ratios and tree rings of larch in Siberia.

    Science.gov (United States)

    Rinne, K T; Saurer, M; Kirdyanov, A V; Loader, N J; Bryukhanova, M V; Werner, R A; Siegwolf, R T W

    2015-11-01

    Significant gaps still exist in our knowledge about post-photosynthetic leaf level and downstream metabolic processes and isotopic fractionations. This includes their impact on the isotopic climate signal stored in the carbon isotope composition (δ(13)C) of leaf assimilates and tree rings. For the first time, we compared the seasonal δ(13)C variability of leaf sucrose with intra-annual, high-resolution δ(13)C signature of tree rings from larch (Larix gmelinii Rupr.). The trees were growing at two sites in the continuous permafrost zone of Siberia with different growth conditions. Our results indicate very similar low-frequency intra-seasonal trends of the sucrose and tree ring δ(13)C records with little or no indication for the use of 'old' photosynthates formed during the previous year(s). The comparison of leaf sucrose δ(13)C values with that in other leaf sugars and in tree rings elucidates the cause for the reported (13)C-enrichment of sink organs compared with leaves. We observed that while the average δ(13)C of all needle sugars was 1.2‰ more negative than δ(13)C value of wood, the δ(13)C value of the transport sugar sucrose was on an average 1.0‰ more positive than that of wood. Our study shows a high potential of the combined use of compound-specific isotope analysis of sugars (leaf and phloem) with intra-annual tree ring δ(13)C measurements for deepening our understanding about the mechanisms controlling the isotope variability in tree rings under different environmental conditions.

  13. Effectiveness of leaded petrol phase-out in Tianjin, China based on the aerosol lead concentration and isotope abundance ratio

    Energy Technology Data Exchange (ETDEWEB)

    Wang Wan [Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Liu Xiande [Chinese Research Academy of Environmental Sciences, Beijing 100012 (China)]. E-mail: liuxdlxd@hotmail.com; Zhao Liwei [Tianjin Environmental Monitoring Center, Tianjin, 300190 (China); Guo, Dongfa [Beijing Research Institute of Uranium Geology, Beijing 100029 (China); Tian Xiaodan [University of Antwerp, UA, B-2610 Wilrijk-Antwerpen (Belgium); Adams, Freddy [University of Antwerp, UA, B-2610 Wilrijk-Antwerpen (Belgium)

    2006-07-01

    The phase-out of leaded petrol has been a measure widely used to reduce atmospheric lead pollution. Since the 1980s, China began to promote unleaded petrol. In order to assess the effectiveness of the measure an isotope fingerprint technique was applied for aerosol samples in the city of Tianjin. After dilute acid leaching, the lead concentration and isotope abundance ratios were determined for 123 samples collected in Tianjin during eight years (1994-2001). The {sup 206}Pb / {sup 207}Pb ratio was lower in summer, when coal combustion emission was low and vehicle exhaust became more important, indicating that the {sup 206}Pb / {sup 207}Pb ratio of leaded petrol in Tianjin is lower than that of aerosol samples. The {sup 206}Pb / {sup 207}Pb ratio gradually increased from 1994 to 2001, a trend that suggests that the contribution from vehicle exhaust was diminishing. Overall, the measurements matched well with national statistical data of leaded and unleaded petrol production. After the nationwide switch to unleaded gasoline, comprehensive control measures are urgently needed to reduce air lead pollution in China, as aerosol lead reduced slightly but remains at a relatively high level.

  14. Effectiveness of leaded petrol phase-out in Tianjin, China based on the aerosol lead concentration and isotope abundance ratio

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wan; Liu, Xiande [Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhao, Liwei [Tianjin Environmental Monitoring Center, Tianjin, 300190 (China); Guo, Dongfa [Beijing Research Institute of Uranium Geology, Beijing 100029 (China); Tian, Xiaodan; Adams, Freddy [University of Antwerp, UA, B-2610 Wilrijk-Antwerpen (Belgium)

    2006-07-01

    The phase-out of leaded petrol has been a measure widely used to reduce atmospheric lead pollution. Since the 1980s, China began to promote unleaded petrol. In order to assess the effectiveness of the measure an isotope fingerprint technique was applied for aerosol samples in the city of Tianjin. After dilute acid leaching, the lead concentration and isotope abundance ratios were determined for 123 samples collected in Tianjin during eight years (1994-2001). The {sup 206}Pb/{sup 207}Pb ratio was lower in summer, when coal combustion emission was low and vehicle exhaust became more important, indicating that the {sup 206}Pb/{sup 207}Pb ratio of leaded petrol in Tianjin is lower than that of aerosol samples. The {sup 206}Pb/{sup 207}Pb ratio gradually increased from 1994 to 2001, a trend that suggests that the contribution from vehicle exhaust was diminishing. Overall, the measurements matched well with national statistical data of leaded and unleaded petrol production. After the nationwide switch to unleaded gasoline, comprehensive control measures are urgently needed to reduce air lead pollution in China, as aerosol lead reduced slightly but remains at a relatively high level. (author)

  15. On the interference of 86Kr2+ during carbon isotope analysis of atmospheric methane using continuous flow combustion – isotope ratio mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. Röckmann

    2013-02-01

    Full Text Available Stable carbon isotope analysis of methane (δ13C of CH4 on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography isotope ratio mass spectrometry coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton can severely interfere during the mass spectrometric measurement leading to significant biases in δ13C of CH4 if krypton is not sufficiently separated during the analysis. The effect comes about by the lateral tailing of the peak of doubly charged 86Kr in the neighbouring m/z, 44, 45, and 46 Faraday cups. Accordingly, the introduced bias is dependent on the chromatographic separation, the Kr to CH4 mixing ratio in the sample, the mass spectrometer source tuning as well as the detector configuration and can amount to up to several permil in δ13C. Apart from technical solutions to avoid this interference we present correction routines to a posteriori remove the bias.

  16. Use of isotope ratio mass spectrometry to differentiate between endogenous steroids and synthetic homologues in cattle: A review

    Energy Technology Data Exchange (ETDEWEB)

    Janssens, Geert, E-mail: Geert.janssens@favv.be [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Courtheyn, Dirk [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); Mangelinckx, Sven [Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice [LUNAM Université, Oniris, Laboratoire d’Etude des Résidus et Contaminants dans les Aliments (LABERCA), F-44307 Nantes (France); De Poorter, Geert [Federal Agency for the Safety of the Food Chain, Directorate General Laboratories, Kruidtuinlaan 55, 1000 Brussels (Belgium); De Kimpe, Norbert [Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000 Ghent (Belgium); Le Bizec, Bruno [LUNAM Université, Oniris, Laboratoire d’Etude des Résidus et Contaminants dans les Aliments (LABERCA), F-44307 Nantes (France)

    2013-04-15

    Graphical abstract: Scheme: Representation of the observed isotope ratios and the relation to exogenous and endogenous natural steroids. AS stands for “amount of steroid”. Highlights: ► The difference between endogenous and exogenous steroids is thoroughly laid out. ► Factors influencing the carbon ratio and the use of Δ{sup 13}C-values are explained. ► Implementation of GC/C/IRMS to detect steroid abuse in cattle is reviewed. ► Alternative methods and upcoming techniques are discussed. ► The differences and similarities with sports doping control are highlighted. -- Abstract: Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the {sup 13}C/{sup 12}C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years.

  17. Re-examining the reliability of tree-ring isotope ratio as a his- torical CO2 proxy

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    To examine the reliability of using tree ring d 13C and the modelof isotopic fractionation in reconstructing atmospheric CO2 levels, we studied the variations of some important parameters of several subtropical species under natural field conditions. It was found that, different from other researchers' results, leaf conductance to CO2 transfer, g, did not change in proportion to the change in rate of CO2 assimilation, A, with the result that intercellular concen- tration of CO2, Ci, could not keep constant. Thus, we con-clude that the use of tree-ring isotope ratios in the recon-struction of atmospheric CO2 variation based on the presup-position that Ci keeps constant during assimilation is not reliable under current circumstances.

  18. Potential of ion chromatography coupled to isotope ratio mass spectrometry via a liquid interface for beverages authentication.

    Science.gov (United States)

    Guyon, Francois; Gaillard, Laetitia; Brault, Audrey; Gaultier, Nicolas; Salagoïty, Marie-Hélène; Médina, Bernard

    2013-12-27

    New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (δ(13)C) analysis was developed to simultaneously quantify δ(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between δ(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area.

  19. Organic Reference Materials for Hydrogen, Carbon, and Nitrogen Stable Isotope-Ratio Measurements : Caffeines, n-Alkanes, Fatty Acid Methyl Esters, Glycines, L-Valines, Polyethylenes, and Oils

    NARCIS (Netherlands)

    Schimmelrnann, Arndt; Qi, Haiping; Coplen, Tyler B.; Brand, Willi A.; Fong, Jon; Meier-Augenstein, Wolfram; Kemp, Helen F.; Toman, Blaza; Ackermann, Annika; Assonov, Sergey; Aerts-Bijma, Anita T.; Brejcha, Ramona; Chikaraishi, Yoshito; Darwish, Tamim; Elsner, Martin; Gehre, Matthias; Geilmann, Heike; Groeing, Manfred; Helie, Jean-Francois; Herrero-Martin, Sara; Meijer, Harro A. J.; Sauer, Peter E.; Sessions, Alex L.; Werner, Roland A.

    2016-01-01

    An international project developed, quality-tested, and determined isotope-delta values of 19 new organic reference materials (RMs) for hydrogen, carbon, and nitrogen stable isotope-ratio measurements, in addition to analyzing pre-existing RMs NBS 22 (oil), IAEA-CH-7 (polyethylene foil), and IAEA-60

  20. Use of stable carbon and nitrogen isotope ratios in size segregated aerosol particles for the O/I penetration evaluation

    Science.gov (United States)

    Garbaras, Andrius; Garbariene, Inga; Masalaite, Agne; Ceburnis, Darius; Krugly, Edvinas; Kvietkus, Kestutis; Remeikis, Vidmantas; Martuzevicius, Dainius

    2015-04-01

    Stable carbon and nitrogen isotope ratio are successfully used in the atmospheric aerosol particle source identification [1, 2], transformation, pollution [3] research. The main purpose of this study was to evaluate the penetration of atmospheric aerosol particles from outdoor to indoor using stable carbon and nitrogen isotope ratios. Six houses in Kaunas (Lithuania) were investigated during February and March 2013. Electrical low pressure impactor was used to measure in real time concentration and size distribution of outdoor aerosol particles. ELPI+ includes 15 channels covering the size range from 0.017 to 10.0 µm. The 25 mm diameter aluminium foils were used to collect aerosol particles. Gravimetric analysis of samples was made using microbalance. In parallel, indoor aerosol samples were collected with a micro-orifice uniform deposition impactor (MOUDI model 110), where the aerosol particles were separated with the nominal D50 cut-off sizes of 0.056, 0.1, 0.18,0.32,0.56, 1.0, 1.8, 3.2, 5.6, 10, 18 μm for impactor stages 1-11, respectively. The impactor was run at a flow rate of 30 L/min. Air quality meters were used to record meteorological conditions (temperature, relative humidity) during the investigated period. All aerosol samples were analyzed for total carbon (TC) and total nitrogen (TN) contents and their isotopic compositions using elemental analyzer (EA) connected to the stable isotope ratio mass spectrometer (IRMS). TC concentration in indoors ranged from 1.5 to 247.5 µg/m3. During the sampling period outdoors TN levels ranged from 0.1 to 10.9 µg/m3. The obtained outdoor δ13C(PM2.5) values varied from -24.21 to -26.3‰, while the δ15N values varied from 2.4 to 11.1 ‰ (average 7.2±2.5 ‰). Indoors carbonaceous aerosol particles were depleted in 13C compared to outdoors in all sampling sites. This depletion in δ13C varied from 0.1 to 3.2 ‰. We think that this depletion occurs due ongoing chemical reactions (oxidation) when aerosol

  1. Study About Origin of Radioactive Cesium in Wild Mushroom in Japan

    OpenAIRE

    鎌田, 素之; 角田, 光淳

    2016-01-01

    Radioactive cesium, released from the Fukushima I nuclear power plant that destroyed by Great East Japan Earthquake, has been detected from various agricultural products. Especially, wild mushrooms are known to assimilate radioactive cesium and other heavy metals. In this study, we focused on the concentration of radioactive cesium in wild mushrooms in Japan, calculated the ratio of 134Cs/137Cs and discussed on their origin whether they were released from the Fukushima I nuclear power plant o...

  2. Identification of sources and production processes of bottled waters by stable hydrogen and oxygen isotope ratios.

    Science.gov (United States)

    Brencic, Mihael; Vreca, Polona

    2006-01-01

    Bottled water is a food product that considerably depends on the environment from which it originates, not only at the place where it is produced, but predominantly on the conditions in the recharge area of the wells captured for bottling. According to their source and the bottling process, bottled waters can be divided into natural and artificially sparkling waters, still and flavoured waters. These waters originate from various parts of the hydrological cycle and their natural origin is reflected in their hydrogen and oxygen stable isotopic compositions (delta(2)H and delta(18)O). A total of 58 domestic and foreign brands and 16 replicates of bottled waters, randomly collected on the Slovene market in September 2004, were analysed for delta(2)H and delta(18)O. The isotopic composition varied between -83 per thousand and -46 per thousand with an average of -66 per thousand for hydrogen, and between -11.9 per thousand and -7.5 per thousand with an average of -9.6 per thousand for oxygen. This investigation helped (1) to determine and test the classification of bottled waters, (2) to determine the natural origin of bottled water, and (3) to indicate differences between the natural and production processes. The production process may influence the isotopic composition of flavoured waters and artificially sparkling waters. No such modification was observed for still and natural sparkling waters. The methods applied, together with hydrological knowledge, can be used for the authentication of bottled waters for regulatory and consumer control applications.

  3. Oxygen isotope ratios in the shell of Mytilus edulis: archives of glacier meltwater in Greenland?

    Science.gov (United States)

    Versteegh, E. A. A.; Blicher, M. E.; Mortensen, J.; Rysgaard, S.; Als, T. D.; Wanamaker, A. D., Jr.

    2012-09-01

    Melting of the Greenland Ice Sheet (GrIS) is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models predicting the influence of ongoing climate change. We investigated a potential meltwater proxy in Godthåbsfjord (West Greenland), where glacier meltwater causes seasonal excursions with lower oxygen isotope water (δ18Ow) values and salinity. The blue mussel (Mytilus edulis) potentially records these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and kitchen middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We investigate its potential as a palaeo-meltwater proxy. First, we confirmed that M. edulis shell calcite oxygen isotope (δ18Oc) values are in equilibrium with ambient water and generally reflect meltwater conditions. Subsequently we investigated if this species recorded the full range of δ18Ow values occurring during the years 2007 to 2010. Results show that δ18Ow values were not recorded at very low salinities (future research will expand on the geographical and temporal range of the shell measurements by sampling mussels in other fjords in Greenland along a south-north gradient, and by sampling shells from raised shorelines and kitchen middens from prehistoric settlements in Greenland.

  4. CNO abundances and carbon isotope ratios in evolved stars of the open clusters NGC 2324, NGC 2477, and NGC 3960

    CERN Document Server

    Tautvaisiene, Grazina; Bragaglia, Angela; Randich, Sofia; Zenoviene, Renata

    2016-01-01

    Our main aim is to determine carbon-to-nitrogen and carbon isotope ratios for evolved giants in the open clusters NGC 2324, NGC 2477, and NGC 3960, which have turn-off masses of about 2 Msun, and to compare them with predictions of theoretical models. High-resolution spectra were analysed using a differential synthetic spectrum method. Abundances of carbon were derived using the C2 Swan (0,1) band heads at 5135 and 5635.5 A. The wavelength interval 7940-8130 A with strong CN features was analysed to determine nitrogen abundances and carbon isotope ratios. The oxygen abundances were determined from the [Oi] line at 6300 A. The mean values of the CNO abundances are [C/Fe]=-0.35+-0.06 (s.d.), [N/Fe]=0.28+-0.05, and [O/Fe]=-0.02+-0.10 in seven stars of NGC 2324; [C/Fe]=-0.26+-0.02, [N/Fe]=0.39+-0.04, and [O/Fe]=-0.11+-0.06 in six stars of NGC 2477; and [C/Fe]=-0.39+-0.04, [N/Fe]=0.32+-0.05, and [O/Fe]=-0.19+-0.06 in six stars of NGC 3960. The mean C/N ratio is equal to 0.92+-0.12, 0.91+-0.09, and 0.80+-0.13, resp...

  5. (135)Cs/(137)Cs isotopic ratio as a new tracer of radiocesium released from the Fukushima nuclear accident.

    Science.gov (United States)

    Zheng, Jian; Tagami, Keiko; Bu, Wenting; Uchida, Shigeo; Watanabe, Yoshito; Kubota, Yoshihisa; Fuma, Shoichi; Ihara, Sadao

    2014-05-20

    Since the Fukushima Daiichi nuclear power plant (FDNPP) accident in 2011, intensive studies of the distribution of released fission products, in particular (134)Cs and (137)Cs, in the environment have been conducted. However, the release sources, that is, the damaged reactors or the spent fuel pools, have not been identified, which resulted in great variation in the estimated amounts of (137)Cs released. Here, we investigated heavily contaminated environmental samples (litter, lichen, and soil) collected from Fukushima forests for the long-lived (135)Cs (half-life of 2 × 10(6) years), which is usually difficult to measure using decay-counting techniques. Using a newly developed triple-quadrupole inductively coupled plasma tandem mass spectrometry method, we analyzed the (135)Cs/(137)Cs isotopic ratio of the FDNPP-released radiocesium in environmental samples. We demonstrated that radiocesium was mainly released from the Unit 2 reactor. Considering the fact that the widely used tracer for the released Fukushima accident-sourced radiocesium in the environment, the (134)Cs/(137)Cs activity ratio, will become unavailable in the near future because of the short half-life of (134)Cs (2.06 years), the (135)Cs/(137)Cs isotopic ratio can be considered as a new tracer for source identification and long-term estimation of the mobility of released radiocesium in the environment.

  6. Annual cyclicity in high-resolution stable carbon and oxygen isotope ratios in the wood of the mangrove tree Rhizophora mucronata

    OpenAIRE

    Verheyden, A.; Gerhard Helle; G. H. Schleser; F. Dehairs; BEECKMAN, H.; Koedam, N.;  

    2004-01-01

    In the present study, the high-resolution stable carbon (13C/12C) and oxygen (18O/16O) isotope ratio profiles in the wood of the mangrove Rhizophora mucronata Lam., a tropical tree species lacking distinct growth rings, were investigated. Variations of both isotope ratios revealed a remarkable annual cyclicity with lowest values occurring at the latewood/earlywood boundary (April–May) and highest values during the transition from earlywood to latewood (October–November). Based on the current ...

  7. Annual cyclicity in high-resolution stable carbon and oxygen isotope ratios in the wood of the mangrove tree Rhizophora mucronata

    OpenAIRE

    Verheyden, A.; Helle, G.; G. H. Schleser; F. Dehairs; BEECKMAN, H.; Koedam, N.

    2004-01-01

    In the present study, the high-resolution stable carbon ((13)C/(12)C) and oxygen ((18)O/(16)O) isotope ratio profiles in the wood of the mangrove Rhizophora mucronata Lam., a tropical tree species lacking distinct growth rings, were investigated. Variations of both isotope ratios revealed a remarkable annual cyclicity with lowest values occurring at the latewood/earlywood boundary (April-May) and highest values during the transition from earlywood to latewood (October-November). Based on the ...

  8. Evaluation technology for burnup and generated amount of plutonium by measurement of xenon isotopic ratio in dissolver off-gas at reprocessing facility (Joint research)

    OpenAIRE

    岡野 正紀; 久野 剛彦; 高橋 一朗; 白水 秀知; Charlton, W. S.; Wells, C. A.; Hemberger, P. H.; 山田 敬二; 酒井 敏雄

    2006-01-01

    The amount of Pu in the spent fuel was evaluated from Xe isotopic ratio in off-gas in reprocessing facility, is related to burnup. Six batches of dissolver off-gas at spent fuel dissolution process were sampled from the main stack in Tokai Reprocessing Plant during BWR fuel reprocessing campaign. Xenon isotopic ratio was determined with GC/MS. Burnup and generated amount of Pu were evaluated with Noble Gas Environmental Monitoring Application code (NOVA), developed by Los Alamos National Labo...

  9. Oxygen isotope ratios in the shell of Mytilus edulis: archives of glacier meltwater in Greenland?

    Directory of Open Access Journals (Sweden)

    T. D. Als

    2012-09-01

    Full Text Available Melting of the Greenland Ice Sheet (GrIS is accelerating and will contribute significantly to global sea level rise during the 21st century. Instrumental data on GrIS melting only cover the last few decades, and proxy data extending our knowledge into the past are vital for validating models predicting the influence of ongoing climate change. We investigated a potential meltwater proxy in Godthåbsfjord (West Greenland, where glacier meltwater causes seasonal excursions with lower oxygen isotope water (δ18Ow values and salinity. The blue mussel (Mytilus edulis potentially records these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and kitchen middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We investigate its potential as a palaeo-meltwater proxy. First, we confirmed that M. edulis shell calcite oxygen isotope (δ18Oc values are in equilibrium with ambient water and generally reflect meltwater conditions. Subsequently we investigated if this species recorded the full range of δ18Ow values occurring during the years 2007 to 2010. Results show that δ18Ow values were not recorded at very low salinities (M. edulis δ18Oc values are suitable in reconstructing past meltwater amounts in most cases, but care has to be taken that shells are collected not too close to a glacier, but rather in the mid region or mouth of the fjord. The focus of future research will expand on the geographical and temporal range of the shell measurements by sampling mussels in other fjords in Greenland along a south-north gradient, and by sampling shells from raised shorelines and kitchen middens from prehistoric settlements in Greenland.

  10. The use of isotope ratios (13C/12C) for vegetable oils authentication

    Science.gov (United States)

    Cristea, G.; Magdas, D. A.; Mirel, V.

    2012-02-01

    Stable isotopes are now increasingly used for the control of the geographical origin or authenticity of food products. The falsification may be more or less sophisticated and its sophistication as well as its costs increases with the improvement of analytical methods. In this study 22 vegetable oils (olive, sunflower, palm, maize) commercialized on Romanian market were investigated by mean of δ13C in bulk oil and the obtained results were compared with those reported in literature in order to check the labeling of these natural products. The obtained results were in the range of the mean values found in the literature for these types of oils, thus providing their accurate labeling.

  11. The carbon isotopes ratio and trace metals content determinations in some Transylvanian fruit juices

    Science.gov (United States)

    Dehelean, A.; Magdas, D. A.; Cristea, G.

    2012-02-01

    This work presents a preliminary study on the carbon isotope signature and trace metal content investigated on the soil-plant-fruit pulp chain. The samples were collected from two Transylvanian areas namely Alba and Salaj. The average value of the δ13C at the soil surface was around δ13C ≈ -27%° and important differences of the δ13C values between the two studied areas were not observed. Meanwhile, differences between fruit pulp of grape juice and the pulp of pear juice relived a difference of about 1.5%° for δ13C values.

  12. Climatic and geographical dependence of the H, C and O stable isotope ratios of Italian wine

    Energy Technology Data Exchange (ETDEWEB)

    Camin, Federica, E-mail: federica.camin@fmach.it [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Dordevic, Nikola [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Radboud University Nijmegen, Institute for Molecules and Materials, Analytical Chemistry, P.O. Box 9010, 6500 GL Nijmegen (Netherlands); Wehrens, Ron; Neteler, Markus; Delucchi, Luca [Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Postma, Geert; Buydens, Lutgarde [Radboud University Nijmegen, Institute for Molecules and Materials, Analytical Chemistry, P.O. Box 9010, 6500 GL Nijmegen (Netherlands)

    2015-01-01

    Graphical abstract: Correlation matrix between (D/H){sub 1}, (D/H){sub 2}, δ{sup 13}C and δ{sup 18}O parameters of wine (4000 samples) and the climatic and geographical characteristics of the areas of origin. - Highlights: • We studied the relationship between wine isotopic data and climate and geography. • We considered (D/H){sub 1}, (D/H){sub 2} and δ{sup 13}C of ethanol and δ{sup 18}O of water of 4000 wines. • δ{sup 18}O, followed by (D/H){sub 1}, had the strongest relationship with climate and location. • The dominant variables were latitude, δ{sup 18}O and δ{sup 2}H of precipitation and temperature. • Relationships and models may be used to predict the isotopic composition of wine. - Abstract: In this study, we investigated the relationship between (D/H){sub 1,} (D/H){sub 2} and δ{sup 13}C of ethanol and δ{sup 18}O of water in wine, and variables describing the climate and the geography of the production area, using exploratory visualisation tools, regression analysis and linear modelling. For the first time, a large amount of data (around 4000 wine samples collected over 11 years in Italy) and all the official isotopic parameters, as well as a large number of significant climatic and geographical descriptors (date of harvest, latitude, longitude, elevation, distance from the sea, amount of precipitation, maximum daily temperature, minimum daily temperature, mean daily temperature, δ{sup 18}O and δ{sup 2}H of precipitation) were considered. δ{sup 18}O, followed by (D/H){sub 1}, was shown to have the strongest relationship with climate and location. The dominant variables were latitude, with a negative relationship, δ{sup 18}O and δ{sup 2}H of precipitation and temperature, both with positive relationships. The identified correlations and models could be used to predict the isotopic composition of authentic wines, offering increased possibilities for detecting fraud and mislabelling.

