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Determination of trace iron in zirconium by isotope dilution-thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

An isotope dilution-thermal ionization mass spectrometry method for the determination of parts-per-million levels of iron in zirconium is required for precise, accurate analyses in studies of the effects of iron on the irradiation deformation of nuclear alloys. A two-stage purification procedure was developed to avoid the signal suppression and interference caused by the zirconium matrix. After sample dissolution and spiking with 54Fe, the bulk of the zirconium is removed by ion exchange chromatography, and the eluted Fe(III) is further purified by micro-solvent extraction into tributyl phosphate-impregnated resin beads. The iron is back-extracted, submicrogram amounts are loaded onto previously outgassed zone-refined Re filaments, and 54/56 ratios are measured at 1170°C. A silica gel/boric acid ionization enhancer is used to obtain stable Fe+ currents as strong as 2 × 10-14. A from nanogram loadings of pure iron. The procedural blank of 20 ± 6 ng is sufficiently low to allow determination of ppm levels of iron in 0.1 g zirconium samples. The analyses of solution standards showed agreement within 2% between measured and expected values, and a good fit, r2 = 0.99997, to a linear regression. The analyses of metal standards exhibited a similar good fit to a linear regression of measured against expected values, and showed good agreement with other methods. The method meets the requirements for zirconium metallurgical studies, and may be extended to other applications.

Elliot, N. L.; Campbell, M. A.; Green, L. W.



Multielement isotope dilution techniques for trace analysis  

Microsoft Academic Search

The results of a typical isotope dilution of cadmium are shown in tabular form--a reproduction of the format produced by the computer densitometer system. The first entry shows the enrichment of the cadmium spike (88.4% ¹°⁶Cd). The second entry is a report of the natural abundance of cadmium in the sample, which was analyzed by mixing 1.00 ml of the

J. A. Carter; J. C. Franklin; D. L. Donohue



Numerical calibration of the Devonian-Carboniferous boundary: Two new U-Pb isotope dilution thermal ionization mass spectrometry single-zircon ages from Hasselbachtal (Sauerland, Germany)  

NASA Astrophysics Data System (ADS)

The Hasselbachtal section (Sauerland, Germany) is an auxiliary global stratotype of the Devonian-Carboniferous boundary and one of the most important reference sections for the evolution of the latest Famennian to earliest Tournaisian pelagic fauna. Biostratigraphically well controlled altered volcanic ash layers (metabentonites) intercalated in the section afford a perfect opportunity for a numerical fixing of this important Paleozoic period boundary. We have performed U-Pb isotope dilution thermal ionization mass spectrometry (ID-TIMS) analyses on (sub)microgram-sized single zircons and zircon fragments extracted from two metabentonites (beds 79 and 70) in the lowermost Tournaisian part of the section. Bed 79 metabentonite is positioned directly above the Devonian-Carboniferous boundary within the Siphonodella sulcata conodont zone. Five concordant analyses form a cluster with a 206Pb/238U concordia age of 360.5 ± 0.8 Ma. Zircons of the next younger metabentonite (bed 70), in the lower Siphonodella duplicata conodont zone, yielded a tightly grouped cluster of 10 concordant analyses with a 206Pb/238U concordia age of 360.2 ± 0.7 Ma. On the basis of these two new single-zircon ages and previously published late Famennian U-Pb ID-TIMS ages, the Devonian-Carboniferous boundary is reinterpolated herein to 360.7 ± 0.7 Ma.

Trapp, Endres; Kaufmann, Bernd; Mezger, Klaus; Korn, Dieter; Weyer, Dieter



Measurement of isotope abundance variations in nature by gravimetric spiking isotope dilution analysis (GS-IDA).  


Subtle variations in the isotopic composition of elements carry unique information about physical and chemical processes in nature and are now exploited widely in diverse areas of research. Reliable measurement of natural isotope abundance variations is among the biggest challenges in inorganic mass spectrometry as they are highly sensitive to methodological bias. For decades, double spiking of the sample with a mix of two stable isotopes has been considered the reference technique for measuring such variations both by multicollector-inductively coupled plasma mass spectrometry (MC-ICPMS) and multicollector-thermal ionization mass spectrometry (MC-TIMS). However, this technique can only be applied to elements having at least four stable isotopes. Here we present a novel approach that requires measurement of three isotope signals only and which is more robust than the conventional double spiking technique. This became possible by gravimetric mixing of the sample with an isotopic spike in different proportions and by applying principles of isotope dilution for data analysis (GS-IDA). The potential and principle use of the technique is demonstrated for Mg in human urine using MC-TIMS for isotopic analysis. Mg is an element inaccessible to double spiking methods as it consists of three stable isotopes only and shows great potential for metabolically induced isotope effects waiting to be explored. PMID:23419016