  13. Stable Nitrogen and Carbon Isotope Ratios Indicate Traditional and Market Food Intake in an Indigenous Circumpolar Population123

    Science.gov (United States)

    Nash, Sarah H.; Bersamin, Andrea; Kristal, Alan R.; Hopkins, Scarlett E.; Church, Rebecca S.; Pasker, Renee L.; Luick, Bret R.; Mohatt, Gerald V.; Boyer, Bert B.; O’Brien, Diane M.

    2012-01-01

    The transition of a society from traditional to market-based diets (termed the nutrition transition) has been associated with profound changes in culture and health. We are developing biomarkers to track the nutrition transition in the Yup’ik Eskimo population of Southwest Alaska based on naturally occurring variations in the relative abundances of carbon and nitrogen stable isotopes (δ15N and δ13C values). Here, we provide three pieces of evidence toward the validation of these biomarkers. First, we analyzed the δ15N and δ13C values of a comprehensive sample of Yup’ik foods. We found that δ15N values were elevated in fish and marine mammals and that δ13C values were elevated in market foods containing corn or sugar cane carbon. Second, we evaluated the associations between RBC δ15N and δ13C values and self-reported measures of traditional and market food intake (n = 230). RBC δ15N values were correlated with intake of fish and marine mammals (r = 0.52; P < 0.0001). RBC δ13C values were correlated with intake of market foods made from corn and sugar cane (r = 0.46; P < 0.0001) and total market food intake (r = 0.46; P < 0.0001). Finally, we assessed whether stable isotope ratios captured population-level patterns of traditional and market intake (n = 1003). Isotopic biomarkers of traditional and market intake were associated with age, community location, sex, and cultural identity. Self-report methods showed variations by age and cultural identity only. Thus, stable isotopes show potential as biomarkers for monitoring dietary change in indigenous circumpolar populations. PMID:22157543

  14. Dating of mine waste in lacustrine sediments using cesium-137

    Science.gov (United States)

    Rember, W. C.; Erdman, T. W.; Hoffmann, M. L.; Chamberlain, V. E.; Sprenke, K. F.

    1993-11-01

    For over a century Medicine Lake in northern Idaho has received heavy-metal-laden tailings from the Coeur d'Alene mining district. Establishing the depositional chronology of the lake bottom sediments provides information on the source and rate of deposition of the tailings. Cesium-137, an isotope produced in the atmosphere by nuclear bomb tests, was virtually absent in the environment prior to 1951, but reached its apex in 1964. Our analysis of cesium-137 in the sediments of Medicine Lake revealed that 14 cm of fine-grained tailings were deposited in the lake from 1951 to 1964 and tailing deposition downstream was greatly reduced by the installation of tailings dams in the district in 1968. Cesium-137 analysis is accomplished by a fairly simple gamma-ray counting technique and should be a valuable tool for analyzing sedimentation in any lacustrine environment that was active during the 1950s and 1960s.

  15. Innovations in Mass Spectrometry for Precise and Accurate Isotope Ratio Determination from Very Small Analyte Quantities (Invited)

    Science.gov (United States)

    Lloyd, N. S.; Bouman, C.; Horstwood, M. S.; Parrish, R. R.; Schwieters, J. B.

    2010-12-01

    This presentation describes progress in mass spectrometry for analysing very small analyte quantities, illustrated by example applications from nuclear forensics. In this challenging application, precise and accurate (‰) uranium isotope ratios are required from 1 - 2 µm diameter uranium oxide particles, which comprise less than 40 pg of uranium. Traditionally these are analysed using thermal ionisation mass spectrometry (TIMS), and more recently using secondary ionisation mass spectrometry (SIMS). Multicollector inductively-coupled plasma mass spectrometry (MC-ICP-MS) can offer higher productivity compared to these techniques, but is traditionally limited by low efficiency of analyte utilisation (sample through to ion detection). Samples can either be introduced as a solution, or sampled directly from solid using laser ablation. Large multi-isotope ratio datasets can help identify provenance and intended use of anthropogenic uranium and other nuclear materials [1]. The Thermo Scientific NEPTUNE Plus (Bremen, Germany) with ‘Jet Interface’ option offers unparalleled MC-ICP-MS sensitivity. An analyte utilisation of c. 4% has previously been reported for uranium [2]. This high-sensitivity configuration utilises a dry high-capacity (100 m3/h) interface pump, special skimmer and sampler cones and a desolvating nebuliser system. Coupled with new acquisition methodologies, this sensitivity enhancement makes possible the analysis of micro-particles and small sample volumes at higher precision levels than previously achieved. New, high-performance, full-size and compact discrete dynode secondary electron multipliers (SEM) exhibit excellent stability and linearity over a large dynamic range and can be configured to simultaneously measure all of the uranium isotopes. Options for high abundance-sensitivity filters on two ion beams are also available, e.g. for 236U and 234U. Additionally, amplifiers with high ohm (1012 - 1013) feedback resistors have been developed to

  16. Near infrared spectroscopy of M dwarfs. IV. A preliminary survey on the carbon isotopic ratios in M dwarfs

    CERN Document Server

    Tsuji, Takashi

    2016-01-01

    Based on the medium resolution near infrared spectra of 13CO (3,1) band, carbon isotopic ratios are estimated in 48 M dwarfs, for which we had determined the carbon and oxygen abundances from CO and H2O lines, respectively. We find clear evidence for the presence of a 13CO feature for the first time in the spectra of M dwarfs. The spectral resolution of our observed data, however, is not high enough to analyze the 13CO feature directly. Instead, we compare observed spectrum with synthetic spectra assuming 12C/13C = 10, 25, 50, 100, and 200 for each of 48 M dwarfs and estimate the best possible 12C/13C ratio by the chi-square analysis. The resulting 12C/13C ratios in M dwarfs distribute from 39 to a lower limit of 200. The mean value of 31 M dwarfs for which 12C/13C ratios are determined is 12C/13C = 87 +- 21 (p.e.), and that of 48 M dwarfs including those with the lower limit of 200 is 12C/13C > 127 +- 41 (p.e.). These results are somewhat larger than the 12C/13C ratio of the present interstellar matter (ISM)...

  17. The influences of cultivation setting on inflorescence lipid distributions, concentrations, and carbon isotope ratios of Cannabis sp.

    Science.gov (United States)

    Tipple, Brett J; Hambach, Bastian; Barnette, Janet E; Chesson, Lesley A; Ehleringer, James R

    2016-05-01

    While much is known about how the growth environment influences many aspects of floral morphology and physiology, little is known about how the growth setting influences floral lipid composition. We explored variations in paraffin wax composition in Cannabis sp., a cash crop grown both indoors and outdoors across the United States today. Given an increased focus on regulation of this crop, there are additional incentives to certify the setting of Cannabis cultivation. To understand the impacts of the growth environment, we studied distributions, concentrations, and carbon isotope ratios of n-alkanes isolated from Cannabis sp. inflorescences to assess if variations within these lipid parameters were related to known growth settings of specimens seized by federal agents. We found that Cannabis plants cultivated under open-field settings had increased inflorescence paraffin wax abundances and greater production of lower molecular weight n-alkanes relative to plants grown in enclosed environments. Further, the carbon isotope ratios of n-C29 from Cannabis plants grown in enclosed environments had relatively lower carbon isotope (δ(13)C) values compared to plants from open-field environments. While this set of observations on seized plant specimens cannot address the particular driver behind these observations, we posit that (a) variations in irradiance and/or photoperiod may influence the distribution and concentration of inflorescence lipids, and (b) the δ(13)C value of source CO2 and lipid concentration regulates the δ(13)C values of inflorescence n-C29 and bulk Cannabis plant materials. Nonetheless, by using a cultivation model based on δ(13)C values of n-C29, the model correctly identified the growth environment 90% of time. We suggest that these lipid markers may be used to trace cultivation methods of Cannabis sp. now and become a more powerful marker in the future, once the mechanism(s) behind these patterns is uncovered.

  18. Determination of 13C/12C Isotope Ratio in Alcohols of Different Origin by 1н Nuclei NMR-Spectroscopy

    Science.gov (United States)

    Dzhimak, S. S.; Basov, A. A.; Buzko, V. Yu.; Kopytov, G. F.; Kashaev, D. V.; Shashkov, D. I.; Shlapakov, M. S.; Baryshev, M. G.

    2017-02-01

    A new express method of indirect assessment of 13C/12C isotope ratio on 1H nuclei is developed to verify the authenticity of ethanol origin in alcohol-water-based fluids and assess the facts of various alcoholic beverages falsification. It is established that in water-based alcohol-containing systems, side satellites for the signals of ethanol methyl and methylene protons in the NMR spectra on 1H nuclei, correspond to the protons associated with 13C nuclei. There is a direct correlation between the intensities of the signals of ethanol methyl and methylene protons' 1H- NMR and their side satellites, therefore, the data obtained can be used to assess 13C/12C isotope ratio in water-based alcohol-containing systems. The analysis of integrated intensities of main and satellite signals of methyl and methylene protons of ethanol obtained by NMR on 1H nuclei makes it possible to differentiate between ethanol of synthetic and natural origin. Furthermore, the method proposed made it possible to differentiate between wheat and corn ethanol.

  19. Use of isotope ratio mass spectrometry to differentiate between endogenous steroids and synthetic homologues in cattle: a review.

    Science.gov (United States)

    Janssens, Geert; Courtheyn, Dirk; Mangelinckx, Sven; Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

    2013-04-15

    Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the (13)C/(12)C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years.

  20. Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

    Science.gov (United States)

    Webster, C. R.; Mahaffy, P. R.; Leshin, L. A.; Atreya, S. K.; Flesch, G. J.; Stern, J.; Christensen, L. E.; Vasavada, A. R.; Owen, T.; Niles, P. B.; Jones, J. H.; Franz, H.

    2013-01-01

    Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biological activity [2]. For Mars, measurements to date have indicated enrichment in all the heavier isotopes consistent with atmospheric escape processes, but with uncertainty too high to tie the results with the more precise isotopic ratios achieved from SNC meteoritic analyses. We will present results to date of H, C and O isotope ratios in CO2 and H2O made to high precision (few per mil) using the Tunable Laser Spectrometer (TLS) that is part of the Sample Analysis at Mars (SAM) instrument suite on MSL s Curiosity Rover.

  1. A Novel Framework for Quantifying past Methane Recycling by Sphagnum-Methanotroph Symbiosis Using Carbon and Hydrogen Isotope Ratios of Leaf Wax Biomarkers

    Science.gov (United States)

    Nichols, Jonathan E.; Isles, Peter D. F.; Peteet, Dorothy M.

    2014-01-01

    The concentration of atmospheric methane is strongly linked to variations in Earth's climate. Currently, we can directly reconstruct the total atmospheric concentration of methane, but not individual terms of the methane cycle. Northern wetlands, dominated by Sphagnum, are an important contributor of atmospheric methane, and we seek to understand the methane cycle in these systems. We present a novel method for quantifying the proportion of carbon Sphagnum assimilates from its methanotrophic symbionts using stable isotope ratios of leaf-wax biomarkers. Carbon isotope ratios of Sphagnum compounds are determined by two competing influences, water content and the isotope ratio of source carbon. We disentangled these effects using a combined hydrogen and carbon isotope approach. We constrained Sphagnum water content using the contrast between the hydrogen isotope ratios of Sphagnum and vascular plant biomarkers. We then used Sphagnum water content to calculate the carbon isotope ratio of Sphagnum's carbon pool. Using a mass balance equation, we calculated the proportion of recycled methane contributed to the Sphagnum carbon pool, 'PRM.' We quantified PRM in peat monoliths from three microhabitats in the Mer Bleue peatland complex. Modern studies have shown that water table depth and vegetation have strong influences on the peatland methane cycle on instrumental time scales. With this new approach, delta C-13 of Sphagnum compounds are now a useful tool for investigating the relationships among hydrology, vegetation, and methanotrophy in Sphagnum peatlands over the time scales of entire peatland sediment records, vital to our understanding of the global carbon cycle through the Late Glacial and Holocene.

  2. High-Precision Instrumentation for CO2 Isotope Ratio Measurements Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Knowing atmospheric 13CO2/12CO2 ratios precisely is important to understanding biogenic and anthroprogenic sources and sinks for carbon. Currently available field...

  3. Comparison of 265 nm Femtosecond and 213 nm Nanosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Pb Isotope Ratio Measurements.

    Science.gov (United States)

    Ohata, Masaki; Nonose, Naoko; Dorta, Ladina; Günther, Detlef

    2015-01-01

    The analytical performance of 265 nm femtosecond laser ablation (fs-LA) and 213 nm nanosecond laser ablation (ns-LA) systems coupled with multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) for Pb isotope ratio measurements of solder were compared. Although the time-resolved signals of Pb measured by fs-LA-MC-ICPMS showed smoother signals compared to those obtained by ns-LA-MC-ICPMS, similar precisions on Pb isotope ratio measurements were obtained between them, even though their operating conditions were slightly different. The mass bias correction of the Pb isotope ratio measurement was carried out by a comparison method using a Pb standard solution prepared from NIST SRM 981 Pb metal isotopic standard, which was introduced into the ICP by a desolvation nebulizer (DSN) via a dual-sample introduction system, and it was successfully demonstrated for Pb isotope ratio measurements for either NIST 981 metal isotopic standard or solder by fs-LA-MC-ICPMS since the analytical results agreed well with the certified value as well as the determined value within their standard deviations obtained and the expanded uncertainty of the certified or determined value. The Pb isotope ratios of solder obtained by ns-LA-MC-ICPMS also showed agreement with respect to the determined value within their standard deviations and expanded uncertainty. From these results, it was evaluated that the mass bias correction applied in the present study was useful and both LA-MC-ICPMS could show similar analytical performance for the Pb isotope ratio microanalysis of metallic samples such as solder.

  4. High-Precision Tungsten Isotopic Analysis by Multicollection Negative Thermal Ionization Mass Spectrometry Based on Simultaneous Measurement of W and (18)O/(16)O Isotope Ratios for Accurate Fractionation Correction.

    Science.gov (United States)

    Trinquier, Anne; Touboul, Mathieu; Walker, Richard J

    2016-02-02

    Determination of the (182)W/(184)W ratio to a precision of ± 5 ppm (2σ) is desirable for constraining the timing of core formation and other early planetary differentiation processes. However, WO3(-) analysis by negative thermal ionization mass spectrometry normally results in a residual correlation between the instrumental-mass-fractionation-corrected (182)W/(184)W and (183)W/(184)W ratios that is attributed to mass-dependent variability of O isotopes over the course of an analysis and between different analyses. A second-order correction using the (183)W/(184)W ratio relies on the assumption that this ratio is constant in nature. This may prove invalid, as has already been realized for other isotope systems. The present study utilizes simultaneous monitoring of the (18)O/(16)O and W isotope ratios to correct oxide interferences on a per-integration basis and thus avoid the need for a double normalization of W isotopes. After normalization of W isotope ratios to a pair of W isotopes, following the exponential law, no residual W-O isotope correlation is observed. However, there is a nonideal mass bias residual correlation between (182)W/(i)W and (183)W/(i)W with time. Without double normalization of W isotopes and on the basis of three or four duplicate analyses, the external reproducibility per session of (182)W/(184)W and (183)W/(184)W normalized to (186)W/(183)W is 5-6 ppm (2σ, 1-3 μg loads). The combined uncertainty per session is less than 4 ppm for (183)W/(184)W and less than 6 ppm for (182)W/(184)W (2σm) for loads between 3000 and 50 ng.

  5. On the accuracy of gamma spectrometric isotope ratio measurements of uranium

    Energy Technology Data Exchange (ETDEWEB)

    Ramebäck, H., E-mail: henrik.ramebeck@foi.se [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Chalmers University of Technology, Department of Chemistry and Chemical Engineering, SE-412 96 Göteborg (Sweden); Lagerkvist, P.; Holmgren, S.; Jonsson, S.; Sandström, B.; Tovedal, A. [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Vesterlund, A. [Swedish Defence Research Agency, FOI, CBRN Defence and Security, SE-901 82 Umeå (Sweden); Chalmers University of Technology, Department of Chemistry and Chemical Engineering, SE-412 96 Göteborg (Sweden); Vidmar, T. [SCK-CEN, Belgian Nuclear Research Centre, Boeretang 200, 2400 Mol (Belgium); Kastlander, J. [Swedish Defence Research Agency, FOI, Defence and Security, Systems and Technology, SE-164 90 Stockholm (Sweden)

    2016-04-11

    The isotopic composition of uranium was measured using high resolution gamma spectrometry. Two acid solutions and two samples in the form of UO{sub 2} pellets were measured. The measurements were done in close geometries, i.e. directly on the endcap of the high purity germanium detector (HPGe). Applying no corrections for count losses due to true coincidence summing (TCS) resulted in up to about 40% deviation in the abundance of {sup 235}U from the results obtained with mass spectrometry. However, after correction for TCS, excellent agreement was achieved between the results obtained using two different measurement methods, or a certified value. Moreover, after corrections, the fitted relative response curves correlated excellently with simulated responses, for the different geometries, of the HPGe detector.

  6. Tropical West Pacific moisture dynamics and climate controls on rainfall isotopic ratios in southern Papua, Indonesia

    Science.gov (United States)

    Permana, Donaldi S.; Thompson, Lonnie G.; Setyadi, Gesang

    2016-03-01

    Understanding the controls on stable isotopologues of tropical rainfall is critical for paleoclimatic reconstruction from tropical ice core records. The southern Papua region, Indonesia, has a unique climate regime that allows for the evaluation of the influence of precipitation and convective activity on seasonal rainfall δ18O. The influence of the El Niño-Southern Oscillation (ENSO) on interannual rainfall δ18O variation is also important for paleoclimate reconstruction. Here we present stable isotope analyses of 1332 rain samples collected daily during the period from January 2013 to February 2014 (ENSO-normal) and December 2014 to September 2015 (El Niño) at various elevation stations (9 to 3945 m above sea level) on the southern slope of the central mountain ranges in Papua. The results suggest an altitude effect with an isotopic lapse rate for δ18O (δD) of -2.4‰/km (-18.2‰/km). The temporal δ18O variability (daily to interannual) is controlled mostly by regional convective activity rather than local/regional precipitation amount. The intraseasonal δ18O variation resembles the Madden-Julian Oscillation cycle with major δ18O depletion events associated with active (wet) phases. Moisture origins, transport pathways, moisture convergence, and raindrop evaporation appear to have no significant seasonal effects on δ18O, leading to the conclusion that condensation temperature controls δ18O depletion associated with convective activity. Seasonal δ18O variation is likely associated with atmospheric temperature at the mean condensation level as indicated by the altitude of latent heat release in the troposphere. Rainfall δ18O (δD) is generally enriched by 1.6‰-2‰ (11‰-15‰) during El Niño than during ENSO-normal periods.

  7. Isotopic compositions of boron in sediments and their implications

    Digital Repository Service at National Institute of Oceanography (India)

    Shirodkar, P.V.; Yingkai, X.

    The abundance and isotopic compositions of boron in sediments from the salt lakes of Qaidam Basin, China have been determined by thermal ionization mass spectrometry of cesium borate. The results show large variations in the isotopic compositions...

  8. Clinical effects of cesium intake.

    Science.gov (United States)

    Melnikov, Petr; Zanoni, Lourdes Zélia

    2010-06-01

    The knowledge about cesium metabolism and toxicity is sparse. Oral intake of cesium chloride has been widely promoted on the basis of the hypothesis referred to as "high pH cancer therapy", a complimentary alternative medicine method for cancer treatment. However, no properly confirmed tumor regression was reported so far in all probability because of neither theoretical nor experimental grounds for this proposal. The aim of the present review was to resume and discuss the material currently available on cesium salts and their applications in medicine. The presence of cesium in the cell does not guarantee high pH of its content, and there is no clinical evidence to support the claims that cancer cells are vulnerable to cesium. Cesium is relatively safe; signs of its mild toxicity are gastrointestinal distress, hypotension, syncope, numbness, or tingling of the lips. Nevertheless, total cesium intakes of 6 g/day have been found to produce severe hypokalemia, hypomagnesemia, prolonged QTc interval, episodes of polymorphic ventricular tachycardia, with or without torsade de pointes, and even acute heart arrest. However, full information on its acute and chronic toxicity is not sufficiently known. Health care providers should be aware of the cardiac complications, as a result of careless cesium usage as alternative medicine.

  9. Investigations on hydrogen isotope ratios of endogenous urinary steroids: reference-population-based thresholds and proof-of-concept.

    Science.gov (United States)

    Piper, Thomas; Thomas, Andreas; Thevis, Mario; Saugy, Martial

    2012-09-01

    Carbon isotope ratio (CIR) analysis has been routinely and successfully used in sports drug testing for many years to uncover the misuse of endogenous steroids. One limitation of the method is the availability of steroid preparations exhibiting CIRs equal to endogenous steroids. To overcome this problem, hydrogen isotope ratios (HIR) of endogenous urinary steroids were investigated as a potential complement; results obtained from a reference population of 67 individuals are presented herein. An established sample preparation method was modified and improved to enable separate measurements of each analyte of interest where possible. From the fraction of glucuronidated steroids; pregnanediol, 16-androstenol, 11-ketoetiocholanolone, androsterone (A), etiocholanolone (E), dehydroepiandrosterone (D), 5α- and 5β-androstanediol, testosterone and epitestosterone were included. In addition, sulfate conjugates of A, E, D, epiandrosterone and 17α- and 17β-androstenediol were considered and analyzed after acidic solvolysis. The obtained results enabled the calculation of the first reference-population-based thresholds for HIR of urinary steroids that can readily be applied to routine doping control samples. Proof-of-concept was accomplished by investigating urine specimens collected after a single oral application of testosterone-undecanoate. The HIR of most testosterone metabolites were found to be significantly influenced by the exogenous steroid beyond the established threshold values. Additionally, one regular doping control sample with an extraordinary testosterone/epitestosterone ratio of 100 without suspicious CIR was subjected to the complementary methodology of HIR analysis. The HIR data eventually provided evidence for the exogenous origin of urinary testosterone metabolites. Despite further investigations on HIR being advisable to corroborate the presented reference-population-based thresholds, the developed method proved to be a new tool supporting modern

  10. Limits and possibilities in the geolocation of humans using multiple isotope ratios (H, O, N, C) of hair from east coast cities of the USA.

    Science.gov (United States)

    Reynard, Linda M; Burt, Nicole; Koon, Hannah E C; Tuross, Noreen

    2016-01-01

    We examined multiple natural abundance isotope ratios of human hair to assess biological variability within and between geographic locations and, further, to determine how well these isotope values predict location of origin. Sampling locations feature differing seasonality and mobile populations as a robust test of the method. Serially-sampled hair from Cambridge, MA, USA, shows lower δ(2)H and δ(18)O variability over a one-year time course than model-predicted precipitation isotope ratios, but exhibits considerable differences between individuals. Along a ∼13° north-south transect in the eastern USA (Brookline, MA, 42.3 ° N, College Park, MD, 39.0 ° N, and Gainesville, FL, 29.7 ° N) δ(18)O in human hair shows relatively greater differences and tracks changes in drinking water isotope ratios more sensitively than δ(2)H. Determining the domicile of humans using isotope ratios of hair can be confounded by differing variability in hair δ(18)O and δ(2)H between locations, differential incorporation of H and O into this protein and, in some cases, by tap water δ(18)O and δ(2)H that differ significantly from predicted precipitation values. With these caveats, randomly chosen people in Florida are separated from those in the two more northerly sites on the basis of the natural abundance isotopes of carbon, nitrogen, hydrogen, and oxygen.

  11. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    Directory of Open Access Journals (Sweden)

    P. Ziveri

    2012-03-01

    Full Text Available The oxygen isotopic composition (δ18O of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from field experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, supporting the idea that the [CO32−] effect on δ18O is universal for unicellular calcifying planktonic organisms. The slopes of the δ18O/[CO32−] relationships range between –0.0243‰ (μmol kg−1−1 (calcareous dinoflagellate T. heimii and the previously published –0.0022‰ (μmol kg−1−1 (non-symbiotic planktonic foramifera Orbulina universa, while C. leptoporus has a slope of –0.0048 ‰ (μmol kg−1−1. We present a simple conceptual model, based on the contribution of δ18O-enriched HCO3 to the CO32− pool in the calcifying vesicle, which can explain the [CO32−] effect on δ18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in calcifying organisms

  12. Impact of historical mining assessed in soils by kinetic extraction and lead isotopic ratios

    Energy Technology Data Exchange (ETDEWEB)

    Camizuli, E., E-mail: estelle.camizuli@u-bourgogne.fr [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Monna, F. [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Bermond, A.; Manouchehri, N.; Besançon, S. [Institut des sciences et industries du vivant et de l' environnement (AgroParisTech), Laboratoire de Chimie Analytique, 16, rue Claude Bernard, 75231 Paris Cedex 05 (France); Losno, R. [UMR 7583, LISA, Universités Paris 7-Paris 12 — CNRS, 61 av. du Gal de Gaulle, 94010 Créteil Cedex (France); Oort, F. van [UR 251, Pessac, Institut National de la Recherche Agronomique, Centre de Versailles-Grignon, RD 10, 78026 Versailles Cedex (France); Labanowski, J. [UMR 7285, IC2MP, Université de Poitiers — CNRS, 4, rue Michel Brunet, 86022 Poitiers (France); Perreira, A. [UMR 6298, ArTeHiS, Université de Bourgogne — CNRS — Culture, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Chateau, C. [UFR SVTE, Université de Bourgogne, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France); Alibert, P. [UMR 6282, Biogeosciences, Université de Bourgogne — CNRS, 6 bd Gabriel, Bat. Gabriel, 21000 Dijon (France)

    2014-02-01

    The aim of this study is to estimate the long-term behaviour of trace metals, in two soils differently impacted by past mining. Topsoils from two 1 km{sup 2} zones in the forested Morvan massif (France) were sampled to assess the spatial distribution of Cd, Cu, Pb and Zn. The first zone had been contaminated by historical mining. As expected, it exhibits higher trace-metal levels and greater spatial heterogeneity than the second non-contaminated zone, supposed to represent the local background. One soil profile from each zone was investigated in detail to estimate metal behaviour, and hence, bioavailability. Kinetic extractions were performed using EDTA on three samples: the A horizon from both soil profiles and the B horizon from the contaminated soil. For all three samples, kinetic extractions can be modelled by two first-order reactions. Similar kinetic behaviour was observed for all metals, but more metal was extracted from the contaminated A horizon than from the B horizon. More surprising is the general predominance of the residual fraction over the “labile” and “less labile” pools. Past anthropogenic inputs may have percolated over time through the soil profiles because of acidic pH conditions. Stable organo-metallic complexes may also have been formed over time, reducing metal availability. These processes are not mutually exclusive. After kinetic extraction, the lead isotopic compositions of the samples exhibited different signatures, related to contamination history and intrinsic soil parameters. However, no variation in lead signature was observed during the extraction experiment, demonstrating that the “labile” and “less labile” lead pools do not differ in terms of origin. Even if trace metals resulting from past mining and metallurgy persist in soils long after these activities have ceased, kinetic extractions suggest that metals, at least for these particular forest soils, do not represent a threat for biota. - Highlights: • Trace

  13. A universal carbonate ion effect on stable oxygen isotope ratios in unicellular planktonic calcifying organisms

    Directory of Open Access Journals (Sweden)

    P. Ziveri

    2011-08-01

    Full Text Available The oxygen isotopic composition (δ18O of calcium carbonate of planktonic calcifying organisms is a key tool for reconstructing both past seawater temperature and salinity. The calibration of paloeceanographic proxies relies in general on empirical relationships derived from experiments on extant species. Laboratory experiments have more often than not revealed that variables other than the target parameter influence the proxy signal, which makes proxy calibration a challenging task. Understanding these secondary or "vital" effects is crucial for increasing proxy accuracy and possibly for developing new biomarkers. We present data from laboratory experiments showing that oxygen isotope fractionation during calcification in the coccolithophore Calcidiscus leptoporus and the calcareous dinoflagellate Thoracosphaera heimii is dependent on carbonate chemistry of seawater in addition to its dependence on temperature. A similar result has previously been reported for planktonic foraminifera, suggesting that the [CO32−] effect on δ18O is universal for unicellular calcifying planktonic organisms. The slopes of the δ18O/[CO32−] relationships range between −0.0243 (μmol kg−1−1 (calcareous dinoflagellate T. heimii and the previously published 0.0022 (μmol kg−1−1 (non-symbiotic planktonic foramifera Orbulina universa, while C. leptoporus has a slope of 0.0048 (μmol kg−1−1. We present a simple conceptual model, based on the contribution of δ18O-enriched HCO3 to the CO32− pool in the calcifying vesicle, which can explain the [CO32−] effect on δ18O for the different unicellular calcifiers. This approach provides a new insight into biological fractionation in

  14. Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry

    Science.gov (United States)

    Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

    2009-01-01

    Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N

  15. THE ALPHA-BRANCHING RATIOS OF THE PB-188, PB-190, PB-192 ISOTOPES

    NARCIS (Netherlands)

    WAUTERS, J; DENDOOVEN, P; DECROCK, P; HUYSE, M; KIRCHNER, R; KLEPPER, O; REUSEN, G; ROECKL, E; VANDUPPEN, P

    1992-01-01

    The a-branching ratios (b)alpha)) of Pb-192, Pb-190, Pb-188 are measured using mass-separated sources. Different experimental set-ups are used - one detector as well as two detector set-ups - thereby detecting the alpha-particles from the parent and/or via alpha-decay formed daughter nuclei, the bet

  16. SIMS analyses of silicon and oxygen isotope ratios for quartz from Archean and Paleoproterozoic banded iron formations

    Science.gov (United States)

    Heck, Philipp R.; Huberty, Jason M.; Kita, Noriko T.; Ushikubo, Takayuki; Kozdon, Reinhard; Valley, John W.

    2011-10-01

    Banded iron formations (BIFs) are chemical marine sediments dominantly composed of alternating iron-rich (oxide, carbonate, sulfide) and silicon-rich (chert, jasper) layers. Isotope ratios of iron, carbon, and sulfur in BIF iron-bearing minerals are biosignatures that reflect microbial cycling for these elements in BIFs. While much attention has focused on iron, banded iron formations are equally banded silica formations. Thus, silicon isotope ratios for quartz can provide insight on the sources and cycling of silicon in BIFs. BIFs are banded by definition, and microlaminae, or sub-mm banding, are characteristic of many BIFs. In situ microanalysis including secondary ion mass spectrometry is well-suited for analyzing such small features. In this study we used a CAMECA IMS-1280 ion microprobe to obtain highly accurate (±0.3‰) and spatially resolved (˜10 μm spot size) analyses of silicon and oxygen isotope ratios for quartz from several well known BIFs: Isua, southwest Greenland (˜3.8 Ga); Hamersley Group, Western Australia (˜2.5 Ga); Transvaal Group, South Africa (˜2.5 Ga); and Biwabik Iron Formation, Minnesota, USA (˜1.9 Ga). Values of δ 18O range from +7.9‰ to +27.5‰ and include the highest reported δ 18O values for BIF quartz. Values of δ 30Si have a range of ˜5‰ from -3.7‰ to +1.2‰ and extend to the lowest δ 30Si values for Precambrian cherts. Isua BIF samples are homogeneous in δ 18O to ±0.3‰ at mm- to cm-scale, but are heterogeneous in δ 30Si up to 3‰, similar to the range in δ 30Si found in BIFs that have not experienced high temperature metamorphism (up to 300 °C). Values of δ 30Si for quartz are homogeneous to ±0.3‰ in individual sub-mm laminae, but vary by up to 3‰ between multiple laminae over mm-to-cm of vertical banding. The scale of exchange for Si in quartz in BIFs is thus limited to the size of microlaminae, or less than ˜1 mm. We interpret differences in δ 30Si between microlaminae as preserved from primary

  17. Lead isotope ratios in six lake sediment cores from Japan Archipelago: Historical record of trans-boundary pollution sources

    Energy Technology Data Exchange (ETDEWEB)

    Hosono, Takahiro, E-mail: hosono@kumamoto-u.ac.jp [Priority Organization for Innovation and Excellence, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Alvarez, Kelly [Priority Organization for Innovation and Excellence, Kumamoto University, 2-39-1 Kurokami, Kumamoto 860-8555 (Japan); Kuwae, Michinobu [Senior Research Fellow Center, Ehime University, 2-5 Bunkyo-cho, Matsuyama 790-8577 (Japan)

    2016-07-15

    Sediment cores from six lakes situated from north to south on the Japanese Archipelago were collected during 2009–2010 to investigate the hypothesis that deposition of lead (Pb) was coming from East Asia (including China, South Korea and eastern part of Russia). Accumulation rates and ages of the lake sediment were estimated by the {sup 210}Pb constant rate of supply model and {sup 137}Cs inputs to reconstruct the historical trends of Pb accumulation. Cores from four lakes located in the north and central Japan, showed clear evidence of Pb pollution with a change in the {sup 206}Pb/{sup 207}Pb and {sup 208}Pb/{sup 207}Pb ratios in the recent sediment as compared to the deeper sediment. Among the six studied lakes, significant inputs of anthropogenic lead emissions were observed at Lake Mikazuki (north Hokkaido in north Japan), Lake Chokai (north of Honshu), and Lake Mikuriga (central part of Honshu). Pb isotopic comparison of collected core sediment and previously reported data for wet precipitation and aerosols from different Asian regions indicate that, before 1900, Pb accumulated in these three lakes was not affected by trans-boundary sources. Lake Mikazuki started to receive Pb emissions from Russia in early 1900s, and during the last two decades, this lake has been affected by trans-boundary Pb pollution from northern China. Lake Chokai has received Pb pollutant from northern China since early 1900s until 2009, whereas for the Lake Mikuriga the major Pb contaminant was transported from southern China during the past 100 years. The results of our study demonstrate that Japan Archipelago has received trans-boundary Pb emissions from different parts of East Asian region depending on location, and the major source region has changed historically. - Highlights: • Historical trend of Pb pollution was recorded in six Japanese Lakes. • Pb concentration and Pb isotope ratios were determined for sediment cores. • High [Pb] and less radiogenic Pb isotope ratios

  18. Preliminary study to characterize plastic polymers using elemental analyser/isotope ratio mass spectrometry (EA/IRMS).

    Science.gov (United States)

    Berto, Daniela; Rampazzo, Federico; Gion, Claudia; Noventa, Seta; Ronchi, Francesca; Traldi, Umberto; Giorgi, Giordano; Cicero, Anna Maria; Giovanardi, Otello

    2017-06-01

    Plastic waste is a growing global environmental problem, particularly in the marine ecosystems, in consideration of its persistence. The monitoring of the plastic waste has become a global issue, as reported by several surveillance guidelines proposed by Regional Sea Conventions (OSPAR, UNEP) and appointed by the EU Marine Strategy Framework Directive. Policy responses to plastic waste vary at many levels, ranging from beach clean-up to bans on the commercialization of plastic bags and to Regional Plans for waste management and recycling. Moreover, in recent years, the production of plant-derived biodegradable plastic polymers has assumed increasing importance. This study reports the first preliminary characterization of carbon stable isotopes (δ(13)C) of different plastic polymers (petroleum- and plant-derived) in order to increase the dataset of isotopic values as a tool for further investigation in different fields of polymers research as well as in the marine environment surveillance. The δ(13)C values determined in different packaging for food uses reflect the plant origin of "BIO" materials, whereas the recycled plastic materials displayed a δ(13)C signatures between plant- and petroleum-derived polymers source. In a preliminary estimation, the different colours of plastic did not affect the variability of δ(13)C values, whereas the abiotic and biotic degradation processes that occurred in the plastic materials collected on beaches and in seawater, showed less negative δ(13)C values. A preliminary experimental field test confirmed these results. The advantages offered by isotope ratio mass spectrometry with respect to other analytical methods used to characterize the composition of plastic polymers are: high sensitivity, small amount of material required, rapidity of analysis, low cost and no limitation in black/dark samples compared with spectroscopic analysis.

  19. Effects of lipid extraction on stable isotope ratios in avian egg yolk: Is arithmetic correction a reliable alternative?

    Science.gov (United States)

    Oppel, S.; Federer, R.N.; O'Brien, D. M.; Powell, A.N.; Hollmén, Tuula E.

    2010-01-01

    Many studies of nutrient allocation to egg production in birds use stable isotope ratios of egg yolk to identify the origin of nutrients. Dry egg yolk contains >50% lipids, which are known to be depleted in 13C. Currently, researchers remove lipids from egg yolk using a chemical lipid-extraction procedure before analyzing the isotopic composition of protein in egg yolk. We examined the effects of chemical lipid extraction on ??13C, ??15N, and ??34S of avian egg yolk and explored the utility of an arithmetic lipid correction model to adjust whole yolk ??13C for lipid content. We analyzed the dried yolk of 15 captive Spectacled Eider (Somateriafischeri) and 20 wild King Eider (S. spectabilis) eggs, both as whole yolk and after lipid extraction with a 2:1 chloroform:methanol solution. We found that chemical lipid extraction leads to an increase of (mean ?? SD) 3.3 ?? 1.1% in ??13C, 1.1 ?? 0.5% in ??15N, and 2.3 ?? 1.1% in ??34S. Arithmetic lipid correction provided accurate values for lipid-extracted S13C in captive Spectacled Eiders fed on a homogeneous high-quality diet. However, arithmetic lipid correction was unreliable for wild King Eiders, likely because of their differential incorporation of macronutrients from isotopically distinct environments during migration. For that reason, we caution against applying arithmetic lipid correction to the whole yolk ??13C of migratory birds, because these methods assume that all egg macronutrients are derived from the same dietary sources. ?? 2010 The American Ornithologists' Union.

  20. Using the Carbon Isotope Ratios of Bison Tooth Enamel and Bone Collagen as a Quantitative Proxy for Reconstructing Grassland Vegetation and Paleotemperatures

    Science.gov (United States)

    Hoppe, K. A.; Paytan, A.; Chamberlain, P.

    2005-12-01

    The carbon isotope ratios of tissues from grazing herbivores reflect the average carbon isotope ratios of local grasslands, which vary with the abundance of cool-season (C-3) versus warm-season (C-4) grasses. Since the C-3/C-4 ratios of grasslands correlate with climate, the carbon isotope ratios of fossil grazers may serve as a proxy for reconstructing paleovegetation and paleoclimatic conditions. Analyses of fossil and subfossil bison hold particular promise for use as a proxy for paleoenvironmental conditions in North America because bison remains are abundant in Holocene and Pleistocene deposits across most of the continent. However, the accuracy and precision of paleoenvironmental reconstructions based on bison is currently uncertain because the relationship between bison isotope and the abundance of C-3 and C-4 grasses has not been precisely quantified across different environments. We have analyzed the carbon isotope ratios of tooth enamel carbonate and bone collagen from 88 modern free ranging bison ( Bison bison) from ten locations in the Central United States. The C-4 biomass at these locations ranged from less than 1 percent to 95 percent of the total grass biomass. The mean carbon isotope ratios of enamel for each population correlated well with the local abundance of C-4 grasses (R2 = 0.93, p = 0.0001) and with variations in mean annual temperatures (R2 = 0.83, p = 0.001). The mean carbon isotope ratios of collagen for each population also correlated well with the C-4 grass abundance (R2 = 0.97, p = 0.0001) and mean annual temperature (R2 = 0.84, p = 0.0002). Enamel and collagen display similar variability (mean standard deviation = 0.7 per mil), and the variability does not change with climate, habitat, or C-4 abundance. These results demonstrate that analyses of the carbon isotope ratios of fossil bison can be used as a quantitative proxy for reconstructing grassland C-3/C-4 ratios and paleotemperatures, and they will serve as a baseline for

  1. Nitrogen stable isotope ratios of anthropgenic organic matter in the coastal environment of Kosirina Bay (Murter Island, Croatia)

    Science.gov (United States)

    Dolenec, T.; Lambaša, Ž.; Lojen, S.; Rogan, N.; Kniewald, G.; Dolenec, M.

    2009-04-01

    In this study stable nitrogen isotopes ratios of particulate matter POM, zooplankton and selected biota such as Anemonia sulcata and Mytilus galloprovincialis were used to assessed the impact of anthropogenically derived organic matter from the untreated domestic sewage, municipal and industrial effluents on the coastal ecosystem of the Kosirina Bay (Murter Island). The differences in δ15N values observed in POM and organisms collected in Kosirina Bay as compared to POM and biota sampled at unaffected sites from the southern part of the Kornati Island and highly impacted Pirovac Bay revealed only a very minor effects of anthropogenic inputs of nutrients and organic matter which most probably derived from a sewage outfall south of the Tužbina Island. However, to get a better insight into the qualitative or quantitative shifts in the structure of aquatic food web caused by pollutants, more extended research on benthic population is needed, as well as a detailed investigation of seasonal variations of abundance and isotopic composition of POM and zooplankton as their presumed food source.

  2. Lead and stable lead isotope ratios in soil, earthworms, and bones of American woodcock (Scolopax minor) from eastern Canada.

    Science.gov (United States)

    Scheuhammer, Anton M; Bond, Della E; Burgess, Neil M; Rodrigue, Jean

    2003-11-01

    A study to discriminate among different possible sources of elevated Pb exposure for American woodcock (Scolopax minor) in eastern Canada is described. Undamaged wing bones excised from young-of-the-year woodcock collected from several locations in southern Ontario, southern Quebec, New Brunswick, and Nova Scotia, Canada, along with soil and earthworm (Aporrectodea tuberculata and Lumbricus rubellus) samples from the same sites, were analyzed for total Pb, and stable Pb isotopes. Ignoring six soil samples with high (> 60 microg/g) Pb concentration from the vicinity of Montreal (QC, Canada), the mean soil-Pb concentration for all sites combined was 19 microg/g (dry wt; n = 64), with a mean 206Pb:207Pb ratio of 1.19, values typical for uncontaminated rural soils in eastern North America. In earthworms, Pb concentrations ranged from 2.4 to 865 (microg/g [dry wt], mean = 24 microg/g). Concentrations of Pb in worms and soils were positively correlated (r = 0.71; p 20 microg/g) had 206Pb:207Pb ratios substantially different from worms and soils sampled from the same areas, even though woodcock feed extensively on soil invertebrates, especially earthworms. The range of 206Pb:207Pb ratios in wing bones of woodcock with elevated Pb exposure was not consistent with exposure to environmental Pb from past gasoline combustion nor Precambrian mining wastes but was consistent with ingestion of spent Pb shotgun pellets.

  3. Plutonium concentration and isotopic ratio in soil samples from central-eastern Japan collected around the 1970s

    Science.gov (United States)

    Yang, Guosheng; Zheng, Jian; Tagami, Keiko; Uchida, Shigeo

    2015-04-01

    Obtaining Pu background data in the environment is essential for contamination source identification and assessment of environmental impact of Pu released from the Fukushima Daiichi nuclear power plant (FDNPP) accident. However, no baseline information on Pu isotopes in Fukushima Prefecture has been reported. Here we analyzed 80 surface soil samples collected from the central-eastern Japan during 1969-1977 for 239+240Pu activity concentration and 240Pu/239Pu atom ratio to establish the baseline before the FDNPP accident. We found that 239+240Pu activity concentrations ranged from 0.004 -1.46 mBq g-1, and 240Pu/239Pu atom ratios varied narrowly from 0.148 to 0.229 with a mean of 0.186 +/- 0.015. We also reconstructed the surface deposition density of 241Pu using the 241Pu/239Pu atom ratio in the Japanese fallout reference material. The obtained results indicated that, for the FDNPP-accident released 241Pu, a similar radiation impact can be estimated as was seen for the global fallout deposited 241Pu in the last decades.

  4. Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax).

    Science.gov (United States)

    Vetter, Walter; Gleixner, Gerd; Armbruster, Wolfgang; Ruppe, Steffen; Stern, Gary A; Braekevelt, Eric

    2005-01-01

    In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.

  5. Statistical methods for improving verification of claims of origin for Italian wines based on stable isotope ratios

    Energy Technology Data Exchange (ETDEWEB)

    Dordevic, N.; Wehrens, R. [IASMA Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy); Postma, G.J.; Buydens, L.M.C. [Radboud University Nijmegen, Institute for Molecules and Materials, Analytical Chemistry, P.O. Box 9010, 6500 GL Nijmegen (Netherlands); Camin, F., E-mail: federica.camin@fmach.it [IASMA Research and Innovation Centre, Fondazione Edmund Mach, via Mach 1, 38010 San Michele all' Adige (Italy)

    2012-12-13

    Highlights: Black-Right-Pointing-Pointer The assessment of claims of origin is of enormous economic importance for DOC and DOCG wines. Black-Right-Pointing-Pointer The official method is based on univariate statistical tests of H, C and O isotopic ratios. Black-Right-Pointing-Pointer We consider 5220 Italian wine samples collected in the period 2000-2010. Black-Right-Pointing-Pointer Multivariate statistical analysis leads to much better specificity and easier detection of false claims of origin. Black-Right-Pointing-Pointer In the case of multi-modal data, mixture modelling provides additional improvements. - Abstract: Wine derives its economic value to a large extent from geographical origin, which has a significant impact on the quality of the wine. According to the food legislation, wines can be without geographical origin (table wine) and wines with origin. Wines with origin must have characteristics which are essential due to its region of production and must be produced, processed and prepared, exclusively within that region. The development of fast and reliable analytical methods for the assessment of claims of origin is very important. The current official method is based on the measurement of stable isotope ratios of water and alcohol in wine, which are influenced by climatic factors. The results in this paper are based on 5220 Italian wine samples collected in the period 2000-2010. We evaluate the univariate approach underlying the official method to assess claims of origin and propose several new methods to get better geographical discrimination between samples. It is shown that multivariate methods are superior to univariate approaches in that they show increased sensitivity and specificity. In cases where data are non-normally distributed, an approach based on mixture modelling provides additional improvements.

  6. [Variation in amount of radioactive cesium before and after cooking dry shiitake and beef].

    Science.gov (United States)

    Nabeshi, Hiromi; Tsutsumi, Tomoaki; Hachisuka, Akiko; Matsuda, Rieko

    2013-01-01

    We investigated the change of radioactive cesium content in food due to cooking in order to estimate the internal radiation exposure due to from radioactive materials in food. Our results revealed that soaking dry shiitake in water decreased the radioactive cesium content by about 50%, compared with that present in uncooked shiitake. Radioactive cesium in beef was decreased by about 10%, 12%, 60-65% and 80% by grilling, frying, boiling and stewing, respectively, compared to uncooked beef. For cooked beef, the decrease in the ratio of radioactive cesium was significantly different among the types of cooking. The decrease ratio of radioactive cesium in boiled and stewed beef was 8 times higher than that in grilled and fried beef.

  7. The OD/OH Isotope Ratio in Comets 8P/Tuttle and C/2012 F6 (Lemmon)

    Science.gov (United States)

    Rousselot, Philippe; Jehin, Emmanuel; Hutsemekers, Damien; Manfroid, Jean; Decock, Alice; Bockelee-Morvan, Dominique

    2016-10-01

    The determination of isotopic ratios in solar system objects is an important source of information about their origin, especially for comets. Among these ratios the D/H is of particular importance because of its sensitivity to fractionation processes and physical environment, and the abundance of hydrogen in the solar system. The main molecule used to derive this ratio in comets is water. So far, apart water, only HCN has permitted to derive D/H ratio and not only upper limits.Most of the existing determinations of D/H in water molecules have been obtained by spectroscopic observations of water lines in the sub-mm or near infrared range [1,2]. So far only one measurement has been based on OD/OH emission lines radicals in the near-UV [3] and another one on the Lyman-alpha D emission [4]. In situ measurements have also been obtained in comets 1P/Halley and 67P/Churyumov-Gerasimenko using mass spectrometer [5,6,7,8].In this work we have used the OH and OD ultraviolet bands at 310 nm observed with the ESO 8-m Very Large Telescope feeding the Ultraviolet-Visual Echelle Spectrograph (UVES) for measuring the D/H ratio in comets 8P/Tuttle and C/2012 F6 (Lemmon). The OH and OD being the photodissociation products of H2O and HDO such observations allow to derive D/H ratio for water molecules. This work constitutes an independant determination of the D/H ratios already published for these comets and based on observations performed in the sub-mm and near infrared range of H2O and HDO lines. We present our modeling, data analysis and numerical values obtained for this ratio.[1] D. Bockelée-Morvan et al., 2015, SSR 197, 47-83 [2] N. Biver et al., 2016, A&A 589, id A78, 11p [3] D. Hutsemékers et al., 2008, A&A 490, L31 [4] H.A. Weaver et al., 2008, LPI Contributions 1405, 8216 [5] H. Balsiger, K. Altwegg, J. Geiss, 1995, JGR 100, 5827 [6] P. Eberhardt et al., 1995, A&A 302, 301 [7] R.H. Brown et al., 2012, PSS 60, 166 [8] K. Alwegg et al., 2015, Science 347, article id. 1261952

  8. Mineral resource of the month: cesium

    Science.gov (United States)

    Angulo, Marc A.