Chew, Gina; Walczyk, Thomas



Determination of Am and Cm in spent nuclear fuels by isotope dilution inductively coupled plasma mass spectrometry and isotope dilution thermal ionization mass spectrometry after separation by high-performance liquid chromatography  

Microsoft Academic Search

Elemental and isotopic determination of americium and curium in spent nuclear fuels is necessary to validate neutronic calculation\\u000a codes and for nuclear waste disposal purposes. Prior to mass spectrometric analysis, it is mandatory to perform separations\\u000a in order to eliminate isobaric interferences between U, Pu, Am and Cm. In the spent fuels samples analyzed, a separation of\\u000a U and Pu

Frédéric Chartier; Michel Aubert; Mireille Pilier




EPA Science Inventory

The development, verification, and application of a method based on isotope dilution gas chromatography-mass spectrometry to determine aqueous trichloroacetic acid (TCAA) at the micrograms per litre level are described. The simultaneous determination of aqueous chloroform is also...


Further development of IDGS: Isotope dilution gamma-ray spectrometry  

SciTech Connect

The isotope dilution gamma-ray spectrometry (IDGS) technique for determining the plutonium concentration and isotopic composition of highly radioactive spent-fuel dissolver solutions has been further developed. Both the sample preparation and the analysis have been improved. The plutonium isotopic analysis is based on high-resolution, low-energy gamma-ray spectrometry. The plutonium concentration in the dissolver solutions then is calculated from the measured isotopic differences among the spike, the dissolver solution, and the spiked dissolver solution. Plutonium concentrations and isotopic compositions of dissolver solutions analyzed from this study agree well with those obtained by traditional isotope dilution mass spectrometry (IDMS) and are consistent with the first IDGS experimental result. With the current detector efficiency, sample size, and a 100-min count time, the estimated precision is {approximately}0.5% for {sup 239}Pu and {sup 240}Pu isotopic analyses and {approximately}1% for the plutonium concentration analysis. 5 refs., 2 figs., 7 tabs.

Li, T.K.; Parker, J.L. (Los Alamos National Lab., NM (United States)); Kuno, Y.; Sato, S.; Kamata, M.; Akiyama, T. (Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan))



Reverse isotope dilution assay and lactose intolerance assay  

US Patent & Trademark Office Database

A "reverse isotope dilution assay" herein, wherein a pathway that produces a given metabolite is assayed by diluting a labelled metabolite produced by a second constitutive pathway. In one aspect, the invention relates to a method for monitoring lactose maldigestion or lactose intolerance in humans. Specifically, the method requires administering a reverse tracer of labeled glucose and unlabeled lactose to an individual and assessing labeled carbon dioxide in breath or blood. If the lactose is digested, the labeled CO.sub.2 produced by the labeled glucose is diluted by the metabolism of the lactose.



Determination of iron in serum and water by resonance ionization isotope dilution mass spectrometry  

Microsoft Academic Search

Resonance ionization mass spectrometry has been used in conjunction with isotope dilution to determine the iron content of SRM 909 (Human Serum) and SRM 1643b (Trace Elements in Water). Iron was thermally vaporized from a filament at 1250 K. A one-wavelength, two-photon ionization scheme was employed utilizing UV light at 283.6 nm provided by a Nd:YAG pumped dye laser with

J. D. Fassett; L. J. Powell; L. J. Moore



Fast and solvent-free quantitation of boar taint odorants in pig fat by stable isotope dilution analysis-dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry.  


Boar taint is a specific off-odour of boar meat products, known to be caused by at least three unpleasant odorants, with very low odour thresholds. Androstenone is a boar pheromone produced in the testes, whereas skatole and indole originate from the microbial breakdown of tryptophan in the intestinal tract. A new procedure, applying stable isotope dilution analysis (SIDA) and dynamic headspace-thermal desorption-gas chromatography/time-of-flight mass spectrometry (dynHS-TD-GC/TOFMS) for the simultaneous quantitation of these boar taint compounds in pig fat was elaborated and validated in this paper. The new method is characterised by a simple and solvent-free dynamic headspace sampling. The deuterated compounds d3-androstenone, d3-skatole and d6-indole were used as internal standards to eliminate matrix effects. The method validation performed revealed low limits of detection (LOD) and quantitation (LOQ) with high accuracy and precision, thus confirming the feasibility of the new dynHS-TD-GC/TOFMS approach for routine analysis. PMID:24731353

Fischer, Jochen; Haas, Torsten; Leppert, Jan; Lammers, Peter Schulze; Horner, Gerhard; Wüst, Matthias; Boeker, Peter



Stable isotope dilution analyses of molybdenum in meteorites.  