    2010-01-01

    The article offers information on cesium, a golden alkali metal derived from the Latin word caesium which means bluish gray. It mentions that cesium is the first element discovered with the use of spectroscopy. It adds that the leading producer and supplier of cesium is Canada and there are 50,000 kilograms of cesium consumed of the world in a year. Moreover, it states that only 85% of the cesium formate can be retrieved and recycled.

  9. Seasonal Variation in the Carbon Isotope Ratio of Ecosystem Respiration in Two Coniferous Forests

    Science.gov (United States)

    McDowell, N. G.; Bowling, D.; Schauer, A.; Irvine, J.; Bond, B. J.; Law, B.; Ehleringer, J. R.

    2003-12-01

    We examined weekly variation in the stable carbon isotope signature of ecosystem respiration (δ 13CR) using the Keeling plot approach at two forests in Oregon USA: a wet (>2300 mm annual precipitation) 20-year-old Pseudotsuga menziesii plantation located in the Coast Range near the Pacific Ocean, and a dry ( ˜520 mm annual precipitation) 250-year-old Pinus ponderosa forest located on the eastern slope of the Cascade Mountains. The two forests experience similar regional weather patterns with wet winters and dry summers, but the coastal site has milder temperatures and greater soil and atmospheric water content. Air was sampled on 51 and 42 separate nights at the Pinus and Pseudotsuga forests, respectively, between 2001 and 2002. Both forests exhibited greater intra-annual variation in δ 13CR than has been previously observed in C3 ecosystems (>8.0 ‰ over the year). Mean annual δ 13CR matched that expected based on annual precipitation, averaging -25.4 ‰ at the Pinus forest and -26.2 ‰ at the Pseudotsuga forest. Variability in δ 13CR at both sites was highest during seasons when rainfall was abundant (autumn, winter and spring) and lowest during summer drought. During the period of drought, soil temperature was positively correlated with δ 13CR at both forests. When all seasons were analyzed, δ 13CR was negatively correlated with soil water content at both forests. The Pseudotsuga forest was more strongly coupled to soil and atmospheric water content than the Pinus forest. This difference could be related to availability of a deep water source at the Pinus forest that buffers it from drought effects. δ 13CR at the Pinus forest was significantly but weakly related to canopy conductance suggesting that δ 13CR is coupled to canopy gas exchange. δ 13CR was significantly correlated between the two forests after removal of outliers associated with extreme, site-specific meteorological events (i.e. local freezes), demonstrating that δ 13CR is coupled

  10. Petrogenesis of the Neoproterozoic bimodal volcanic rocks along the western margin of the Yangtze Block: New constraints from Hf isotopes and Fe/Mn ratios

    Institute of Scientific and Technical Information of China (English)

    LI Xianhua; QI Changshi; LIU Ying; LIANG Xirong; TU Xianglin; XIE Liewen; YANG Yueheng

    2005-01-01

    High-precision major element and Hf isotope data are reported for the Neoproterozoic Suxiong volcanic rocks along the western margin of the Yangtze Block. These volcanic rocks have variable εHf(T) values and Fe/Mn ratios. The relatively primitive basalts have high Fe/Mn ratios and high Hf-Nd isotopic compositions, indicating that they were generated by partial melting of garnet clinopyroxene in mantle plume at high pressure. Thus, the Suxiong basalts are genetically related to the proposed Neoproterozoic superplume. On the contrary, a few differentiated basalts have low Fe/Mn ratios and low Hf-Nd isotopic compositions. They are likely to experience assimilation-fractional crystallization process. The Suxiong rhyolites have consistent Hf and Nd model ages of 1.3-1.4 Ga. They are likely generated by shallow dehydration melting of pre-existing young arc igneous rocks associated with the basaltic underplating/intrusion in a continental rift.

  11. Recent applications on isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles

    Science.gov (United States)

    Becker, J. Sabine; Sela, Hagit; Dobrowolska, Justina; Zoriy, Miroslav; Becker, J. Susanne

    2008-02-01

    Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have proved themselves to be powerful and sensitive inorganic mass spectrometric techniques for analysing stable and radioactive isotopes in different application fields because of their high sensitivity, low detection limits, good accuracy and precision. New applications of ICP-MS focus on tracer experiments and the development of isotope dilution techniques together with nanoflow injections for the analysis of small volumes of biological samples. Today, LA-ICP-MS is the method of choice for direct determination of metals, e.g., on protein bands in gels after the gel electrophoresis of protein mixtures. Tracer experiments using highly enriched 65Cu were utilized in order to study the formation of metal-binding bovine serum proteins. A challenging task for LA-ICP-MS is its application as an imaging mass spectrometric technique for the production of isotope images (e.gE, from thin sections of brain tissues stained with neodymium). In this paper, we demonstrate the application of imaging mass spectrometry on single particles (zircon and uranium oxide). Single Precambrian zircon crystals from the Baltic Shield were investigated with respect to isotope ratios using LA-ICP-MS for age dating. The U-Pb age was determined from the isochrone with (1.48 ± 0.14) × 109 a. Using isotope ratio measurements on 10 nuclear uranium oxide single particles the 235U/238U isotope ratio was determined to be 0.032 ± 0.004. This paper describes recent developments and applications of isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles.

  12. Analysis on the Isotopic Ratio of Picogram Pu by TIMS%皮克量级钚同位素丰度比的TIMS分析

    Institute of Scientific and Technical Information of China (English)

    杨天丽; 龙开明; 刘雪梅; 刘钊; 汤磊

    2005-01-01

    The isotopic abundance ratios for Pu at 6.7 pg level were measured by thermal surface ionization mass spectrometry (TIMS). During the preparation of Pu samples carbon power was used as an emitting and stabilizing reagent, which increase the collection efficiency, the ion current intense and the ion emission stability for Pu. The measurment results indicate that the relative standard deviation of 2.7% for the isotopic abundance ratios of 240Pu to 239Pu is achieved when the 240Pu ion current is 8-20 cps.

  13. Water vapour {sup 18}O/{sup 16}O isotope ratio in surface air in New England, USA

    Energy Technology Data Exchange (ETDEWEB)

    Xuhui Lee [Yale Univ., New Haven, CT (United States). School of Forestry and Environmental Studies; Smith, Ronald; Williams, John [Yale Univ., New Haven, CT (United States). Dept. of Geology and Geophysics

    2006-09-15

    In this paper, we report the results of the analysis of two high-resolution time-series of water vapour {sup 18}O/{sup 16}O ratio {delta}{sub v} in surface air observed in Connecticut, USA. On an annual time-scale, {delta}{sub v} is a linear function of ln w, where w is water vapour mixing ratio, and is approximated by a Rayleigh distillation model with partial (80%) rainout. On time scales a few days, {delta}{sub v} shows considerable variations, often exceeding 20 per mil, and is higher in the wetting phase than in the drying phase of a weather cycle. In precipitation events, the vapour in the surface layer is in general brought to state of equilibrium with falling raindrops but not with snowflakes. On a diurnal time-scale, a peak-to-peak variation of 1-2 per mil is observed at a coastal site. At an interior site, evidence of a diurnal pattern is present only on days of low humidity. Our results suggest that the intercept parameter of the Keeling plot is an ambiguous quantity and should not be interpreted as being equivalent to the isotopic signature of evapotranspiration.

  14. The 35Cl/37Cl isotopic ratio in dense molecular clouds: HIFI observations of hydrogen chloride towards W3A

    CERN Document Server

    Cernicharo, J; Daniel, F; Agundez, M; Caux, E; de Graauw, T; De Jonge, A; Kester, D; Leduc, H G; Steinmetz, E; Stutzki, J; Ward, J S

    2010-01-01

    We report on the detection with the HIFI instrument on board the Herschel satellite of the two hydrogen chloride isotopologues, H35Cl and H37Cl, towards the massive star-forming region W3A. The J=1-0 line of both species was observed with receiver 1b of the HIFI instrument at 625.9 and 624.9 GHz. The different hyperfine components were resolved. The observations were modeled with a non-local, non-LTE radiative transfer model that includes hyperfine line overlap and radiative pumping by dust. Both effects are found to play an important role in the emerging intensity from the different hyperfine components. The inferred H35Cl column density (a few times 1e14 cm^-2), and fractional abundance relative to H nuclei (~7.5e^-10), supports an upper limit to the gas phase chlorine depletion of ~200. Our best-fit model estimate of the H35Cl/H37Cl abundance ratio is ~2.1+/-0.5, slightly lower, but still compatible with the solar isotopic abundance ratio (~3.1). Since both species were observed simultaneously, this is the...

  15. Cesium diffusion in graphite

    Energy Technology Data Exchange (ETDEWEB)

    Evans, R.B. III; Davis, W. Jr.; Sutton, A.L. Jr.

    1980-05-01

    Experiments on diffusion of /sup 137/Cs in five types of graphite were performed. The document provides a completion of the report that was started and includes a presentation of all of the diffusion data, previously unpublished. Except for data on mass transfer of /sup 137/Cs in the Hawker-Siddeley graphite, analyses of experimental results were initiated but not completed. The mass transfer process of cesium in HS-1-1 graphite at 600 to 1000/sup 0/C in a helium atmosphere is essentially pure diffusion wherein values of (E/epsilon) and ..delta..E of the equation D/epsilon = (D/epsilon)/sub 0/ exp (-..delta..E/RT) are about 4 x 10/sup -2/ cm/sup 2//s and 30 kcal/mole, respectively.

  16. Determination of urea kinetics by isotope dilution with [C-13]urea and gas chromatography isotope ratio mass spectrometry (GC-IRMS) analysis

    NARCIS (Netherlands)

    Kloppenburg, Wybe; Wolthers, BG; Stellaard, F; Elzinga, H; Tepper, T; deJong, PE; Huisman, RM

    1997-01-01

    1. Stable urea isotopes can be used to study urea kinetics in humans, The use of stable urea isotopes far studying urea kinetic parameters in humans on a large scale is hampered by the high costs of the labelled material, We devised a urea dilution for measurement of the distribution volume, product

  17. Near-infrared spectroscopy of M dwarfs. IV. A preliminary survey on the carbon isotopic ratio in M dwarfs*

    Science.gov (United States)

    Tsuji, Takashi

    2016-10-01

    Carbon isotopic ratios are estimated in 48 M dwarfs based on the medium resolution near infrared spectra (λ/Δ λ ≈ 20000) of the 13CO (3,1) band. We find clear evidence for the presence of a 13CO feature for the first time in the spectra of M dwarfs. Spectral resolution of our observed data, however, is not high enough to analyze the 13CO feature directly. Instead, we compare the observed spectrum with synthetic spectra assuming 12C/13C = 10, 25, 50, 100, and 200 for each of 48 M dwarfs and estimate the best possible 12C/13C ratio by chi-square analysis. The resulting 12C/13C ratios in M dwarfs distribute from 39 to a lower limit of 200. The mean value of 31 M dwarfs for which 12C/13C ratios are determined (i.e., excluding those with the lower limit only) is (12C/13C)dM = 87 ± 21 (p.e.), and that of 48 M dwarfs including those with the lower limit of 200 is (12C/13C)dM > 127 ± 41 (p.e.). These results are somewhat larger than the 12C/13C ratio of the present interstellar matter (ISM) determined from the molecular lines observed in the millimeter and optical wavelength regions. Since the amount of 13C in the ISM has increased with time due to mass loss from evolved stars, the 12C/13C ratios in M dwarfs, reflecting those of the past ISM, should be larger than those of the present ISM. In M dwarfs, log 13C/12C plotted against log AC shows a large scatter without clear dependence on the metallicity. This result shows a marked contrast to log 16O/12C (= log AO/AC) plotted against log AC, which shows a rather tight correlation with a larger value at the lower metallicity. Such a contrast can be a natural consequence of 16O and 12C being primary products in stellar nuclear synthesis while 13C is a secondary product, at least partly.

  18. Quantitative Reconstruction of Sulfur Deposition Using a Mixing Model Based on Sulfur Isotope Ratios in Tree Rings.

    Science.gov (United States)

    Ishida, Takuya; Tayasu, Ichiro; Takenaka, Chisato

    2015-11-01

    Quantification of sulfur (S) deposition is critical to deciphering the environmental archive of S in terrestrial ecosystems. Here we propose a mixing model that quantifies S deposition based on the S isotope ratio (δS) in tree rings. We collected samples from Japanese cedar ( D. Don) stumps from two sites: one near Yokkaichi City (YOK), which is well known for having the heaviest S air pollution in the world, and one at Inabu-cho (INA) in central Japan, which has been much less affected by air pollution. The δS profiles at both sites are consistent with S air pollution and contributions of anthropogenic S. The minimum value in YOK is lower than the δS values of anthropogenic S or any other possible source. Because the δS in the tree rings is affected by fractionation in the forest ecosystems, we used a mixing model to account for the isotope effects and to distinguish the sources of S. Based on the model results, we infer that the peak of S emissions at YOK occurred sometime between the late 1960s and early 1970s (489 mmol m yr). This estimated value is comparable with the highest reported values in Europe. This is the first quantitative estimate of anthropogenic input of S in forest systems based on δS in tree rings. Our results suggest that tree ring data can be used when monitoring stations of atmospheric S are lacking and that estimates of S deposition using δS in tree rings will advance our understanding of the local-scale S dynamics and the effect of human activities on it.

  19. Separating Autotrophic and Heterotrophic Contributions to Soil Respiration in Maize-Based Agroecosystems Using Stable Carbon Isotope Ratio Mass Spectrometry.

    Science.gov (United States)

    Amos, B.; Walters, D. T.; Madhavan, S.; Arkebauer, T. J.; Scoby, D. L.

    2005-12-01

    Any effort to establish a carbon budget for a growing crop by means of a thorough accounting of all C sources and sinks will require the ability to discriminate between autotrophic and heterotrophic contributions to soil surface CO2 flux. Autotrophic soil respiration (Ra) is defined as combined root respiration and the respiration of soil microorganisms residing in the rhizosphere and using root-derived carbohydrates as an energy source, while heterotrophic respiration (Rh) is defined as the respiration of soil microorganisms and macroorganisms not directly under the influence of the live root system and using SOM as an energy source. We partition soil surface CO2 flux into its autotrophic and heterotrophic components by combining root exclusion with stable carbon isotope techniques in production scale (~65 ha) maize-based agroecosystems. After flux measurements, small chambers are placed on collars in both root excluded shields and in non-root excluded soil, ambient headspace CO2 is removed using a soda lime trap, and soil-respired C is allowed to collect in the chambers. Soil respiration samples are then collected in 12mL evacuated exetainers and analyzed for δ13C by means of a Finnigan Delta-S isotope ratio mass spectrometer interfaced with a Thermo Finnigan GasBench II and a cryogenic trap to increase CO2 concentration. These δ13C measurements were made throughout the 2005 growing season in maize fields representing three agroecosystems: irrigated continuous maize, irrigated maize-soybean rotation, and rainfed maize soybean rotation. Estimates of autotrophic and heterotrophic soil respiration along with other results of this study will be presented.

  20. Stable isotope ratio analysis of breastfeeding and weaning practices of children from medieval Fishergate House York, UK.

    Science.gov (United States)

    Burt, Nicole M

    2013-11-01

    Rib collagen of 51 juveniles and 11 adult females from the late medieval Fishergate House cemetery site (York, UK) were analyzed using nitrogen and carbon stable isotope ratio analysis to determine the weaning age for this population and to reconstruct diet. The juveniles' ages ranged from fetal to 5-6 years, while the females were of reproductive age. Previous researchers suggested that the children from Fishergate House might have been weaned later than the medieval British norm of 2 years, based on a mortality peak at 4-6 years of age. The results show weaning was complete by 2 years of age, agreeing with previous British weaning studies. The adult female δ(15) N values have a mean of 11.4‰ ± 1.1‰ and the δ(13) C values have a mean of -19.4‰ ± 0.4‰. These findings are consistent with previous isotopic studies of female diet in York during this period, though slightly lower. The weaned juvenile nitrogen values were found to be higher than the adult females (12.4‰ ± 1.0‰ for δ(15) N and -19.7‰ ± 0.5‰ for δ(13) C), which might indicate a dependence on higher trophic level proteins such as marine fish or pork. Marine fish is considered a high status food and children are considered low-status individuals at this time, making this a particularly interesting finding. Weaning does not appear to coincide with peak mortality, suggesting environment factors may be playing a larger role in child mortality at Fishergate House.

  1. The spatial patterns of water management practices are reflected in the strontium isotope ratios of human hair

    Science.gov (United States)

    Tipple, B. J.; Valenzuela, L. O.; Ehleringer, J.

    2012-12-01

    Element concentrations and isotopes of human tissues are commonly used to understand how emissions and processes within urban ecosystems affect health. Thus, it is important to understand how these elements are incorporated and flow through the urban environment and are ultimately incorporated into human tissues. Here, we designed an experiment to identify the relative importance of strontium (Sr) sources (bedrock, dust, food, and water) to hair Sr isotope ratios (87Sr/86Sr). To understand the contribution of Sr to human hair, we collected hair from individuals living in Salt Lake City, Utah. In addition to sample location, we compiled information regarding age, sex, ethnicity, and dietary habits. We found a significant association between 87Sr/86Sr value of hair and collection location. There were no significant relationships between 87Sr/86Sr value of hair and age, ethnicity, or sex. We had not predicted a relationship between 87Sr/86Sr values and collection location, because of the close proximities of sites to one another (all within an 8-km radius). We found that tap water 87Sr/86Sr values across the Salt Lake Valley varied with water management practice and this variation corresponded to hair 87Sr/86Sr value. These data suggest an additional geographically controlled source of Sr may be an important contributor to the 87Sr/86Sr value of hair. These findings suggest that local water is an important source of Sr in human hair and that hair is a sensitive temporal carrier of this environmental information. These observations have important implications to future studies of humans with regard to urban ecology, human health, forensic sciences, and anthropology.

  2. Carbon isotope ratios in logged and unlogged boreal forests: Examination of the potential for determining wildlife habitat use

    Science.gov (United States)

    France, Robert

    1996-03-01

    Due to assimilation of recycled CO2 from litter decomposition and photosynthetic changes in carbon fractionation at low light levels, the foliage at the base of a forest is often more depleted in13C compared to that exposed to the atmosphere in either the canopy or in open clearings. This is referred to as the canopy effect. African research has indicated that these habitat differences in foliar δ13C can be substantial enough to affect the carbon isotope ratios of resident fauna. Previous work documenting a 30-year chronology on moose teeth from Isle Royale National Park indicated a progressive depletion in13C and suggested that this could be due to forest regrowth following extensive burning. The present study examined the assumption implicit in this hypothesis that foliar δ13C varies between open and closed boreal forest sites. I found a marginal canopy effect of 2‰ δ13C difference between upper canopy and ground flora for a forest in northwestern Ontario and an average difference of 1.2‰ in under- and mid-story vegetation between closed forests and open clear-cuts. Because of these small differences, the utility of carbon isotope analysis in quantifying temporally integrated exploitation of deforested habitats will be low for northern boreal locations. In denser forests, such as those in the tropics or western North American where the canopy effect can be expected to be much greater, δ13C analysis may still offer some promise for determining selection by wildlife of disturbed habitats.

  3. High Precision 142Nd/144Nd and 143Nd/144Nd Isotope Ratio Measurements in Rock Samples

    Science.gov (United States)

    Ali, A.; Srinivasan, G.

    2009-05-01

    The long-lived 147Sm-143Nd system with a half-life (T1/2) of 106 Gyr is generally used for geochronology. The short-lived 146Sm-142Nd system (T1/2= 103 Myr) is used as a geological tracer to track early (˜500 Ma) silicate differentiation [1] events in different planetary bodies. The isotope composition measurements by thermal ionization mass spectrometry (TIMS) require purification of Nd using chemical separation methods. This is important as an impure sample will give both a very poor ion yield and cause beam instability in the mass spectrometer, potentially resulting in a poor analysis [2]. The separation of Nd for 143Nd isotope measurement is, fairly straightforward because there is no isobaric interference of any other REE. While 142Nd isotope analysis needs chemically separated Nd fraction to be ˜100% Ce-free as latter is composed of a substantial amount of 142Ce isotope. A 4-steps technique, modified from Caro et al., [3], for the separation of Nd is established at the Cosmochemistry Laboratory of University of Toronto, Canada and applied to the measurement of Nd isotope ratios in geological reference sample BCR-2 (USGS, Columbia River basalt) using TIMS. Results of the isotopic ratios obtained for BCR-2 are in good agreement with published values [e.g., 4]. Analytical work on the samples discovered as the oldest rocks on Earth [5] from Nuvvuagittuq greenstone belt in Québec, Canada and various meteorites is in progress. An account of the procedures involved is briefly described here. All working solutions and acids were prepared using >18.2 MΩ.cm-1 H2O from a Milli-Q water system. Experiments were performed under Class 100 clean work bench with acid-cleaned apparatus and plastic-ware. The whole rock powders were weighed (20-30 mg) and dissolved in a mixture of HF and HNO3 using PFA vials and heated at 110°C. Further decomposition was done in Teflon bomb in the oven at 205°C. Later on contents of the Teflon bomb were transferred to vials and fluorides

  4. Source identification of particulate organic matter in view of land uses in Shingil Creek using carbon, nitrogen and oxygen isotope ratios.

    Science.gov (United States)

    Kim, Dahae; Lee, Yeonjung; Ock, Giyoung; Kang, Sujin; Kim, Minseob; Choi, Jongwoo; Shin, Kyung-Hoon

    2016-04-01

    Anthropogenic inputs influence the quality and quantity of organic matter, which is important for recycling of nutrients and chemical elements. Stable isotope techniques are useful for distinguishing the origin of organic matter by using the characteristics that are distinctive between sources. Artificial Lake Shihwa, especially the Shingil creek is typically under the strong anthropogenic pressure with continuous continental inputs from various sources. Hence in this study, the characteristics and sources of organic matter in water and surface sediment of the Shingil creeks in the rural, urban, and industrial areas were evaluated by using carbon, nitrogen and oxygen isotope ratios, by analyzing samples collected during the rainy season and dry season. Among the input sources, the organic matter derived from industrial regions showed distinct nitrogen isotope values compared to other sites. Further studies including other techniques such as hydrogen isotope will provide an insight into the development of a strategy for effective water quality management in Lake Shihwa

  5. D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types-I,-II,IIS, and -III

    Science.gov (United States)

    Schimmelmann, Arndt; Lewan, Michael D.; Wintsch, Robert P.

    1999-11-01

    Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381°C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330°C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ≈ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381°C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350°C for 72 h, or 330°C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115°C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected

  6. D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

    Science.gov (United States)

    Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

    1999-01-01

    Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected

  7. Multi-elemental Gd, Eu, Sm, Nd isotope ratio measurements by liquid chromatography coupled to MC-ICPMS with variable Faraday cup configurations during elution.

    Science.gov (United States)

    Guéguen, Florence; Nonell, Anthony; Isnard, Hélène; Vio, Laurent; Chartier, Frédéric

    2017-01-01

    The high-precision isotopic characterization of actinides and fission products in nuclear samples is fundamental for various applications such as the management of spent nuclear fuel or the validation of neutronic calculation codes. However multi-elemental isotope ratio measurements by mass spectrometric techniques are hampered by the presence of both spectral and non-spectral interferences as complex sample matrices are encountered in such topics, but also due to the lack of high precision mass spectrometers able to cover the entire mass spectrum. This work describes a new LC-MC-ICPMS approach allowing simultaneous high-precision and multi-elemental isotope ratio measurements of four fission products of interest for nuclear issues (Nd, Sm, Eu, Gd) within a single elution run. Variable motorized Faraday cup configurations were successively used during a specifically designed elution procedure in order to take into account the non-natural Nd, Sm, Eu, Gd isotopic compositions encountered in irradiated nuclear samples. This new method, involving the relevant isotopic reference standard injection timings for on-line mass bias corrections, was validated by the analysis of a simulated fission product fraction from a (235)U-irradiated target. Reproducibilities better than 2‰ (k=2), comparable to those obtained by off-line measurements and the classic sample-standard bracketing mass bias correction approach, were obtained for all isotope ratios, except those involving isotopes with a transient signal peak apex lower than 100mV, for which the reproducibilities were comprised between 2‰ and 6‰.

  8. Excitation function and isomeric ratio of Tc-isotopes from the {sup 93}Nb(α, xn) reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kim, K. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Kim, G.N., E-mail: gnkim@knu.ac.kr [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Naik, H. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Rediochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai 400085 (India); Zaman, M. [Department of Physics, Kyungpook National University, Daegu 702-701 (Korea, Republic of); Yang, S.-C.; Song, T.-Y. [Nuclear Data Center, Korea Atomic Energy Research Institute, Daejeon 305-353 (Korea, Republic of); Guin, R.; Das, S.K. [Variable Energy Cyclotron Centre, 1/AF Bidhan Nagar, Kolkata 700064 (India)

    2015-03-15

    The excitation functions of {sup 94–96}Tc isotopes and independent isomeric ratios of {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc from the {sup 93}Nb(α, xn) reaction within the energy range below 40 MeV have been determined by using a stacked-foil activation and an off-line γ-ray spectrometric technique at the Variable Energy Cyclotron Center, Kolkota, India. The excitation function of {sup 94–96}Tc in the {sup 93}Nb(α, xn) reaction was also calculated by using the computer code TALYS 1.6. The present data are found to be in general agreement with the literature data but have similar trend with some deviation from calculated data of the TALYS 1.6 code. The isomeric ratios of {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc in the {sup 93}Nb(α, xn) reactions from the present work and literature data were compared with similar data in the {sup 93}Nb({sup 3}He, xn) and {sup 96}Mo(p, xn) reactions. In all the three reactions, the isomeric ratios increase with the increasing excitation energy. However, at all excitation energies, the isomeric ratios of {sup 93m, g}Tc, {sup 94m, g}Tc, and {sup 95m, g}Tc in the {sup 93}Nb(α, xn) and {sup 93}Nb({sup 3}He, xn) reactions are higher than those in the {sup 96}Mo(p, xn) reactions, which indicate the role of input angular momentum besides excitation energy. Above the excitation energy of 35–55 MeV, the isomeric ratios of {sup 95m, g}Tc, {sup 94m, g}Tc, and {sup 93m, g}Tc decrease in all the {sup 93}Nb(α, xn), {sup 93}Nb({sup 3}He, xn) and {sup 96}Mo(p, xn) reactions. This decreasing trend at higher excitation energy indicates the starting of pre-equilibrium reaction, which depends on the target, projectile, and type of reaction products.

  9. Cesium chloride-induced torsades de pointes.

    Science.gov (United States)

    Wiens, Matthew; Gordon, Wendy; Baulcomb, Daisy; Mattman, Andre; Mock, Tom; Brown, Robert

    2009-09-01

    The chloride salt of cesium, a group 1A element, is gaining popularity as an alternative treatment of advanced cancers. Cesium chloride has primarily been used in cardiovascular research for arrhythmogenesis in animals because of its potassium-blocking effects. The present report describes a 45-year-old woman with metastatic breast cancer who experienced repeated episodes of torsades de pointes polymorphic ventricular tachycardia after several months of oral cesium therapy. There was a clear temporal relationship between cesium ingestion and the arrhythmia, which later resolved following discontinuation of cesium therapy. Serial cesium plasma and whole blood levels were measured over the ensuing six months and pharmacokinetic analysis was performed.

  10. Improvements in Precise and Accurate Isotope Ratio Determination via LA-MC-ICP-MS by Application of an Alternative Data Reduction Protocol

    Science.gov (United States)

    Fietzke, J.; Liebetrau, V.; Guenther, D.; Frische, M.; Zumholz, K.; Hansteen, T. H.; Eisenhauer, A.

    2008-12-01

    An alternative approach for the evaluation of isotope ratio data using LA-MC-ICP-MS will be presented. In contrast to previously applied methods it is based on the simultaneous responses of all analyte isotopes of interest and the relevant interferences without performing a conventional background correction. Significant improvements in precision and accuracy can be achieved when applying this new method and will be discussed based on the results of two first methodical applications: a) radiogenic and stable Sr isotopes in carbonates b) stable chlorine isotopes of pyrohydrolytic extracts. In carbonates an external reproducibility of the 87Sr/86Sr ratios of about 19 ppm (RSD) was achieved, an improvement of about a factor of 5. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170±0.000007 (2SE) was determined, which agrees well with the value of 0.7091741±0.0000024 (2SE) reported for modern sea water [1,2]. Stable chlorine isotope ratios were determined ablating pyrohydrolytic extracts with a reproducibility of about 0.05‰ (RSD). For basaltic reference material JB1a and JB2 chlorine isotope ratios were determined relative to SMOC (standard mean ocean chlorinity) δ37ClJB-1a = (-0.99±0.06) ‰ and δ37ClJB-1a = (-0.60±0.03) ‰ (SD), respectively, in accordance with published data [3]. The described strategies for data reduction are considered to be generally applicable for all isotope ratio measurements using LA-MC-ICP-MS. [1] J.M. McArthur, D. Rio, F. Massari, D. Castradori, T.R. Bailey, M. Thirlwall, S. Houghton, Palaeogeo. Palaeoclim. Palaeoeco., 2006, 242 (126), doi: 10.1016/j.palaeo.2006.06.004 [2] J. Fietzke, V. Liebetrau, D. Guenther, K. Guers, K. Hametner, K. Zumholz, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 955-961, doi:10.1039/B717706B [3] J. Fietzke, M. Frische, T.H. Hansteen and A. Eisenhauer, J. Anal. At. Spectrom., 2008, 23, 769-772, doi:10.1039/B718597A

  11. Diode laser absorption spectrometry for (CO2)-C-13/(CO2)-C-12 isotope ratio analysis : Investigation on precision and accuracy levels

    NARCIS (Netherlands)

    Castrillo, A; Casa, G; Kerstel, E; Gianfrani, L

    2005-01-01

    Near-infrared laser spectroscopy is used to measure the C-13/C-12 isotope abundance ratio in gas phase carbon dioxide. The spectrometer, developed expressly for field applications, is based on a 2 mu m distributed feedback diode laser in combination with sensitive wavelength modulation detection. It

  12. Simultaneous Determination of the 2H/1H, 17O/16O, and 18O/16O Isotope Abundance Ratios in Water by Means of Laser Spectrometry

    NARCIS (Netherlands)

    Kerstel, E.R.Th.; Trigt, R. van; Dam, N.J.; Reuss, J.; Meijer, H.A.J.

    1999-01-01

    We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative H-2/H-1, O-17/O-16, and O-18/O-16 isotope abundance ratios in water. The method uses a narrow Line width color center laser to record the direct absorption spect

  13. Determination of low isotopic enrichment of L-[1-C-13]valine by gas chromatography combustion isotope ratio mass spectrometry : a robust method for measuring protein fractional synthetic rates in vivo

    NARCIS (Netherlands)

    Reijngoud, DJ; Hellstern, G; Elzinga, H; de Sain-van der Velden, MG; Okken, A; Stellaard, F

    1998-01-01

    A method was developed for measuring protein fractional synthetic rates using the N-methoxycarbonylmethyl ester (MCM) derivative of L-[1-C-13]valine and on-line gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). The derivatization procedure can be performed rapidly and GC sep

  14. Parsec-scale Variations in the 7Li i/6Li i Isotope Ratio Toward IC 348 and the Perseus OB 2 Association

    Science.gov (United States)

    Knauth, D. C.; Taylor, C. J.; Ritchey, A. M.; Federman, S. R.; Lambert, D. L.

    2017-01-01

    Measurements of the lithium isotopic ratio in the diffuse interstellar medium from high-resolution spectra of the Li i λ6708 resonance doublet have now been reported for a number of lines of sight. The majority of the results for the 7Li/6Li ratio are similar to the solar system ratio of 12.2, but the line of sight toward o Per, a star near the star-forming region IC 348, gave a ratio of about two, the expected value for gas exposed to spallation and fusion reactions driven by cosmic rays. To examine the association of IC 348 with cosmic rays more closely, we measured the lithium isotopic ratio for lines of sight to three stars within a few parsecs of o Per. One star, HD 281159, has 7Li/6Li ≃ 2 confirming production by cosmic rays. The lithium isotopic ratio toward o Per and HD 281159 together with published analyses of the chemistry of interstellar diatomic molecules suggest that the superbubble surrounding IC 348 is the source of the cosmic rays. Based on observations obtained with the Hobby-Eberly Telescope, which is a joint project of the University of Texas at Austin, the Pennsylvania State University, Ludwig-Maximilians-Universität München, and Georg-August-Universität Göttingen.

  15. Stable carbon isotope ratios and intrinsic water-use efficiency of Miocene fossil leaves compared to modern congeners

    Energy Technology Data Exchange (ETDEWEB)

    Marshall, J.D.; Zhang, J.; Rember, W.C.; Jennings, D.; Larson, P. (Univ. of Idaho, Moscow, ID (United States))

    1994-06-01

    Miocene fossil leaves of forest trees were extracted from the Clarkia, Idaho fossil beds and their stable carbon isotope ratios were analyzed. Fossils had higher lignin concentrations and lower cellulose concentrations that modern leaves due to diagenesis and the HF used to extract the fossils. Therefore, [delta][sup 13]C of extracted fossil lignin was compared to that of modern lignin. Fossil lignin [delta][sup 13]C was significantly different from that of congeneric modern leaves (paired t-test, P<0.0001), but was 1.9% less negative. Gymnosperms (Metasequoia, Taxodium) were less negative than angiosperms (e.g., Magnolia, Quercus, Acer, Persea), but no difference between evergreen and deciduous species was detected. Using published estimates of the concentration and [delta][sup 13]C of atmospheric CO[sub 2] during the Miocene was estimated the CO[sub 2] partial pressure gradient across the stomata (intrinsic water-use efficiency). Intrinsic water-use efficiency was at least 70% higher during this past [open quotes]greenhouse[close quotes] period than at present.

  16. Radium Isotope Ratios as Tracers for Estimating the Influence of Changjiang Outflow Water to the Adjacent Seas

    Science.gov (United States)

    Kim, K.; Kim, S.

    2006-12-01

    In order to understand the influence of Changjiang (Yangtze River) outflow water to the adjacent seas during rainy and draught seasons, we studied the origin and mixing of surface water masses in the East China Sea and the South Sea of Korea. We used Ra-228/Ra-226 activity ratio and salinity as two conservative tracers in three end-members: Changjiang water (CW); Yellow Sea water (YSW); and Kuroshio water (KW). Radium isotopes in each 300-liter of surface water samples were extracted by passing through manganese-fiber cartridges, dissolved in hydroxylamine hydrochloride solution, coprecipitated as barium sulfate, dried and measured by gamma-ray spectroscopy. Results show that surface water of the East China Sea includes all three end-member waters during the rainy season, in the order of KW (50-80%), YSW (20-50%) and CW (5-15%). Surface water of the South Sea of Korea, however, includes a little fraction of, or almost no, CW in drought season. These are the preliminary results from an ongoing 6-year project ending in 2009 which aims to predict the influence of heavily polluted Changjiang outflow water to the adjacent seas after the completion of the gigantic Three Gorges (Sanxia) Dam.

  17. Correlation between the synthetic origin of methamphetamine samples and their 15N and 13C stable isotope ratios.

    Science.gov (United States)

    Billault, Isabelle; Courant, Frédérique; Pasquereau, Léo; Derrien, Solène; Robins, Richard J; Naulet, Norbert

    2007-06-12

    The active ingredient of ecstasy, N-methyl-3,4-methyldioxyphenylisopropylamine (MDMA) can be manufactured by a number of easy routes from simple precursors. We have synthesised 45 samples of MDMA following the five most common routes using N-precursors from 12 different origins and three different precursors for the aromatic moiety. The 13C and 15N contents of both the precursors and the MDMA samples derived therefrom were measured by isotope ratio mass spectrometry coupled to an elemental analyser (EA-IRMS). We show that within-pathway correlation between the 15N content of the precursor and that of the derived MDMA can be strong but that no general pattern of correlation can be defined. Rather, it is evident that the delta15N values of MDMA are strongly influenced by a combination of the delta15N values of the source of nitrogen used, the route by which the MDMA is synthesised, and the experimental conditions employed. Multivariate analysis (PCA) based on the delta15N values of the synthetic MDMA and of the delta15N and delta13C values of the N-precursors leads to good discrimination between the majority of the reaction conditions tested.

  18. Correlation between the synthetic origin of methamphetamine samples and their {sup 15}N and {sup 13}C stable isotope ratios

    Energy Technology Data Exchange (ETDEWEB)

    Billault, Isabelle [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France)]. E-mail: Isabelle.Billault@univ-nantes.fr; Courant, Frederique [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France); Pasquereau, Leo [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France); Derrien, Solene [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France); Robins, Richard J. [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France); Naulet, Norbert [Laboratoire d' Analyse Isotopique et Electrochimique de Metabolismes, CNRS UMR6006, University of Nantes, BP 92208, 44322 Nantes (France)

    2007-06-12

    The active ingredient of ecstasy, N-methyl-3,4-methyldioxyphenylisopropylamine (MDMA) can be manufactured by a number of easy routes from simple precursors. We have synthesised 45 samples of MDMA following the five most common routes using N-precursors from 12 different origins and three different precursors for the aromatic moiety. The {sup 13}C and {sup 15}N contents of both the precursors and the MDMA samples derived therefrom were measured by isotope ratio mass spectrometry coupled to an elemental analyser (EA-IRMS). We show that within-pathway correlation between the {sup 15}N content of the precursor and that of the derived MDMA can be strong but that no general pattern of correlation can be defined. Rather, it is evident that the {delta} {sup 15}N values of MDMA are strongly influenced by a combination of the {delta} {sup 15}N values of the source of nitrogen used, the route by which the MDMA is synthesised, and the experimental conditions employed. Multivariate analysis (PCA) based on the {delta} {sup 15}N values of the synthetic MDMA and of the {delta} {sup 15}N and {delta} {sup 13}C values of the N-precursors leads to good discrimination between the majority of the reaction conditions tested.

  19. Riparian forest potential to retain sediment and carbon evaluated by the {sup 137}Cs fallout and carbon isotopic ratio techniques

    Energy Technology Data Exchange (ETDEWEB)

    Pires, Luiz F. [Universidade Estadual de Ponta Grossa (UEPG), PR (Brazil). Lab. de Fisica Aplicada a Solos e Ciencias Ambientais], e-mail: lfpires@uepg.br, e-mail: luizfpires@gmail.com; Bacchi, Osny O.S.; Reichardt, Klaus; Filippe, Joseline [Centro de Energia Nuclear na Agricultura (CENA/USP), Piracicaba, SP (Brazil). Lab. de Fisica dos Solos; Correchel, Vladia [Universidade Federal de Goias (UFG), Goiania, GO (Brazil)

    2009-07-01

    Riparian forests can provide an important service for aquatic ecosystems by sequestering hill slope-derived sediments. However, the width of a riparian buffer zone required to filter sediments is not yet well-understood. Here are used two complementary tracers to measure sediment retention. The {sup 137}Cs technique and the soil carbon isotopic ratios ({delta} {sup 13}C) are utilized to investigate sediment deposition and erosion rates on a slope transect cultivated with sugarcane followed by a secondary riparian forest zone in Iracemapolis, State of Sao Paulo, Brazil. The {sup 137}Cs technique and the {delta} {sup 13}C analysis showed that the width of a riparian vegetation in accordance to a Brazilian Environmental Law (N. 4.771/65) was not sufficient in trapping sediments coming from agricultural lands, but indicated the importance of these forests as a conservation measure at the watershed scale. The complementary {delta} {sup 13}C analysis together with soil morphology aspects allowed a better interpretation of the sediment redistribution along the sugarcane and riparian forest transect. (author)

  20. Isotope ratio by HRGC-MS of citrus Junos tanaka (yuzu) essential oils: m/z 137/136 of terpene hydrocarbons.

    Science.gov (United States)

    Sawamura, M; Ito, T; Une, A; Ukeda, H; Yamasaki, Y

    2001-12-01

    The isotope ratios of monoterpene hydrocarbons in Citrus junos Tanaka (yuzu) essential oils from different origins were determined by ordinary high-resolution gas chromatography-mass spectrometry (HRGC-MS). Both intensities of the molecular mass peaks (m/z 136) and of the isotope peaks (m/z 137) of monoterpene hydrocarbons were measured by single-ion monitoring with an MS analysis. The isotope ratios (m/z 137/136) of the ten monoterpene hydrocarbons commonly contained in citrus essential oils, alpha-pinene, beta-pinene, sabinene, myrcene, alpha-phellandrene, alpha-terpinene, limonene, gamma-terpinene, beta-phellandrene and terpinolene, were determined in yuzu samples of the highest commercial quality from 42 different production districts. Statistical treatment of these data by the t-test and sign test revealed significant differences of the isotope effects in each yuzu sample. It is suggested that this technique will be applicable for evaluating the quality, genuineness and origin of citrus fruits and their products. The isotope fingerprints were also demonstrated in several citrus fruits other than the yuzu samples.

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

    Science.gov (United States)

    Revesz, Kinga M.; Landwehr, Jurate M.

    2002-01-01

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

  2. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    Energy Technology Data Exchange (ETDEWEB)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-03-01

    ABSTRACT In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Due to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for orbitrap analyzers are very well documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LSAPGD microplasma and the inherent IR measurement qualities of orbitrap analyzers. Important to the IR performance, the various operating parameters of the orbitrap sampling interface, HCD dissociation stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1 %RSD can be achieved, with values of 1-3 %RSD observed for low-abundance species. The results suggest that the LSAPGD is a very good candidate for field deployable MS analysis and that the high resolving powers of the orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision isotope ratios.

  3. Compound-specific stable carbon isotope ratios of phenols and nitrophenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide

    Energy Technology Data Exchange (ETDEWEB)

    Irei, Satoshi, E-mail: irei.satoshi@nies.go.jp [Centre for Atmospheric Chemistry, Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario M3J 1P3 (Canada); Climate Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario M3H 5T4 (Canada); Rudolph, Jochen [Centre for Atmospheric Chemistry, Department of Chemistry, York University, 4700 Keele Street, Toronto, Ontario M3J 1P3 (Canada); Huang, Lin [Climate Research Division, Atmospheric Science and Technology Directorate, Science and Technology Branch, Environment Canada, 4905 Dufferin Street, Toronto, Ontario M3H 5T4 (Canada)

    2013-07-05

    Graphical abstract: -- Highlights: •For GCC–IRMS analysis, an approach avoiding impact of NO{sub 2} on δ{sup 13}C was demonstrated. •Carbon isotope fractionations during derivatizing reactions here were negligible. •Except some labile compounds, the overall bias of the method here was −0.21‰. •Even for the labile compounds, measurement biases ranged +1.2‰ to −1.4‰. •Real sample analysis demonstrates usefulness of the method for fractionation study. -- Abstract: We developed an analytical method for measuring compound-specific stable carbon isotope ratios (δ{sup 13}C) of phenols and nitrophenols in filter samples of particulate organic matter. The method was tested on 13 phenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), together with four nonphenolic compounds. The data obtained by our method required two specific corrections for the determination of valid δ{sup 13}C values: (1) for nitro compounds, the routine correction with use of m/z 46 for the contribution of {sup 12}C{sup 17}O{sup 16}O molecules) to m/z 45 was modified due to impact of NO{sub 2} on the m/z 46 trace, and (2) for the derivatized phenols, measured δ{sup 13}C values were corrected for the shift in δ{sup 13}C due to the addition of carbon atoms from the BSTFA moiety. Analysis of standard-spiked filters showed that overall there was a small compound-dependent bias in the δ{sup 13}C values: the average bias ± the standard error of the mean of −0.21 ± 0.1‰ for the standard compounds tested, except 3-methylcatechol, methylhydroquinone, 4-methyl-2-nitrophenol, and 2,6-dimethyl-4-nitrophenol, whereas the average biases ± the standard errors of the mean for those were +1.2 ± 0.3‰, +1.2 ± 0.2‰, −1.2 ± 0.2‰, and −1.4 ± 0.5‰, respectively, when the injected mass of a derivatized compound exceeded 15 ngC. In situations where such small biases and uncertainties are acceptable, the method described here could be used to obtain valuable

  4. Diet and habitat of the saiga antelope during the late Quaternary using stable carbon and nitrogen isotope ratios

    Science.gov (United States)

    Jürgensen, Jonathan; Drucker, Dorothée G.; Stuart, Anthony J.; Schneider, Matthias; Buuveibaatar, Bayarbaatar; Bocherens, Hervé

    2017-03-01

    Saiga antelope (Saiga tatarica) is one of the typical late Pleistocene species of the cold and arid mammoth steppe that covered a large area of northern hemisphere. The species is currently endangered and persists only in small areas of Central Asian steppe and desert ecosystems. The investigation of the ecology of the Pleistocene saiga using stable isotope ratios (δ13C, δ15N) aimed to decipher how different their diet and habitat were from those observed nowadays in relict populations. Up to 76 samples of bone collagen of ancient saiga from Western Europe, Siberia and Eastern Beringia were analysed and compared with 52 samples of hair and bone collagen of modern specimens from Kazahkstan, Russia and Mongolia. The δ13C values of the ancient saiga do not exhibit a clear trend over time. They cover the same range of values as the modern ones, from a C3-dominated to a C3-C4-dominated mixed diet (including probably Chenopodiaceae). In contrast, the δ15N values of fossil saigas are more variable and lower on average than the extant ones. The lowest δ15N values of ancient saiga are found around the Last Glacial Maximum, reflecting the influence of the cold conditions at that time. On the other hand, fossil saiga occupying the same regions as the historical and modern populations exhibit high δ15N values similar to the modern ones, confirming ecological continuity over time. Modern saiga is thus occupying just one of its potential diverse habitats they used in the past. Therefore, the extant saiga is not a refugee species confined to a suboptimal habitat. During the late Pleistocene, the saiga occupied a separate niche compared with the other ungulates of the mammoth steppe. However, this species could also adapt to a lichen-dominated diet normally seen in reindeer, leading to an isotopic overlap between the two species in south-western France and Alaska around the Last Glacial Maximum. This adaptation allowed a geographical expansion that does not correspond to a

  5. Observations of molecular hydrogen mixing ratio and stable isotopic composition at the Cabauw tall tower in the Netherlands

    Science.gov (United States)

    Batenburg, A. M.; Popa, M. E.; Vermeulen, A. T.; van den Bulk, W. C. M.; Jongejan, P. A. C.; Fisher, R. E.; Lowry, D.; Nisbet, E. G.; Röckmann, T.

    2016-12-01

    Measurements of the stable isotopic composition (δD(H2) or δD) of atmospheric molecular hydrogen (H2) are a useful addition to mixing ratio (χ(H2)) measurements for understanding the atmospheric H2 cycle. δD datasets published so far consist mostly of observations at background locations. We complement these with observations from the Cabauw tall tower at the CESAR site, situated in a densely populated region of the Netherlands. Our measurements show a large anthropogenic influence on the local H2 cycle, with frequently occurring pollution events that are characterized by χ(H2) values that reach up to ≈1 ppm and low δD values. An isotopic source signature analysis yields an apparent source signature below -400‰, which is much more D-depleted than the fossil fuel combustion source signature commonly used in H2 budget studies. Two diurnal cycles that were sampled at a suburban site near London also show a more D-depleted source signature (≈-340‰), though not as extremely depleted as at Cabauw. The source signature of the Northwest European vehicle fleet may have shifted to somewhat lower values due to changes in vehicle technology and driving conditions. Even so, the surprisingly depleted apparent source signature at Cabauw requires additional explanation; microbial H2 production seems the most likely cause. The Cabauw tower site also allowed us to sample vertical profiles. We found no decrease in χ(H2) at lower sampling levels (20 and 60 m) with respect to higher sampling levels (120 and 200 m). There was a significant shift to lower median δD values at the lower levels. This confirms the limited role of soil uptake around Cabauw, and again points to microbial H2 production during an extended growing season, as well as to possible differences in average fossil fuel combustion source signature between the different footprint areas of the sampling levels. So, although knowledge of the background cycle of H2 has improved over the last decade, surprising

  6. Ore genesis constraints on the Idaho Cobalt Belt from fluid inclusion gas, noble gas isotope, and ion ratio analyses

    Science.gov (United States)

    Hofstra, Albert H.; Landis, Gary P.

    2012-01-01

    The Idaho cobalt belt is a 60-km-long alignment of deposits composed of cobaltite, Co pyrite, chalcopyrite, and gold with anomalous Nb, Y, Be, and rare-earth elements (REEs) in a quartz-biotite-tourmaline gangue hosted in Mesoproterozoic metasedimentary rocks of the Lemhi Group. It is the largest cobalt resource in the United States with historic production from the Blackbird Mine. All of the deposits were deformed and metamorphosed to upper greenschist-lower amphibolite grade in the Cretaceous. They occur near a 1377 Ma anorogenic bimodal plutonic complex. The enhanced solubility of Fe, Co, Cu, and Au as chloride complexes together with gangue biotite rich in Fe and Cl and gangue quartz containing hypersaline inclusions allows that hot saline fluids were involved. The isotopes of B in gangue tourmaline are suggestive of a marine source, whereas those of Pb in ore suggest a U ± Th-enriched source. The ore and gangue minerals in this belt may have trapped components in fluid inclusions that are distinct from those in post-ore minerals and metamorphic minerals. Such components can potentially be identified and distinguished by their relative abundances in contrasting samples. Therefore, we obtained samples of Co and Cu sulfides, gangue quartz, biotite, and tourmaline and post-ore quartz veins as well as Cretaceous metamorphic garnet and determined the gas, noble gas isotope, and ion ratios of fluid inclusion extracts by mass spectrometry and ion chromatography. The most abundant gases present in extracts from each sample type are biased toward the gas-rich population of inclusions trapped during maximum burial and metamorphism. All have CO2/CH4 and N2/Ar ratios of evolved crustal fluids, and many yield a range of H2-CH4-CO2-H2S equilibration temperatures consistent with the metamorphic grade. Cretaceous garnet and post-ore minerals have high RH and RS values suggestive of reduced sulfidic conditions. Most extracts have anomalous 4He produced by decay of U and Th and

  7. A combustion setup to precisely reference δ13C and δ2H isotope ratios of pure CH4 to produce isotope reference gases of δ13C-CH4 in synthetic air

    Directory of Open Access Journals (Sweden)

    H. Schaefer

    2012-09-01

    Full Text Available Isotope records of atmospheric CH4 can be used to infer changes in the biogeochemistry of CH4. One factor currently limiting the quantitative interpretation of such changes are uncertainties in the isotope measurements stemming from the lack of a unique isotope reference gas, certified for δ13C-CH4 or δ2H-CH4. We present a method to produce isotope reference gases for CH4 in synthetic air that are precisely anchored to the VPDB and VSMOW scales and have δ13C-CH4 values typical for the modern and glacial atmosphere. We quantitatively combusted two pure CH4 gases from fossil and biogenic sources and determined the δ13C and δ2H values of the produced CO2 and H2O relative to the VPDB and VSMOW scales within a very small analytical uncertainty of 0.04‰ and 0.7‰, respectively. We found isotope ratios of −39.56‰ and −56.37‰ for δ13C and −170.1‰ and −317.4‰ for δ2H in the fossil and biogenic CH4, respectively. We used both CH4 types as parental gases from which we mixed two filial CH4 gases. Their δ13C was determined to be −42.21‰ and −47.25‰ representing glacial and present atmospheric δ13C-CH4. The δ2H isotope ratios of the filial CH4 gases were found to be −193.1‰ and −237.1‰, respectively. Next, we mixed aliquots of the filial CH4 gases with ultrapure N2/O2 (CH4 ≤ 2 ppb producing two isotope reference gases of synthetic air with CH4 mixing ratios near atmospheric values. We show that our method is reproducible and does not introduce isotopic fractionation for δ13C within the uncertainties of our detection limit (we cannot conclude this for δ2H because our system is currently not prepared for δ2H-CH4 measurements in air samples. The general principle of our method can be applied to produce synthetic isotope reference gases targeting δ2H-CH4 or other gas species.

  8. Elucidating microbial processes in nitrate- and sulfate-reducing systems using sulfur and oxygen isotope ratios: The example of oil reservoir souring control

    Science.gov (United States)

    Hubert, Casey; Voordouw, Gerrit; Mayer, Bernhard

    2009-07-01

    Sulfate-reducing bacteria (SRB) are ubiquitous in anoxic environments where they couple the oxidation of organic compounds to the production of hydrogen sulfide. This can be problematic for various industries including oil production where reservoir "souring" (the generation of H 2S) requires corrective actions. Nitrate or nitrite injection into sour oil fields can promote SRB control by stimulating organotrophic nitrate- or nitrite-reducing bacteria (O-NRB) that out-compete SRB for electron donors (biocompetitive exclusion), and/or by lithotrophic nitrate- or nitrite-reducing sulfide oxidizing bacteria (NR-SOB) that remove H 2S directly. Sulfur and oxygen isotope ratios of sulfide and sulfate were monitored in batch cultures and sulfidic bioreactors to evaluate mitigation of SRB activities by nitrate or nitrite injection. Sulfate reduction in batch cultures of Desulfovibrio sp. strain Lac15 indicated typical Rayleigh-type fractionation of sulfur isotopes during bacterial sulfate reduction (BSR) with lactate, whereas oxygen isotope ratios in unreacted sulfate remained constant. Sulfur isotope fractionation in batch cultures of the NR-SOB Thiomicrospira sp. strain CVO was minimal during the oxidation of sulfide to sulfate, which had δ18O SO4 values similar to that of the water-oxygen. Treating an up-flow bioreactor with increasing doses of nitrate to eliminate sulfide resulted in changes in sulfur isotope ratios of sulfate and sulfide but very little variation in oxygen isotope ratios of sulfate. These observations were similar to results obtained from SRB-only, but different from those of NR-SOB-only pure culture control experiments. This suggests that biocompetitive exclusion of SRB took place in the nitrate-injected bioreactor. In two replicate bioreactors treated with nitrite, less pronounced sulfur isotope fractionation and a slight decrease in δ18O SO4 were observed. This indicated that NR-SOB played a minor role during dosing with low nitrite and that

  9. Accurate determination of Curium and Californium isotopic ratios by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) in 248Cm samples for transmutation studies

    Energy Technology Data Exchange (ETDEWEB)

    Gourgiotis, A.; Isnard, H.; Aubert, M.; Dupont, E.; AlMahamid, I.; Cassette, P.; Panebianco, S.; Letourneau, A.; Chartier, F.; Tian, G.; Rao, L.; Lukens, W.

    2011-02-01

    The French Atomic Energy Commission has carried out several experiments including the mini-INCA (INcineration of Actinides) project for the study of minor-actinide transmutation processes in high intensity thermal neutron fluxes, in view of proposing solutions to reduce the radiotoxicity of long-lived nuclear wastes. In this context, a Cm sample enriched in {sup 248}Cm ({approx}97 %) was irradiated in thermal neutron flux at the High Flux Reactor (HFR) of the Laue-Langevin Institute (ILL). This work describes a quadrupole ICP-MS (ICP-QMS) analytical procedure for precise and accurate isotopic composition determination of Cm before sample irradiation and of Cm and Cf after sample irradiation. The factors that affect the accuracy and reproducibility of isotopic ratio measurements by ICP-QMS, such as peak centre correction, detector dead time, mass bias, abundance sensitivity and hydrides formation, instrumental background, and memory blank were carefully evaluated and corrected. Uncertainties of the isotopic ratios, taking into account internal precision of isotope ratio measurements, peak tailing, and hydrides formations ranged from 0.3% to 1.3%. This uncertainties range is quite acceptable for the nuclear data to be used in transmutation studies.

  10. Improvement in Thermal-Ionization Mass Spectrometry (TIMS) using Total Flash Evaporation (TFE) method for lanthanides isotope ratio measurements in transmutation targets

    Energy Technology Data Exchange (ETDEWEB)

    Mialle, S.; Gourgiotis, A.; Aubert, M.; Stadelmann, G.; Gautier, C.; Isnard, H. [Commissariat a l' Energie Atomique, CEA Saclay, DEN/DPC/SECR/LANIE, 91191 Gif sur Yvette (France); Chartier, F. [Commissariat a l' Energie Atomique, CEA Saclay, DEN/DPC, 91191 Gif sur Yvette (France)

    2011-07-01

    The experiments involved in the PHENIX french nuclear reactor to obtain precise and accurate data on the total capture cross sections of the heavy isotopes and fission products require isotopic ratios measurements with uncertainty of a few per mil. These accurate isotopic ratio measurements are performed with mass spectrometer equipped with multi-collector system. The major difficulty for the analyses of these actinides and fission products is the low quantity of the initial powder enclosed in steel container (3 to 5 mg) and the very low quantities of products formed (several {mu}g) after irradiation. Specific analytical developments are performed by Thermal Ionization Mass Spectrometry (TIMS) to be able to analyse several nanograms of elements with this technique. A specific method of acquisition named Total Flash Evaporation was adapted in this study in the case of lanthanide measurements for quantity deposited on the filament in the order of 2 ng and applied on irradiated fuel. To validate the analytical approach and discuss about the accuracy of the data, the isotopic ratios obtained by TIMS are compared with other mass spectrometric techniques such as Multiple-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS). (authors)

  11. (238)U/(235)U isotope ratios of crustal material, rivers and products of hydrothermal alteration: new insights on the oceanic U isotope mass balance.

    Science.gov (United States)

    Noordmann, Janine; Weyer, Stefan; Georg, R Bastian; Jöns, Svenja; Sharma, Mukul

    2016-01-01

    In this study, the U isotope composition, n((238)U)/n((235)U), of major components of the upper continental crust, including granitic rocks of different age and post-Archaean shales, as well as that of rivers (the major U source to the oceans) was investigated. Furthermore, U isotope fractionation during the removal of U at mid-ocean ridges, an important sink for U from the oceans, was investigated by the analyses of hydrothermal water samples (including low- and high-temperature fluids), low-temperature altered basalts and calcium carbonate veins. All analysed rock samples from the continental crust fall into a limited range of δ(238)U between -0.45 and -0.21 ‰ (relative to NBL CRM 112-A), with an average of -0.30 ± 0.15 ‰ (2 SD, N = 11). Despite differences in catchment lithologies, all major rivers define a relatively narrow range between -0.31 and -0.13 ‰, with a weighted mean isotope composition of -0.27 ‰, which is indistinguishable from the estimate for the upper continental crust (-0.30 ‰). Only some tributary rivers from the Swiss Alps display a slightly larger range in δ(238)U (-0.29 to +0.01 ‰) and lower U concentrations (0.87-3.08 nmol/kg) compared to the investigated major rivers (5.19-11.69 nmol/kg). These findings indicate that only minor net U isotope fractionation occurs during weathering and transport of material from the continental crust to the oceans. Altered basalts display moderately enriched U concentrations (by a factor of 3-18) compared to those typically observed for normal mid-ocean ridge basalts. These, and carbonate veins within altered basalts, show large U isotope fractionation towards both heavy and light U isotope compositions (ranging from -0.63 to +0.27 ‰). Hydrothermal water samples display low U concentrations (0.3-1 nmol/kg) and only limited variations in their U isotope composition (-0.43 ± 0.25 ‰) around the seawater value. Nevertheless, two of the investigated fluids display

  12. Pb-concentrations and Pb-isotope ratios in soils collected along an east-west transect across the United States

    Science.gov (United States)

    Reimann, Clemens; Smith, David B.; Woodruff, Laurel G.; Flem, Belinda

    2011-01-01

    Analytical results for Pb-concentrations and isotopic ratios from ca. 150 samples of soil A horizon and ca. 145 samples of soil C horizon collected along a 4000-km east–west transect across the USA are presented. Lead concentrations along the transect show: (1) generally higher values in the soil A-horizon than the C-horizon (median 21 vs. 16.5 mg/kg), (2) an increase in the median value of the soil A-horizon for central to eastern USA (Missouri to Maryland) when compared to the western USA (California to Kansas) (median 26 vs. 20 mg/kg) and (3) a higher A/C ratio for the central to eastern USA (1.35 vs. 1.14). Lead isotopes show a distinct trend across the USA, with the highest 206Pb/207Pb ratios occurring in the centre (Missouri, median A-horizon: 1.245; C-horizon: 1.251) and the lowest at both coasts (e.g., California, median A-horizon: 1.195; C-horizon: 1.216). The soil C-horizon samples show generally higher 206Pb/207Pb ratios than the A-horizon (median C-horizon: 1.224; A-horizon: 1.219). The 206Pb/207Pb-isotope ratios in the soil A horizon show a correlation with the total feldspar content for the same 2500-km portion of the transect from east-central Colorado to the Atlantic coast that shows steadily increasing precipitation. No such correlation exists in the soil C horizon. The data demonstrate the importance of climate and weathering on both Pb-concentration and 206Pb/207Pb-isotope ratios in soil samples and natural shifts thereof in the soil profile during soil-forming processes.

  13. Mars Atmospheric Composition, Isotope Ratios and Seasonal Variations: Overview and Updates of the SAM Measurements at Gale Crater

    Science.gov (United States)

    Webster, C. R.; Mahaffy, P. R.; Atreya, S. K.; Conrad, P. G.; Franz, H.; Trainer, M. G.; Wong, M. H.; Mischna, M. A.; Flesch, G.; Farley, K. A.; Owen, T. C.; Niles, P. B.; Jones, J. H.; Christensen, L. E.; Martín-Torres, J.; Zorzano, M. P.

    2014-12-01

    We will summarize the in situ measurements of atmospheric composition and the isotopic ratios of D/H in water, 13C/12C, 18O/16O, 17O/16O, and 13C18O/12C16O in carbon dioxide, 38Ar/36Ar, xKr/84Kr, and 15N/14N made in the martian atmosphere at Gale Crater from the Curiosity Rover using the Sample Analysis at Mars (SAM)'s Quadrupole Mass Spectrometer (QMS) and Tunable Laser Spectrometer (TLS). With data over 700 sols since the Curiosity landing, we will discuss evidence and implications for changes on seasonal and other timescales. We will also present results for continued methane and methane enrichment experiments over this time period. Comparison between our measurements in the modern atmosphere and those of martian meteorites like ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing. References:[1] Mahaffy P. R. et al., Science, 341, 263-266, 2013, doi:10.1126/science.1237966. [2] Webster C. R. et al. (2013), Science, 341, 260-263, doi:10.1126/science.1237961. [3] Wong, M. H. et al. (2013), Geophys. Res. Lett., doi:10.1002/2013GL057840. [4] Atreya S. K. et al (2013), Geophys. Res. Lett., 40, 1-5, doi:10.1002/2013GL057763. The research described here was supported by the National Aeronautics and Space Administration (NASA).

  14. Multispectroscopic and Isotopic Ratio Analysis To Characterize the Inorganic Binder Used on Pompeian Pink and Purple Lake Pigments.

    Science.gov (United States)

    Marcaida, Iker; Maguregui, Maite; Morillas, Héctor; García-Florentino, Cristina; Knuutinen, Ulla; Carrero, Jose Antonio; Fdez-Ortiz de Vallejuelo, Silvia; Pitarch Martı́, Africa; Castro, Kepa; Madariaga, Juan Manuel

    2016-06-21

    Because of the fact that pigments are not ubiquitous in the archeological record, the application of noninvasive analytical methods is a necessity. In this work, pink and purple lake pigments recovered from the excavations of the ancient city of Pompeii (Campania, Italy) and preserved in their original bowls at the Naples National Archaeological Museum (Italy) were analyzed to characterize the composition of their inorganic binders (mordants). In situ preliminary analyses using a hand-held energy dispersive X-ray fluorescence spectrometer (HH-ED-XRF) allowed us to determine the use of an aluminosilicate enriched in Cu and Pb. Scanning electron microscopy coupled to energy dispersive X-ray spectrometry (SEM-EDS) and benchtop ED-XRF analyses confirmed these results, while inductively coupled plasma mass spectrometry (ICPMS) allowed one to determine the concentration of major, minor, and trace elements. The use of other techniques such as X-ray diffraction (XRD), and micro-Raman and infrared spectroscopies allowed one to characterize the pigments at the molecular level. The high concentration of Cu detected in the pigments (1228-12937 μg g(-1)) could be related to the addition of Cu salts to obtain the desired final hue. The concentrations of Pb (987-2083 μg g(-1)) was also remarkable. Lead isotopic ratio analysis ((206)Pb/(207)Pb) suggested a possible origin related to the leaching of the ancient lead pipes from Pompeii and the subsequent transfer to the buried pigments or to the inorganic binder. Molecular analysis also showed that the binder is composed of an allophane-like clay. Moreover, it was possible to determine that to obtain the final purple hue of a specific pigment, Pompeian blue pigment was also mixed into the dyed clay.

  15. Late Paleogene topography of the Central Rocky Mountains and western Great Plains region using hydrogen isotope ratios in volcanic glass

    Science.gov (United States)

    Rossetto, G.; Fricke, H. C.; Cassel, E. J.; Evanoff, E.

    2015-12-01

    The Central Rocky Mountains (CRM), located in southern Wyoming, Colorado, and northern New Mexico, are characterized by the highest elevation basins (up to 2500 m) and mountains (over 4000 m) in the North American Cordillera. The timing and drivers for surface uplift of the CRM have not been conclusively determined. The goal of this study is to constrain the timing of surface uplift of the CRM by comparing hydrogen isotope ratios of hydration waters (δDglass) in late Paleogene volcanic glasses preserved in felsic tuffs deposited in CRM basins to δDglass values from glasses of similar age (34.9 to 32.2 Ma) preserved in tuffs from the surrounding Great Plains. The tuffs deposited in the Great Plains, to the north and east of the CRM, are currently at elevations of 1100-1600 m. Volcanic glass hydrates shortly after deposition, preserving the δD of ancient meteoric water on geologic timescales, and can thus be used as a proxy for ancient precipitation δD values. Volcanic glasses from the CRM have δDglass values that are an average of ~31‰ higher than δDglass values from the Great Plains, while modern day precipitation δD values in the CRM are ~25‰ lower than δD values in the Great Plains. These results suggest that the uplift of the CRM relative to the surrounding Great Plains occurred after ~32 Ma. This requires a mechanism such as mantle upwelling or differential crustal hydration, not solely Laramide tectonism, to uplift the CRM to current elevations. Elevation, however, may not have been the only control on the spatial distribution of precipitation δD values across the western US. Similar to the modern, mixing of Pacific and Gulf coast air masses likely occurred during the latest Paleogene, driving regional variability in δD values of precipitation.

  16. Compound-specific stable carbon isotope ratios of phenols and nitrophenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide.

    Science.gov (United States)

    Irei, Satoshi; Rudolph, Jochen; Huang, Lin

    2013-07-01

    We developed an analytical method for measuring compound-specific stable carbon isotope ratios (δ(13)C) of phenols and nitrophenols in filter samples of particulate organic matter. The method was tested on 13 phenols derivatized with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA), together with four nonphenolic compounds. The data obtained by our method required two specific corrections for the determination of valid δ(13)C values: (1) for nitro compounds, the routine correction with use of m/z 46 for the contribution of (12)C(17)O(16)O molecules) to m/z 45 was modified due to impact of NO2 on the m/z 46 trace, and (2) for the derivatized phenols, measured δ(13)C values were corrected for the shift in δ(13)C due to the addition of carbon atoms from the BSTFA moiety. Analysis of standard-spiked filters showed that overall there was a small compound-dependent bias in the δ(13)C values: the average bias±the standard error of the mean of -0.21±0.1‰ for the standard compounds tested, except 3-methylcatechol, methylhydroquinone, 4-methyl-2-nitrophenol, and 2,6-dimethyl-4-nitrophenol, whereas the average biases±the standard errors of the mean for those were +1.2±0.3‰, +1.2±0.2‰, -1.2±0.2‰, and -1.4±0.5‰, respectively, when the injected mass of a derivatized compound exceeded 15 ngC. In situations where such small biases and uncertainties are acceptable, the method described here could be used to obtain valuable information about δ(13)C values. We also analyzed a real filter sample to demonstrate the practical applicability of the method.

  17. Effect of Rare Earth Elements on Exchange Performances of Cesium Ion-Sieve

    Institute of Scientific and Technical Information of China (English)

    张惠源; 王榕树; 林灿生; 张先业

    2003-01-01

    The exchange performances and the distribution coefficient of Cesium Ion-Sieve (Cs-IS) for cesium and for some rare earth elements were compared. In particular, the effects of neodymium on the cesium ion exchange and the Cs+ selectivity variation on Cs-IS owing to introduction of rare earth elements into HLLW were studied. Though rare earth elements exhibit a small influence on the distribution coefficient for Cs+, they impair Cs-exchange capacity of Cs-IS to some extent. This interruption on the selectivity to Cs+ can be significantly eliminated provided an appropriate ratio of liquid to solid V:m is used.

  18. A study of radionuclides, metals and stable lead isotope ratios in sediments and soils in the vicinity of natural U-mineralisation areas in the Northern Territory

    Energy Technology Data Exchange (ETDEWEB)

    Frostick, A., E-mail: Alison.Frostick@cdu.edu.au [Charles Darwin University, School of Environment and Life Sciences, Darwin NT 0909 (Australia); ERISS, GPO Box 461, Darwin NT 0801 (Australia); Bollhoefer, A. [ERISS, GPO Box 461, Darwin NT 0801 (Australia); Parry, D. [AIMS, PO Box 41775, Casuarina NT 0811 (Australia)

    2011-10-15

    Australian guidelines recommend that tailings materials from uranium (U) mining and milling be contained without any detrimental impact on the environment for at least 1000 years. Natural analogue sites are being investigated to determine if they can provide data on the rates of natural erosion processes which occur over these timescales, for input into predictive geomorphic computer models. This paper presents radionuclide, metal and stable lead (Pb) isotope data from sediment cores and surface soils in the vicinity of two mineralised areas in the Alligator Rivers Region. Surface scrapes from the natural Anomaly no. 2, south of the Ranger mineral lease, exhibit radiogenic {sup 206}Pb/{sup 207}Pb and {sup 208}Pb/{sup 207}Pb ratios, and elevated U and metal concentrations typical for a near surface U anomaly. In contrast, samples taken from the Koongarra mineral lease (KML) show radionuclide activity and metal concentrations similar to natural areas elsewhere in the Alligator Rivers Region and Pb isotope ratios are closer to present day average crustal ratios (PDAC), as the orebodies at KML are covered by surficial sand. A sediment core collected from Anbangbang Billabong, downstream of KML, exhibits small variations in Pb isotope ratios that indicate that approximately 1% of the upper sediments in the sediment core may be derived from material originating from the U anomaly at Koongarra.

  19. Use of isotope ratios to assess sources of Pb and Zn dispersed in the environment during mining and ore processing within the Orlovka-Spokoinoe mining site (Russia)

    Energy Technology Data Exchange (ETDEWEB)

    Dolgopolova, A. [Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom)]. E-mail: allad@nhm.ac.uk; Weiss, D.J. [Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom); Department of Earth Science and Engineering, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom); Seltmann, R. [Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom); Kober, B. [Institute of Environmental Geochemistry, Im Neuenheimer Feld 234, D-69120 Heidelberg (Germany); Mason, T.F.D. [Department of Earth Science and Engineering, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom); Coles, B. [Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom); Department of Earth Science and Engineering, Imperial College London, Prince Consort Road, London SW7 2BP (United Kingdom); Stanley, C.J. [Centre for Russian and Central EurAsian Mineral Studies (CERCAMS), Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD (United Kingdom)

    2006-04-15

    Element concentrations, element ratios and Pb and Zn isotope data are reported for different geologic samples (barren and ore-bearing granites and host rocks), technogenic products (ore concentrates and tailings) and biologic samples (lichens and birch leaves) from the Orlovka-Spokoinoe mining district, Eastern Transbaikalia, Russia, with the aim to trace the sources of Pb and Zn at a local level within the mining site. Lichens and birch leaves were used as receptors of contamination within the mining site. Pb/Zr and Zn/Zr values indicated Pb and Zn enrichment relative to host rocks. Zn isotope data of 15 geologic and 11 lichen samples showed different Zn isotopic signatures with the total range for the geologic suite of -0.4 per mille to +1.2 per mille and for lichens of +0.4 per mille to +1.4 per mille in {delta} {sup 66}Zn relative to Lyon JMC Zn standard. The source of isotopically heavy Zn within the Orlovka-Spokoinoe mining site could be potentially associated with long-range atmospheric aerosols that also contributed Pb to the studied mining site. Our results demonstrated that Zn isotopes might be used as new tools for Zn source assessment.

  20. Iodine-to-calcium ratios in carbonates suggest a primary origin for the Precambrian Lomagundi and Shuram carbon isotope excursions

    Science.gov (United States)

    Hardisty, D. S.; Lu, Z.; Planavsky, N. J.; Osburn, M. R.; Bekker, A.; Lyons, T. W.

    2013-12-01

    Systematic increases in iodine-to-calcium ratios (I/Ca) in carbonates from both the Precambrian Lomagundi and Shuram carbonate carbon isotope (δ13Ccarb) excursion intervals suggest primary origins for these events. Iodate (IO3-), the oxidized iodine species, is the exclusive species incorporated into carbonates. The high redox sensitivity of IO3- to deoxygenation requires highly oxidizing fluids for IO3- production, making I/Ca in platform carbonates a simple indicator of the presence of oxidizing fluids in the surface ocean. Similarly, redox sensitivity makes the proxy host susceptible to diagenetic iodine loss during carbonate recrystallization in reducing pore fluids. Recent work has shown carbonates to experience near-complete iodine loss during dolomitization in the Permian, and work from our group evaluating modern and recent carbonates demonstrate the potential for diagenetic iodine loss during carbonate recrystallization. In some cases, however, such as meteoric aragonite-to-calcite transitions, oxidizing pore fluids have the potential to buffer IO3- concentrations, causing negligible alteration to primary I/Ca despite negative shifts in δ13Ccarb. These results highlight that diagenetic alterations to I/Ca and δ13Ccarb need not always be coupled, but importantly, no observed scenario promotes post-depositional addition of iodine to carbonates. This means that, independent of δ13Ccarb, systematic, stratigraphic increases in I/Ca ratios observed in the carbonate record are most easily interpreted as resulting from depositional controls such as surface ocean redox or shifts in the total marine iodine reservoir. From this, increasing I/Ca ratios coincident with rising and falling δ13Ccarb trends for the Paleoproterozic Lomagundi and Neoproterozoic Shuram events, respectively, support suggestions of a primary origin for the δ13Ccarb excursions. Significant increase in I/Ca in dolomites deposited during the Lomagundi excursion, rising from blank values in

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

    Science.gov (United States)

    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.

  2. Analysis of household ignitable liquids and their post-combustion weathered residues using compound-specific gas chromatography-combustion-isotope ratio mass spectrometry.

    Science.gov (United States)

    Schwartz, Zeland; An, Yan; Konstantynova, Kateryna I; Jackson, Glen P

    2013-12-10

    The continuing rise in home and vehicular arson cases involving the use of ignitable liquids continues to be an area of concern for criminal and civil investigators. In this study, the compound-specific δ(13)C values of various components of four flammable household chemicals were measured using a single quadrupole mass spectrometer and an isotope ratio mass spectrometer as simultaneous detectors for a gas chromatograph. Whereas compound-specific carbon isotope ratios were able to discriminate between different sources of neat (pre-combustion) ignitable liquids, analyses of the post-combustion residues were problematic. Weathering caused by combustion resulted in a significant increase in the (13)C content of specific peaks relative to the neat liquids (i.e. less negative delta values) such that the isotopic comparison of pre- and post-combustion residues resulted in fractionation ranging from 0 to +10‰. Because of the current lack of understanding of isotopic fractionation during combustion, and because of problems encountered with co-elution in the more complex samples, compound-specific IRMS does not appear to be suitable for fire debris analysis. The comparison of non-combusted or non-weathered ignitable liquids is much more reliable, especially for relatively simple mixtures, and is best suited for exclusionary purposes until such time as a comprehensive database of samples is developed. Without a measure of the population variance, one cannot presently predict the false positive identification rate for the comparison of two ignitable liquids; i.e. the probability that two random ignitable liquid samples have indistinguishable isotope ratios.

  3. Moessbauer study of Fe{sup 3+}/Fe{sup 2+} ratio in amphiboles to search correlation with hydrogen isotope fractionation

    Energy Technology Data Exchange (ETDEWEB)

    Waczek, Zsofia [University of Lausanne, Institut de Mineralogie et Geochimie, Anthropole (Switzerland); Kuzmann, Ernoe; Homonnay, Zoltan, E-mail: homonnay@ludens.elte.hu [Eoetvoes University, Institute of Chemistry (Hungary); Vennemann, Torsten [University of Lausanne, Institut de Mineralogie et Geochimie, Anthropole (Switzerland)

    2009-04-15

    There is a general lack of understanding of the hydrogen isotope fractionations between different experimental approaches both at higher and at lower temperatures of exchange. The complexity of bonding related with the hydroxyl ion in most hydrous minerals makes theoretical treatments rather difficult. Though some of the differences between experimental findings have recently been shown to be related to pressure effects that influence the hydrogen isotope fractionation properties of water, some other factors may also have significance. One of the major unknowns is the compositional control, especially the Fe-content and effects of variable Fe{sup 3+}/Fe{sup 2+} ratios on hydrogen isotope fractionations between minerals and fluids (Suzuoki and Epstein, Geochim Cosmochim Acta 40:1229-1240, 1976; Chacko et al. 2001). We have studied a series of amphibole samples by Moessbauer spectroscopy, EPMA and TC-EA-IRMS to examine for possible correlations between D/H fractionation and Fe{sup 2+} to Fe{sup 3+} ratio/total iron content. Our measurements show that this correlation may exist for one particular origin of samples, but local conditions of mineral formation (most probably chemical composition and reactions accompanying the formation of minerals) may be more important in controlling the hydrogen isotope composition of minerals.

  4. Determination of the concentration of nitrogenous bio-organic compounds using an isotope ratio mass spectrometer operating in continuous flow mode.

    Science.gov (United States)

    Tea, Illa; Kosieradzka, Katarzyna; Antheaume, Ingrid; Gentil, Emmanuel; Robins, Richard J

    2011-09-01

    The quality of the determination of compound-specific isotopic content at natural abundance by gas chromatography-isotope ratio measurement-mass spectrometry (GC-irm-MS) relies on the stability of the voltage generated by the ion detector Faraday cages. The application of GC-irm-MS to the determination of δ(13)C (‰) and δ(15)N (‰) is now routine. However, for numerous applications, it is necessary to determine both the isotope content (δ(15)N) and the quantity (in micromoles) of analyte present. We now show that it is possible for nitrogen-containing compounds to measure how much analyte is present with an irm mass spectrometer linked to a GC by exploiting the integrated N(2) total ion current intensity (Vs) generated by measuring the (15)N/(14)N isotope ratio. The method is validated over a range of concentration (2-70 mmol/L) and δ(15)N (-70 to +50‰) values for six molecules of diverse chemical nature and functionality (nortropine, norpseudotropine, nortropinone, cysteine, taurine, glutathione). It is shown that once the ion current is calibrated, the quantitative values are of a comparable quality to those obtained from GC with flame ionization detection (GC-FID). In addition, it is demonstrated that over a definable range, the δ(15)N (‰) value is independent of the quantity of analyte introduced, confirming the validity of this method.

  5. Measuring Sulfur Isotope Ratios from Solid Samples with the Sample Analysis at Mars Instrument and the Effects of Dead Time Corrections

    Science.gov (United States)

    Franz, H. B.; Mahaffy, P. R.; Kasprzak, W.; Lyness, E.; Raaen, E.

    2011-01-01

    The Sample Analysis at Mars (SAM) instrument suite comprises the largest science payload on the Mars Science Laboratory (MSL) "Curiosity" rover. SAM will perform chemical and isotopic analysis of volatile compounds from atmospheric and solid samples to address questions pertaining to habitability and geochemical processes on Mars. Sulfur is a key element of interest in this regard, as sulfur compounds have been detected on the Martian surface by both in situ and remote sensing techniques. Their chemical and isotopic composition can belp constrain environmental conditions and mechanisms at the time of formation. A previous study examined the capability of the SAM quadrupole mass spectrometer (QMS) to determine sulfur isotope ratios of SO2 gas from a statistical perspective. Here we discuss the development of a method for determining sulfur isotope ratios with the QMS by sampling SO2 generated from heating of solid sulfate samples in SAM's pyrolysis oven. This analysis, which was performed with the SAM breadboard system, also required development of a novel treatment of the QMS dead time to accommodate the characteristics of an aging detector.

  6. Matrix and energy effects during in-situ determination of Cu isotope ratios by ultraviolet-femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lazarov, Marina, E-mail: m.lazarov@mineralogie.uni-hannover.de; Horn, Ingo

    2015-09-01

    Copper isotope compositions in Cu-bearing metals and minerals have been measured by deep (194 nm) ultraviolet femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (UV-fsLA-MC-ICP-MS). Pure Cu-metal, brass, and several Cu-rich minerals (chalcopyrite, enargite, covellite, malachite and cuprite) have been investigated. A long-term reproducibility of better than 0.08‰ at the 95% confidence limit on the NIST SRM 976 (National Institute of Standards and Technology) Cu-metal standard has been achieved with this technique. The δ{sup 65}Cu values for all samples have been calculated by standard-sample-standard bracketing with NIST SRM 976. All analyses have been carried out using Ni as a mass discrimination monitor added by nebulization prior to entering the plasma torch. For further verification samples have been analysed by conventional solution nebulization MC-ICP-MS and the results obtained have been compared with those from UV-fsLA-MC-ICP-MS. Several potential matrix-induced molecular interferences on the mineral copper isotope ratio, such as ({sup 32}S{sup 33}S){sup +} and ({sup 32}S-{sup 16}O{sup 17}O){sup +} do not affect the Cu isotope measurements on sulfides, while hydrides, such as Zn–H or doubly-charged Sn{sup 2+} that interfere Ni isotopes can be either neglected or stripped by calculation. Matrix independent Cu-isotope measurements are sensitive to the energy density (fluence) applied onto the sample and can produce artificial shifts in the obtained δ{sup 65}Cu values which are on the order of 3‰ for Cu-metal, 0.5‰ for brass and 0.3‰ for malachite when using energy density of up to 2 J/cm{sup 2} for ablation. A positive correlation between applied energy density and the magnitude of the isotope ratio shift has been found in the energy density range from 0.2 to 1.3 J/cm{sup 2} which is below the ablation threshold for ns-laser ablation. The results demonstrate that by using appropriate low fluence it is possible

  7. Lead as transient geochemical tracers in the environment: Assessing high precision isotope ratio measurements in lichens, peat, and silicates using multi-collector ICP-MS

    Science.gov (United States)

    Weiss, D. J.; Kober, B.; Mason, T. F.; Dolgopolova, A.; Coles, B. J.; Gallagher, K.; Leroux, G.; Spiro, B.; Seltmann, R.

    2003-04-01

    In recent years, MC-ICP-MS has become a powerful tool to measure Pb isotopes with high precision and accuracy. Yet, this technique is still relatively new, and the complexities related to using an ICP ion source for high precision isotope measurements are only now becoming apparent. In addition, most analytical development work so far has focussed on synthetic solutions and silicate material. Given the great importance of Pb isotopes in environmental geochemical studies, however, a careful assessment of analytical procedures for environmental samples is clearly needed and warranted. Consequently, we present here a study of the analytical performance of the Imperial College/Natural History Museum (IC/NHM) IsoProbe MC-ICPMS with respect to high precision Pb isotope measurements in peat, lichen and silicates. After acid digestion, the samples were passed through an exchange column using a new procedure developed at the University of Heidelberg (Kober, in prep.). This chemistry yielded quantitative recoveries and allowed a high sample throughput as only one column passage was needed to achieve stable ion beam signals. Selected samples were also analysed on a Finnegan MAT261 TIMS. Typical internal precisions of 10-35 ppm (1se) were achieved on all Pb isotope ratios in all matrices. Measurements of Pb 981 NIST standards spiked with Tl 997 NIST showed that the certified NBS Tl ratio had to be adjusted daily up to 2.38993 in order to obtain accurate data. The reproducibility for the synthetic standard over a three month period using daily optimised Tl values (but with no 2σ outlier rejection routine applied) was below 300 ppm for all ratios (including the 208Pb/204Pb ratio). On peak zeroing (OPZ) and half mass baseline correction procedures gave similar precisions. However, the accuracies on the 204 ratios were significantly worse using half mass baseline correction for Pb/Tl ratios less than 2. This behaviour is consistent with tailing of 205Tl onto the 204Pb peak

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

    Science.gov (United States)

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

    2001-01-01

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

  9. Determination of the absolute 32S/34S ratio of IAEA-S-1 reference material and V-CDT sulfur isotope standard

    Institute of Scientific and Technical Information of China (English)

    丁悌平; 白瑞梅; 李延河; 万德芳; 邹晓秋; 张青莲

    1999-01-01

    The absolute 32S/34S ratios of IAEA-S-1 reference material and V-CDT standard are determined. For cross-checking, two sets of synthetic isotope mixtures are prepared from high purity 32S and 34S-enriched materials in different forms: the first set is prepared from BaSO4 whereas the second is prepared from Ag2S. The sulfur isotope analyses are done by using SF6 method with a MAT-251 EM mass spectrometer. The resulting 32S/34S ratio of IAEAS-1 reference material is 22.656 4±0. 006 0, and that of V-CDT is 22. 649 6±0. 006 0.

  10. Determination of trace element concentrations and stable lead, uranium and thorium isotope ratios by quadrupole-ICP-MS in NORM and NORM-polluted sample leachates

    Energy Technology Data Exchange (ETDEWEB)

    Mas, J.L., E-mail: ppmasb@us.es [Dpto. Fisica Aplicada I, EPS, Universidad de Sevilla, 41012 Sevilla (Spain); Villa, M. [Servicio de Radioisotopos, Centro de Investigacion, Tecnologia e Innovacion (CITIUS), Universidad de Sevilla, Avda. Reina Mercedes 4b, 41012 Sevilla (Spain); Dpto. Fisica Aplicada II, ETS de Arquitectura, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Sevilla (Spain); Hurtado, S. [Servicio de Radioisotopos, Centro de Investigacion, Tecnologia e Innovacion (CITIUS), Universidad de Sevilla, Avda. Reina Mercedes 4b, 41012 Sevilla (Spain); Garcia-Tenorio, R. [Dpto. Fisica Aplicada II, ETS de Arquitectura, Universidad de Sevilla, Avda. Reina Mercedes 2, 41012 Sevilla (Spain)

    2012-02-29

    Highlights: Black-Right-Pointing-Pointer Polluted sediment and NORM samples. Black-Right-Pointing-Pointer An efficient yet fast process allowing multi-parametric determinations in <3 days. Black-Right-Pointing-Pointer Trace element concentrations, Pb, Th and U isotope ratios with a single instrument. - Abstract: This work focuses on the monitoring of the potential pollution in scenarios that involve NORM-related industrial activities (environmental or in-door scenarios). The objective was to develop a method to determine extent and origin of the contamination, suitable for monitoring (i.e. simple, fast and economical) and avoiding the use of too many different instruments. It is presented a radiochemical method that allows the determination of trace element concentrations and {sup 206}Pb/{sup 207}Pb/{sup 208}Pb, {sup 238}U/{sup 234}U and {sup 232}Th/{sup 230}Th isotope ratios using a single sample aliquot and a single instrument (ICP-QMS). Eichrom UTEVA{sup Registered-Sign} extraction chromatography minicolumns were used to separate uranium and thorium in sample leachates. Independent ICP-MS determinations of uranium and thorium isotope ratios were carried out afterwards. Previously a small aliquot of the leachate was used for the determination of trace element concentrations and lead isotope ratios. Several radiochemical arrangements were tested to get maximum performances and simplicity of the method. The performances of the method were studied in terms of chemical yields of uranium and thorium and removal of the potentially interfering elements. The established method was applied to samples from a chemical industry and sediments collected in a NORM-polluted scenario. The results obtained from our method allowed us to infer not only the extent, but also the sources of the contamination in the area.

  11. Evaporative Control on Soil Water Isotope Ratios: Implications for Atmosphere-Land Surface Water Fluxes and Interpretation of Terrestrial Proxy Records

    Science.gov (United States)

    Kaushik, A.; Noone, D. C.; Berkelhammer, M. B.; O'Neill, M.

    2014-12-01

    The moisture balance of the continental boundary layer plays an important role in regulating the exchange of water and energy between the land surface and atmosphere. Near-surface moisture balance is controlled by a number of factors including precipitation, infiltration and evapotranspiration. Measurements of stable isotope ratios in water can be exploited to better understand the mechanisms controlling atmosphere-land surface water fluxes. Understanding the processes that set sub-surface water isotope ratios can prove useful for refining paleoclimate interpretations of stable oxygen and hydrogen isotope-based proxies. We present in situ tower-based measurements of stable isotope ratios of water (δD and δ18O) in vapor, precipitation and soil from the Boulder Atmospheric Observatory, a semi-arid tall-tower site in Erie, Colorado, from July 2012 to September 2014. Near surface profiles from 0 to 10 m were measured approximately every ninety minutes. Soil profiles from 0 to 30 cm, the region of maximum variability, were sampled on a weekly basis and cryogenically extracted for stable water isotope measurement. Evaporation-proof bulk rain collectors provided precipitation samples at this site. Results show disequilibrium exists between surface vapor and soil water isotopes, with the top 10 cm of soil water approaching equilibrium with the surface vapor right after a rain event because of high infiltration and saturation at the surface. At this semi-arid site with little vegetation, evaporative exchange is the main driver for soil water fluxes as the soil dries, corroborated by soil Dexcess profiles showing progressive enrichment through evaporation. In addition, when nighttime surface temperatures are cooler than deep soil, as is the case in many arid and semi-arid environments, upward vapor diffusion from the soil leads to dew formation at the surface which then contributes to surface vapor values. We use these observations to constrain a Craig-Gordon evaporation

  12. Deciphering petrogenic processes using Pb isotope ratios from time-series samples at Bezymianny and Klyuchevskoy volcanoes, Central Kamchatka Depression

    Science.gov (United States)

    Kayzar, Theresa M.; Nelson, Bruce K.; Bachmann, Olivier; Bauer, Ann M.; Izbekov, Pavel E.

    2014-10-01

    The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956-present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts-basaltic andesites are more radiogenic than Bezymianny andesites (208Pb/204Pb = 37.850-37.903, 207Pb/204Pb = 15.468-15.480, and 206Pb/204Pb = 18.249-18.278 at Bezymianny; 208Pb/204Pb = 37.907-37.949, 207Pb/204Pb = 15.478-15.487, and 206Pb/204Pb = 18.289-18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.

  13. Determination of trace element concentrations and stable lead, uranium and thorium isotope ratios by quadrupole-ICP-MS in NORM and NORM-polluted sample leachates.

    Science.gov (United States)

    Mas, J L; Villa, M; Hurtado, S; García-Tenorio, R

    2012-02-29

    This work focuses on the monitoring of the potential pollution in scenarios that involve NORM-related industrial activities (environmental or in-door scenarios). The objective was to develop a method to determine extent and origin of the contamination, suitable for monitoring (i.e. simple, fast and economical) and avoiding the use of too many different instruments. It is presented a radiochemical method that allows the determination of trace element concentrations and 206Pb/207Pb/208Pb, 238U/234U and 232Th/230Th isotope ratios using a single sample aliquot and a single instrument (ICP-QMS). Eichrom UTEVA® extraction chromatography minicolumns were used to separate uranium and thorium in sample leachates. Independent ICP-MS determinations of uranium and thorium isotope ratios were carried out afterwards. Previously a small aliquot of the leachate was used for the determination of trace element concentrations and lead isotope ratios. Several radiochemical arrangements were tested to get maximum performances and simplicity of the method. The performances of the method were studied in terms of chemical yields of uranium and thorium and removal of the potentially interfering elements. The established method was applied to samples from a chemical industry and sediments collected in a NORM-polluted scenario. The results obtained from our method allowed us to infer not only the extent, but also the sources of the contamination in the area.

  14. Tree rings as Pb pollution archives? A comparison of 206Pb/207Pb isotope ratios in pine and other environmental media.

    Science.gov (United States)

    Bindler, Richard; Renberg, Ingemar; Klaminder, Jonatan; Emteryd, Ove

    2004-02-05

    Tree rings, if validated as an environmental archive for pollution, would provide a convenient, geographically widespread archive for studying the temporal and spatial distribution of atmospheric pollutants. We collected tree-ring records from Scots pine (Pinus sylvestris L.), ranging in age from 100 to 300 years and from one spruce (Picea abies), from sites in southern and northern Sweden and analyzed their stable lead isotopic composition (206Pb/207Pb). These results are compared to the Pb isotopic composition in soil profiles from each of the sites and temporal changes in the 206Pb/207Pb ratio in peat and lake sediment deposits in Sweden. The mineral soils at each site are characterized by high 206Pb/207Pb ratios (> 1.35), while the ratios in the mor layer are low (1.14-1.16) and characterized by atmospheric lead pollution. The 206Pb/207Pb ratios of the tree rings, typically approximately 1.18-1.20, indicate a significant (10-30%) contribution of Pb derived from the underlying mineral soil. While peat and lake sediment records show that the 206Pb/207Pb ratio of atmospheric deposition has varied over time, with a pronounced trough between approximately 1930 and 1990, the tree rings show no similar trend. Further comparison of published Pb isotope data from other tree-ring records with time series from peat bogs and herbarium samples also shows poor agreement, and indicates that tree rings always contain a mixture of pollution Pb and Pb from the underlying mineral soil. The majority of Pb in the wood is derived from atmospheric pollution either directly, through aerial interception, or indirectly, through uptake from the large pool of accumulated pollution Pb in the soil. Since the Pb isotope ratios of the wood indicate that some natural Pb is taken up into the tree, then it must also be concluded that some fraction of the pollution Pb in the wood is likewise taken up from the forest soil. Based on the Pb isotope analyses, we can only conclude that dendrochemical

  15. Determining water sources in the boundary layer from tall tower profiles of water vapor and surface water isotope ratios after a snowstorm in Colorado

    Directory of Open Access Journals (Sweden)

    D. Noone

    2013-02-01

    Full Text Available The D/H isotope ratio is used to attribute boundary layer humidity changes to the set of contributing fluxes for a case following a snowstorm in which a snow pack of about 10 cm vanished. Profiles of H2O and CO2 mixing ratio, D/H isotope ratio, and several thermodynamic properties were measured from the surface to 300 m every 15 min during four winter days near Boulder, Colorado. Coeval analysis of the D/H ratios and CO2 concentrations find these two variables to be complementary with the former being sensitive to daytime surface fluxes and the latter particularly indicative of nocturnal surface sources. Together they capture evidence for strong vertical mixing during the day, weaker mixing by turbulent bursts and low level jets within the nocturnal stable boundary layer during the night, and frost formation in the morning. The profiles are generally not well described with a gradient mixing line analysis because D/H ratios of the end members (i.e., surface fluxes and the free troposphere evolve throughout the day which leads to large uncertainties in the estimate of the D/H ratio of surface water flux. A mass balance model is constructed for the snow pack, and constrained with observations to provide an optimal estimate of the partitioning of the surface water flux into contributions from sublimation, evaporation of melt water in the snow and evaporation from ponds. Results show that while vapor measurements are important in constraining surface fluxes, measurements of the source reservoirs (soil water, snow pack and standing liquid offer stronger constraint on the surface water balance. Measurements of surface water are therefore essential in developing observational programs that seek to use isotopic data for flux attribution.

  16. 我国城市大气颗粒物的铅同位素丰度比%Lead Isotope Abundance Ratios of Urban Atmospheric Aerosols in China

    Institute of Scientific and Technical Information of China (English)

    刘咸德; 李显芳; 李冰

    2004-01-01

    Determined with ICP-MS, new isotope abundance ratio data of lead for Beijing and Changdao aerosols was presented, in comparison with literature data for Chinese urban aerosols. 206Pb/207Pb ratio falls into a range from 1.13 to 1.18 for urban aerosols and less influenced by vehicle exhaust emission after phase-out of leaded petrol in 2000 in China. Major lead pollution sources may probably include coal combustion, oil combustion,re-suspended dust, metallurgical industry and use and production of cement.

  17. Fundamental study of cesium decontamination from soil by superconducting magnet

    Energy Technology Data Exchange (ETDEWEB)

    Igarashi, Susumu, E-mail: igarashi@qb.see.eng.osaka-u.ac.jp; Mishima, Fumihito; Akiyama, Yoko, E-mail: yoko-ak@see.eng.osaka-u.ac.jp; Nishijima, Shigehiro

    2013-11-15

    Highlights: •The method for the soil decontamination by the superconducting magnet is proposed. •Cesium ion can be absorbed by Prussian blue in potassium iodide wash fluid. •It is possible to recover Cs{sup +} ion-adsorbing Prussian blue with a high rate by HGMS. •It is expected that HGMS can be applied to the actual soil decontamination. -- Abstract: The radioactive substances have been spread out all over the surrounding area of Fukushima Daiichi Nuclear Power Plant caused by the accident in March 2011. Decontamination and volume reduction of radioactive substances, especially cesium ion, are desired issue. This study proposed a decontamination method of the soil by the magnetic separation using superconducting magnet. Cesium ion was adsorbed by Prussian blue in the potassium iodide solution. We succeeded in separating selectively the cesium ion-adsorbed Prussian blue out of the liquid phase by high gradient magnetic separation. High recovery ratio of the Prussian blue was achieved by this method.

  18. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer.

    Science.gov (United States)

    Hoegg, Edward D; Barinaga, Charles J; Hager, George J; Hart, Garret L; Koppenaal, David W; Marcus, R Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs. Graphical Abstract ᅟ.

  19. Preliminary Figures of Merit for Isotope Ratio Measurements: The Liquid Sampling-Atmospheric Pressure Glow Discharge Microplasma Ionization Source Coupled to an Orbitrap Mass Analyzer

    Science.gov (United States)

    Hoegg, Edward D.; Barinaga, Charles J.; Hager, George J.; Hart, Garret L.; Koppenaal, David W.; Marcus, R. Kenneth

    2016-08-01

    In order to meet a growing need for fieldable mass spectrometer systems for precise elemental and isotopic analyses, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) has a number of very promising characteristics. One key set of attributes that await validation deals with the performance characteristics relative to isotope ratio precision and accuracy. Owing to its availability and prior experience with this research team, the initial evaluation of isotope ratio (IR) performance was performed on a Thermo Scientific Exactive Orbitrap instrument. While the mass accuracy and resolution performance for Orbitrap analyzers are well-documented, no detailed evaluations of the IR performance have been published. Efforts described here involve two variables: the inherent IR precision and accuracy delivered by the LS-APGD microplasma and the inherent IR measurement qualities of Orbitrap analyzers. Important to the IR performance, the various operating parameters of the Orbitrap sampling interface, high-energy collisional dissociation (HCD) stage, and ion injection/data acquisition have been evaluated. The IR performance for a range of other elements, including natural, depleted, and enriched uranium isotopes was determined. In all cases, the precision and accuracy are degraded when measuring low abundance (<0.1% isotope fractions). In the best case, IR precision on the order of 0.1% RSD can be achieved, with values of 1%-3% RSD observed for low-abundance species. The results suggest that the LS-APGD is a promising candidate for field deployable MS analysis and that the high resolving powers of the Orbitrap may be complemented with a here-to-fore unknown capacity to deliver high-precision IRs.

  20. Nucleosynthesis in AGB stars traced by isotopic ratios. I - Determining the stellar initial mass by means of the $^{17}$O/$^{18}$O ratio

    CERN Document Server

    De Nutte, R; Olofsson, H; Lombaert, R; de Koter, A; Karakas, A; Milam, S; Ramstedt, S; Stancliffe, R J; Homan, W; Van de Sande, M

    2016-01-01

    The aim of this paper is to investigate the $^{17}$O/$^{18}$O ratio for a sample of AGB stars, containing M-, S- and C-type stars. These ratios are evaluated in relation to fundamental stellar evolution parameters: the stellar initial mass and pulsation period. This study is the first to explore these oxygen ratios for a sample covering the three spectral types. Circumstellar $^{13}$C$^{16}$O, $^{12}$C$^{17}$O and $^{12}$C$^{18}$O line observations were obtained for a sample of nine stars with various single-dish long-wavelength facilities. These data have been fully reduced and analyzed. The line intensity ratios obtained from these observations are then related directly to the surface $^{17}$O/$^{18}$O abundance ratio. Stellar evolution models predict the $^{17}$O/$^{18}$O ratio to be a sensitive function of initial mass and to remain constant throughout the entire TP-AGB phase for stars less massive than 5 M$_{\\odot}$. This allows the measured ratio to function as an effective method of determining the ini...

  1. Distribution characteristics of ¹³⁷Cs, Pu isotopes and ²⁴¹Am in soil in Korea.

    Science.gov (United States)

    Lee, S H; Oh, J S; Lee, J M; Lee, K B; Park, T S; Lujaniene, G; Valiulis, D; Sakalys, J

    2013-11-01

    Cesium-137, Plutonium isotopes and (241)Am were studied in soil samples collected from Korea between 2006 and 2008 to provide information on the distribution and origin of Pu isotopes and (241)Am. The vertical profiles of radionuclides showed higher activity concentrations at the surface layer and then gradually decreased with depth. A good correlation between (137)Cs and (239,240)Pu was observed, whereas a poor relationship between (137)Cs and (241)Am was found. The (238)Pu/(239,240)Pu, (241)Am/(239,240)Pu and (239,240)Pu/(137)Cs activity ratios were concordant to those of the global fallout ratios. Furthermore, the atomic ratios of (240)Pu/(239)Pu in the samples provided the information of Pu depositional history and the origin of Pu isotopes in Korea.

  2. Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China

    Energy Technology Data Exchange (ETDEWEB)

    Li, Junxia; Wang, Yanxin, E-mail: yx.wang@cug.edu.cn; Xie, Xianjun

    2016-02-15

    In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000–10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ{sup 37}Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility. - Highlights: • Natural high arsenic, fluoride and iodine groundwater co-occur with saline water.

  3. Inferences on Late Holocene climate from stable carbon and oxygen isotope ratio variability in soil and land snail shells from archaeological site 41KM69 in Texas, USA

    Science.gov (United States)

    Paul, D.; Mauldin, R.; Munoz, C. M.

    2011-12-01

    Well-preserved land snail shell excavate from archaeological site 41KM69 in Texas, USA, span the past 2200 years and provide an opportunity to explore the paleoclimate implications of isotopic variability in archaeological shell carbonates, bulk soil carbonates and soil organic matter. Terrestrial snail shells belonging to three genera (Polygyra, Rabdotus, and Helicina) were hand-picked from the 120 cm thick soil profile, for stable isotopic analyses. A wood charcoal radiocarbon date constrains samples below 100 cm depth in our soil profile to be ~2200 14C yr BP. Isotopic composition of modern adult snail specimens (n=24) and plants (n=18), collected from the study area, were determined for comparison with the archaeological data sets. All isotopic analyses were performed at the University of Texas at San Antonio using a Thermo Finnigan Gasbench II and a Costech Elemental Analyzer (EA) attached online to a DeltaPlus XP Stable Isotope Ratio Mass Spectrometer in continuous flow mode. Carbon isotopic compositions of both modern (-12.72 to -5.49%) and archaeological (-5.34 to -8.99%) adult snail shell carbonates suggest significant (> 60%) input of C3 plants into the diet of the snails over the past 2200 yrs. Oxygen isotopic compositions of archaeological and modern shells vary from -2.21% to -0.71% and -2.88 to +0.99%), respectively. This suggests that isotopic composition of environmental water (mainly rainwater) available at the time of shell growth was similar to that of the present day. A linearly decreasing trend in δ13C of soil organic matter from -22.83% at 2200 14C yr BP to -25.61% for modern samples imply progressively increasing abundance of C3 plants up to the present day. This implies a progressively wetter climate, or decreasing summer rainfall and less severe water stress conditions, in agreement with other studies on Holocene climate change in the southern Great Plains of USA. The studies, in general, document warm/arid conditions at ~ 2000 BP and

  4. Sulfur isotope analysis of cinnabar from Roman wall paintings by elemental analysis/isotope ratio mass spectrometry--tracking the origin of archaeological red pigments and their authenticity.

    Science.gov (United States)

    Spangenberg, Jorge E; Lavric, Jost V; Meisser, Nicolas; Serneels, Vincent

    2010-10-15

    The most valuable pigment of the Roman wall paintings was the red color obtained from powdered cinnabar (Minium Cinnabaris pigment), the red mercury sulfide (HgS), which was brought from mercury (Hg) deposits in the Roman Empire. To address the question of whether sulfur isotope signatures can serve as a rapid method to establish the provenance of the red pigment in Roman frescoes, we have measured the sulfur isotope composition (δ(34)S value in ‰ VCDT) in samples of wall painting from the Roman city Aventicum (Avenches, Vaud, Switzerland) and compared them with values from cinnabar from European mercury deposits (Almadén in Spain, Idria in Slovenia, Monte Amiata in Italy, Moschellandsberg in Germany, and Genepy in France). Our study shows that the δ(34)S values of cinnabar from the studied Roman wall paintings fall within or near to the composition of Almadén cinnabar; thus, the provenance of the raw material may be deduced. This approach may provide information on provenance and authenticity in archaeological, restoration and forensic studies of Roman and Greek frescoes.

  5. Stable nitrogen isotope ratios of macrophytes and associated periphyton along a nitrate gradient in two subtropical, spring-fed streams

    DEFF Research Database (Denmark)

    De Brabandere, Loreto; Frazer, Thomas K.; Montoya, Joseph P.

    2007-01-01

    , macrophytes and periphyton as a consequence of isotopic fractionation associated with preferential use of 14NO3-. This hypothesis was tested in two spring-fed river systems, the Chassahowitzka and Homosassa rivers, along Florida’s central Gulf of Mexico coast. 3. In general, d15N values of nitrate...

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

    Science.gov (United States)

    McLaughlin, Karen; Kendall, Carol; Silva, Steven R.; Young, Megan; Paytan, Adina

    2006-09-01

    A seasonal analysis assesing variations in the oxygen isotopic composition of dissolved inorganic phosphate (DIP) was conducted in the San Francisco Bay estuarine system, California. Isotopic fractionation of oxygen in DIP (exchange of oxygen between phosphate and environmental water) at surface water temperatures occurs only as a result of enzyme-mediated, biological reactions. Accordingly, if phospate demand is low relative to input and phosphate is not heavily cycled in the ecosystem, the oxygen isotopic composition of DIP (δ18Op) will reflect the isotopic composition of the source of phosphate to the system. Such is the case for the North San Francisco Bay, an anthropogenically impacted estuary with high surface water phosphate concentrations. Variability in the δ18Op in the bay is primarily controlled by mixing of water masses with different δ18Op signatures. The δ18Op values range from 11.4‰ at the Sacramento River to 20.1‰ at the Golden Gate. Deviations from the two-component mixing model for the North Bay reflect additional, local sources of phosphate to the estuary that vary seasonally. Most notably, deviations from the mixing model occur at the confluence of a major river into the bay during periods of high river discharge and near wastewater treatment outlets. These data suggest that δ18Op can be an effective tool for identifying P point sources and understanding phosphate dynamics in estuarine systems.

  7. Validation of Chlorine and Oxygen Isotope Ratio Analysis to Differentiate Perchlorate Sources and to Document Perchlorate Biodegradation

    Science.gov (United States)

    2011-12-01

    67 ii 4.5 SUMMARY OF LONG ISLAND PERCHLORATE SOURCE STUDY .......................... 67 5.0 SUMMARY AND CONCLUSIONS...Chilean nitrate fertilizer. 4.5 SUMMARY OF LONG ISLAND PERCHLORATE SOURCE STUDY The stable isotope results (δ37Cl, δ18O, and Δ17O) for ClO4- and key

  8. Oxygen isotope ratios in the shell of Mytilus edulis: archives of glacier meltwater in Greenland?

    DEFF Research Database (Denmark)

    Versteegh, E. A. A.; Blicher, Martin E.; Mortensen, J.

    2012-01-01

    these variations, because it precipitates its shell calcite in oxygen isotopic equilibrium with ambient seawater. As M. edulis shells are known to occur in raised shorelines and kitchen middens from previous Holocene warm periods, this species may be ideal in reconstructing past meltwater dynamics. We investigate...... raised shorelines and kitchen middens from prehistoric settlements in Greenland....

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

    Science.gov (United States)

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

    1998-05-01

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

  10. Dose-dependent response of nitrogen stable isotope ratio to proportion of legumes in diet to authenticate lamb meat produced from legume-rich diets.

    Science.gov (United States)

    Devincenzi, T; Delfosse, O; Andueza, D; Nabinger, C; Prache, S

    2014-01-01

    This study investigated the dose-dependent response in lamb meat of stable nitrogen isotope ratio to the dietary proportion of legumes, and the ability of the nitrogen isotope signature of the meat to authenticate meat produced from legume-rich diets. Four groups of nine male Romane lambs grazing a cocksfoot pasture were supplemented with different levels of fresh alfalfa forage to obtain four dietary proportions of alfalfa (0%, 25%, 50% and 75%) for 98 days on average before slaughter (groups L0, L25, L50 and L75). We measured the stable nitrogen isotope ratio in the forages and in the longissimus thoracis muscle. The δ(15)N value of the meat decreased linearly with the dietary proportion of alfalfa. The distribution of the δ(15)N values of the meat discriminated all the L0 lambs from the L75 lambs, and gave a correct classification score of 85.3% comparing lambs that ate alfalfa with those that did not.

  11. Carbon Isotope Ratios Of Carbon Dioxide In The Urban Salt Lake Valley, Utah USA: Source And Long-Term Monitoring Observations

    Science.gov (United States)

    Ehleringer, J.; Lai, C.; Strong, C.; Pataki, D. E.; Bowling, D. R.; Schauer, A. J.; Bush, S.

    2011-12-01

    A high-precision, decadal record of carbon isotope ratios in atmospheric carbon dioxide has been produced for the urbanized Salt Lake Valley, Utah USA. These data complement a similar time series of atmospheric carbon dioxide concentrations for different locations in the same urban region. This isotopic record includes diurnal and nocturnal observations based on flask (IRMS-based) and continuous (TDL-based) measurement systems. These data reveal repeatable diurnal and seasonal variations in the anthropogenic and biogenic carbon sources that can be used to reconstruct different source inputs. As the Salt Lake Valley is an isolated urban region, the impacts of local anthropogenic inputs can be distinguished from regional patterns as measured by NOAA at the rural Wendover monitoring station 200 km to the west of the Salt Lake Valley. Complementary data, such as vehicle exhaust, emission from power plants and household furnaces, plant and soil organic matter, are also provided to quantify the carbon isotope ratios of the predominant anthropogenic and biogenic sources within the Salt Lake Valley. The combined source and long-term observational values will be made freely available and their utility is discussed for modeling efforts including urban metabolism modeling and atmospheric trace gas modeling.

  12. Biogeochemistry of sulfur in the Vienna Woods: Study of sulfur stable isotope ratios by MC-ICP-MS as indicator of biogeochemical S cycling

    Science.gov (United States)

    Hanousek, Ondrej; Berger, Torsten W.; Prohaska, Thomas

    2014-05-01

    Sulfur entering forest ecosystems originates mainly from combustion of fossil fuels. This source of sulfur has been strongly (by more than 95 %) reduced in last decades and recently, higher sulfur output (in soil solution or stream water) than sulfur input (in rain water) in an ecosystem was registered in many monitored forest ecosystems. This unbalance may be caused by weathering of sulfur-bearing rocks, desorption of sulfur adsorbed in soil in the past or (re)mineralization of organic sulfur compounds. This 'negative' balance leads to mobilization of base cations along with SO42- and as such to an acidification of soils. As hypothesis, δ34S/32S depletion in stream water will be observed if a considerable proportion of atmospherically deposited sulfate is cycled through the organic S pool. Rain water and soil solutions samples were collected for this study at 3 sites (beech stands) in the Vienna Woods, Austria twice a month from May 2010 to April 2012. Due to the expected sulfate concentration gradient with respect to the distance from a tree, sampling was carried out at 5 intervals from a stem. The sulfur concentration in the samples was determined by ion chromatography. Sulfur isotope ratios (δ34S/32SV CDT) were analyzed by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in edge-resolution mode. The method was validated using IAEA-S-1 and IAEA-S-2 isotopic certified reference materials. The combined standard uncertainty of the measurement (uc = 0.10 %, k = 1) proves the suitability of the developed method. The concentration of sulfur in rain water showed expected behavior, with a seasonal maximum in winter months, in contrast to the corresponding δ34S/32SV CDT isotope ratios, where no or low seasonal trends were observed. The sulfur isotope ratios in soil solution samples show a dependence on the distance from a tree stem and the sampling depth with lower δ34S/32SV CDT ratios as compared to the precipitation. The measured isotopic

  13. Contrasting Sr isotope ratios in plagioclase from different formations of the mid-Miocene Columbia River Basalt Group

    Science.gov (United States)

    Starkel, W. A.; Wolff, J.; Eckberg, A.; Ramos, F.

    2008-12-01

    Many early Columbia River Basalt flows of the Steens and Imnaha Formations are characterized by abundant, texturally complex, coarse plagioclase phenocrysts. In Imnaha lavas, the feldspars typically have more radiogenic 87Sr/86Sr than whole rock and matrix, and may exhibit complex isotopic zoning that is not correlated with An content. Imnaha plagioclase grains are interpreted as variably-contaminated crystals produced when high-crystallinity mid-crustal basaltic intrusions exchanged interstitial melt with adjacent partly-melted crustal rock; this isotopically variable debris was then remobilized by subsequent intrusion of mantle-derived basalt and brought to the surface as an isotopically heterogeneous mixture. In contrast, plagioclase grains in the texturally very similar Steens lavas are isotopically near-homogeneous and 87Sr/86Sr is not significantly displaced from that of the bulk rock. This is consistent with magma- crust interaction at low degrees of crustal melting during the early stages of the Columbia River flood basalt episode, where Steens and Imnaha lavas were erupted from distinct magma systems hosted by different types of crust that exerted different degrees of isotopic leverage on the mantle-derived magmas [1]. Thermal input to the Steens system declined at the same time as the Imnaha magmatic flux increased to ultimately produce the huge outpouring of Grande Ronde lavas, which are mixtures of mantle- and crust-derived liquids, the latter produced during high degrees of crustal melting during the time of peak magmatic flux. [1] Wolff et al. (2008) Nature Geoscience 1, 177-180.

  14. Changes of Leaf Morphological, Anatomical Structure and Carbon Isotope Ratio with the Height of the Wangtian Tree (Parashorea chinensis) in Xishuangbanna, China

    Institute of Scientific and Technical Information of China (English)

    Chun-Xia He; Ji-Yue Li; Ping Zhou; Ming Guo; Quan-Shui Zheng

    2008-01-01

    Leaf morphological and anatomical structure and carbon isotope ratio (δ13C) change with increasing tree height. To determine how tree height affects leaf characteristics, we measured the leaf area, specific leaf mass (ratio of leaf mass to leaf area [LMA]), thickness of the total leaf, cuticle, epidermis, palisade and sponge mesophyll, stomata traits and δ13C at different heights of Parashorea chinensis with methods of light and scanning electron microscopy (SEM) and isotope-ratio mass spectrometry. The correlation and stepwise regression between tree height and leaf structure traits were carried out with SPSS software. The results showed that leaf structures and δ13C differed significantly along the tree height gradient. The leaf area, thickness of sponge mesophyll and size of stomata decreased with increasing height, whereas the thickness of lamina, palisade mesophyll, epidermis, and cuticle, ratios of palisade to spongy thickness, density of stomata and vascular bundles, LMA and δ13C increased with tree height. Tree height showed a significant relationship with all leaf Indices and the most significant relationship was with epidermis thickness, leaf area, cuticle thickness, δ13C. The δ13C value showed a significantly positive relationship with LMA (R = 0.934). Our results supported the hypothesis that the leaf structures exhibited more xeromorphic characteristics with the increasing gradient of tree height.

  15. Changes of leaf morphological, anatomical structure and carbon isotope ratio with the height of the Wangtian tree (Parashorea chinensis) in Xishuangbanna, China.

    Science.gov (United States)

    He, Chun-Xia; Li, Ji-Yue; Zhou, Ping; Guo, Ming; Zheng, Quan-Shui

    2008-02-01

    Leaf morphological and anatomical structure and carbon isotope ratio (delta13C) change with increasing tree height. To determine how tree height affects leaf characteristics, we measured the leaf area, specific leaf mass (ratio of leaf mass to leaf area [LMA]), thickness of the total leaf, cuticle, epidermis, palisade and sponge mesophyll, stomata traits and delta13C at different heights of Parashorea chinensis with methods of light and scanning electron microscopy (SEM) and isotope-ratio mass spectrometry. The correlation and stepwise regression between tree height and leaf structure traits were carried out with SPSS software. The results showed that leaf structures and delta13C differed significantly along the tree height gradient. The leaf area, thickness of sponge mesophyll and size of stomata decreased with increasing height, whereas the thickness of lamina, palisade mesophyll, epidermis, and cuticle, ratios of palisade to spongy thickness, density of stomata and vascular bundles, LMA and delta13C increased with tree height. Tree height showed a significant relationship with all leaf indices and the most significant relationship was with epidermis thickness, leaf area, cuticle thickness, delta13C. The delta13C value showed a significantly positive relationship with LMA (R = 0.934). Our results supported the hypothesis that the leaf structures exhibited more xeromorphic characteristics with the increasing gradient of tree height.

  16. [On-line method for measurement of the carbon isotope ratio of atmospheric methane and its application to atmosphere of Yakela condensed gas field].

    Science.gov (United States)

    Tang, Jun-Hong; Bao, Zheng-Yu; Xiang, Wu; Qiao, Sheng-Ying; Li, Bing

    2006-01-01

    An on-line method for measurement of the 13C/12C ratio of methane by a gas chromatography/high-temperature conversion/ isotope ratio mass spectrometry (GC/C/MS) technique was developed. This method is less laborious, more rapid (45 min), of high precision (+/- 0.4 x 10(-3)) and by using a small amount of sample (about 200 mL of atmosphere). Its application to isotopic characterization, and hence methane source identification, was demonstrated by examination of atmosphere sample collected in Yakela condensed gas field, China. The average 13C/12C ratio of atmospheric methane in Yakela field was -45.0 x 10(-3) heavier by 1.2 x 10(-3) -2.0 x 10(-3) than the global average. This is caused by seepage and diffusing of methane from Yakela condensed gas reservoir. The concentrations of atmospheric methane in daytimes are found to be lower than those in nighttimes, and the corresponding 13C/12C ratios in daytimes are lighter compared to those in nighttimes, a phenomena probably caused by the fact that a small part of methane from Yakela condensate reservoir is consumed in soil's surface under sunlight.

  17. Cold cesium molecules produced directly in a magneto-optical trap

    Institute of Scientific and Technical Information of China (English)

    Zhang Hong-Shan; Ji Zhong-Hua; Yuan Jin-Peng; Zhao Yan-Ting; Ma Jie; Wang Li-Rong; Xiao Lian-Tuan; Jia Suo-Tang

    2011-01-01

    We report on the observation of ultracold ground electric-state cesium molecules produced directly in a magnetooptical trap with a good signal-to-noise ratio.These molecules arise from the photoassociation of magneto-optical trap lasers and they are detected by resonantly enhanced multiphoton ionization technology.The production rate of ultracold cesium molecules is up to 4× 104 s-1.We measure the characteristic time of the ground electric-state cesium molecules generated in the experiment and investigate the Cs2+ molecular ion intensity as a function of the trapping laser intensity and the ionization pulse laser energy.We conclude that the production of cold cesium molecules may be enhanced by using appropriate experimental parameters,which is useful for future experiments involving the production and trapping of ultracold ground electric-state molecules.

  18. Easy Extraction Method To Evaluate δ13C Vanillin by Liquid Chromatography-Isotopic Ratio Mass Spectrometry in Chocolate Bars and Chocolate Snack Foods.

    Science.gov (United States)

    Bononi, Monica; Quaglia, Giancarlo; Tateo, Fernando

    2015-05-20

    An easy extraction method that permits the use of a liquid chromatography-isotopic ratio mass spectrometry (LC-IRMS) system to evaluate δ(13)C of vanillin in chocolate products and industrial flavorings is presented. The method applies the determination of stable isotopes of carbon to discriminate between natural vanillin from vanilla beans and vanillin from other sources (mixtures from beans, synthesis, or biotechnology). A series of 13 chocolate bars and chocolate snack foods available on the Italian market and 8 vanilla flavorings derived from industrial quality control processes were analyzed. Only 30% of products considered in this work that declared "vanilla" on the label showed data that permitted the declaration "vanilla" according to European Union (EU) Regulation 1334/2008. All samples not citing "vanilla" or "natural flavoring" on the label gave the correct declaration. The extraction method is presented with data useful for statistical evaluation.

  19. A gas chromatography/pyrolysis/isotope ratio mass spectrometry system for high-precision deltaD measurements of atmospheric methane extracted from ice cores.

    Science.gov (United States)

    Bock, Michael; Schmitt, Jochen; Behrens, Melanie; Möller, Lars; Schneider, Robert; Sapart, Celia; Fischer, Hubertus

    2010-03-15

    Air enclosures in polar ice cores represent the only direct paleoatmospheric archive. Analysis of the entrapped air provides clues to the climate system of the past in decadal to centennial resolution. A wealth of information has been gained from measurements of concentrations of greenhouse gases; however, little is known about their isotopic composition. In particular, stable isotopologues (deltaD and delta(13)C) of methane (CH(4)) record valuable information on its global cycle as the different sources exhibit distinct carbon and hydrogen isotopic composition. However, CH(4) isotope analysis is limited by the large sample size required and the demanding analysis as high precision is required. Here we present a highly automated, high-precision online gas chromatography/pyrolysis/isotope ratio monitoring mass spectrometry (GC/P/irmMS) technique for the analysis of deltaD(CH(4)). It includes gas extraction from ice, preconcentration, gas chromatographic separation and pyrolysis of CH(4) from roughly 500 g of ice with CH(4) concentrations as low as 350 ppbv. Ice samples with approximately 40 mL air and only approximately 1 nmol CH(4) can be measured with a precision of 3.4 per thousand. The precision for 65 mL air samples with recent atmospheric concentration is 1.5 per thousand. The CH(4) concentration can be obtained along with isotope data which is crucial for reporting ice core data on matched time scales and enables us to detect flaws in the measurement procedure. Custom-made script-based processing of MS raw and peak data enhance the system's performance with respect to stability, peak size dependency, hence precision and accuracy and last but not least time requirement.

  20. Source inference of exogenous gamma-hydroxybutyric acid (GHB) administered to humans by means of carbon isotopic ratio analysis: novel perspectives regarding forensic investigation and intelligence issues.

    Science.gov (United States)

    Marclay, François; Saudan, Christophe; Vienne, Julie; Tafti, Mehdi; Saugy, Martial

    2011-05-01

    γ-Hydroxybutyric acid (GHB) is an endogenous short-chain fatty acid popular as a recreational drug due to sedative and euphoric effects, but also often implicated in drug-facilitated sexual assaults owing to disinhibition and amnesic properties. Whilst discrimination between endogenous and exogenous GHB as required in intoxication cases may be achieved by the determination of the carbon isotope content, such information has not yet been exploited to answer source inference questions of forensic investigation and intelligence interests. However, potential isotopic fractionation effects occurring through the whole metabolism of GHB may be a major concern in this regard. Thus, urine specimens from six healthy male volunteers who ingested prescription GH