Isotope dilution mass spectrometry is an ideal analytical technique to measure the elemental abundance of Mo in C1 carbonaceous chondrites and the metallic and troilite phases of iron meteorites. The mean abundance of Mo in two C1 meteorites is 0.909+/-0.040 microg/g which corresponds to a value of 2.55 atoms Mo with respect to Si equal to 10(6) atoms, which is identical to the currently accepted solar system abundance. The partitioning of Mo between the metallic and sulfide phases in the Mundrabilla iron meteorite was found to be 6.0+/-0.2 microg/g and 8.6+/-0.3 microg/g, respectively. A new, precise Mo concentration of 1.54+/-0.04 microg/g for the Geochemical Reference Standard BCR-1 is also reported. PMID:11220597

Wieser, M E; De Laeter, J R



Isotopic thermal diffusion of krypton  

NASA Astrophysics Data System (ADS)

Isotopic thermal diffusion factors have been determined for krypton in the temperature range from 243.0 K up to 777.5 K. A theoretical comparison is reported for the exponential-six model and two sets of parameters are discussed. Some references are also made for several multiparametric models.

Cunha, M. Áurea; Laranjeira, M. F.



Accurate determination of 87Rb\\/ 86Sr and 147Sm\\/ 144Nd ratios by inductively-coupled-plasma mass spectrometry in isotope geoscience: an alternative to isotope dilution analysis  

Microsoft Academic Search

The precise determination of 87Rb\\/86Sr and 147Sm\\/144Nd ratios in rocks and minerals is essential for isotope geology and geochronology. These determinations usually involve isotope dilution analysis, which requires the use of expensive isotopic spikes, consumes a significant fraction of precious thermal ionization mass spectrometer working time and, due to the repeated measurement of Rb isotopes, causes the performance of the

Pilar Montero; Fernando Bea



Oxygen and hydrogen isotopes in thermal waters at Zunil, Guatemala  

SciTech Connect

Enthalpy-chloride relations suggest that a deep reservoir exists at Zunil with a temperature near 300/sup 0/C. Water from that reservoir moves to shallower and cooler local reservoirs, where it mixes with diluted water and then attains a new water-rock chemical equilibrium. This mixed water, in turn, generally is further diluted before being discharged from thermal springs. The stable-isotopic composition of the thermal water indicates that recharge for the deep water at Zunil comes mainly from local sources. The presence of measurable tritium, which suggests that the deep water has been underground about 20 to 30 years, also indicates a local source for the recharge.

Fournier, R.O.; Hanshaw, B.B.; Urrutia Sole, J.F.



Mechanism of thermal transport in dilute nanocolloids.  


Thermal conduction modes in a nanocolloid (nanofluid) are quantitatively assessed by combining linear response theory with molecular dynamics simulations. The microscopic heat flux is decomposed into three additive fluctuation modes, namely, kinetic, potential, and collision. For low volume fractions (<1%) of nanosized platinum clusters which interact strongly with xenon host liquid, a significant thermal conductivity enhancement results from the self correlation in the potential flux. Our findings reveal a molecular-level mechanism for enhanced thermal conductivity in nanocolloids with short-ranged attraction and offer predictions that can be experimentally tested. PMID:17358654

Eapen, Jacob; Li, Ju; Yip, Sidney



Quantitation of DNA adducts by stable isotope dilution mass spectrometry  

PubMed Central

Exposure to endogenous and exogenous chemicals can lead to the formation of structurally modified DNA bases (DNA adducts). If not repaired, these nucleobase lesions can cause polymerase errors during DNA replication, leading to heritable mutations potentially contributing to the development of cancer. Due to their critical role in cancer initiation, DNA adducts represent mechanism-based biomarkers of carcinogen exposure, and their quantitation is particularly useful for cancer risk assessment. DNA adducts are also valuable in mechanistic studies linking tumorigenic effects of environmental and industrial carcinogens to specific electrophilic species generated from their metabolism. While multiple experimental methodologies have been developed for DNA adduct analysis in biological samples – including immunoassay, HPLC, and 32P-postlabeling – isotope dilution high performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) generally has superior selectivity, sensitivity, accuracy, and reproducibility. As typical DNA adducts concentrations in biological samples are between 0.01 – 10 adducts per 108 normal nucleotides, ultrasensitive HPLC-ESI-MS/MS methodologies are required for their analysis. Recent developments in analytical separations and biological mass spectrometry – especially nanoflow HPLC, nanospray ionization MS, chip-MS, and high resolution MS – have pushed the limits of analytical HPLC-ESI-MS/MS methodologies for DNA adducts, allowing researchers to accurately measure their concentrations in biological samples from patients treated with DNA alkylating drugs and in populations exposed to carcinogens from urban air, drinking water, cooked food, alcohol, and cigarette smoke.

Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory



Quantitative Analysis by Isotopic Dilution Using Mass Spectroscopy: The Determination of Caffeine by GC-MS.  

ERIC Educational Resources Information Center

Describes a laboratory technique for quantitative analysis of caffeine by an isotopic dilution method for coupled gas chromatography-mass spectroscopy. Discusses caffeine analysis and experimental methodology. Lists sample caffeine concentrations found in common products. (MVL)

Hill, Devon W.; And Others



Application of isotope dilution ICP-MS techniques to quantitative proteomics.  


ICP-MS techniques based on isotope dilution analysis can be regarded as an emerging tool in quantitative protein analysis. Well-known concepts, for example species-specific and unspecific isotope dilution analysis, which promoted accurate and precise quantification in elemental speciation studies, have nowadays been transferred to the analysis of large biomolecules, e.g. proteins. Besides detection of heteroatom-containing proteins, the artificial introduction of metal-containing labels has attracted much attention and, as a consequence, ICP-MS-based isotope dilution techniques can serve as a valuable quantification tool. In particular, because isotope dilution ICP-MS techniques can enable absolute protein quantification, they can be regarded as an attractive technique in current and prospective proteomics. In this review, recent developments and applications will be highlighted and critically assessed. PMID:20532485

Bettmer, Jörg



An algorithm for U-Pb isotope dilution data reduction and uncertainty propagation  

NASA Astrophysics Data System (ADS)

High-precision U-Pb geochronology by isotope dilution-thermal ionization mass spectrometry is integral to a variety of Earth science disciplines, but its ultimate resolving power is quantified by the uncertainties of calculated U-Pb dates. As analytical techniques have advanced, formerly small sources of uncertainty are increasingly important, and thus previous simplifications for data reduction and uncertainty propagation are no longer valid. Although notable previous efforts have treated propagation of correlated uncertainties for the U-Pb system, the equations, uncertainties, and correlations have been limited in number and subject to simplification during propagation through intermediary calculations. We derive and present a transparent U-Pb data reduction algorithm that transforms raw isotopic data and measured or assumed laboratory parameters into the isotopic ratios and dates geochronologists interpret without making assumptions about the relative size of sample components. To propagate uncertainties and their correlations, we describe, in detail, a linear algebraic algorithm that incorporates all input uncertainties and correlations without limiting or simplifying covariance terms to propagate them though intermediate calculations. Finally, a weighted mean algorithm is presented that utilizes matrix elements from the uncertainty propagation algorithm to propagate random and systematic uncertainties for data comparison between other U-Pb labs and other geochronometers. The linear uncertainty propagation algorithms are verified with Monte Carlo simulations of several typical analyses. We propose that our algorithms be considered by the community for implementation to improve the collaborative science envisioned by the EARTHTIME initiative.

McLean, N. M.; Bowring, J. F.; Bowring, S. A.



Characterizing uranium oxide reference particles for isotopic abundances and uranium mass by single particle isotope dilution mass spectrometry.  


Uranium and plutonium particulate test materials are becoming increasingly important as the reliability of measurement results has to be demonstrated to regulatory bodies responsible for maintaining effective nuclear safeguards. In order to address this issue, the Institute for Reference Materials and Measurements (IRMM) in collaboration with the Institute for Transuranium Elements (ITU) has initiated a study to investigate the feasibility of preparing and characterizing a uranium particle reference material for nuclear safeguards, which is finally certified for isotopic abundances and for the uranium mass per particle. Such control particles are specifically required to evaluate responses of instruments based on mass spectrometric detection (e.g. SIMS, TIMS, LA-ICPMS) and to help ensuring the reliability and comparability of measurement results worldwide. In this paper, a methodology is described which allows quantifying the uranium mass in single micron particles by isotope dilution thermal ionization mass spectrometry (ID-TIMS). This methodology is characterized by substantial improvements recently achieved at IRMM in terms of sensitivity and measurement accuracy in the field of uranium particle analysis by TIMS. The use of monodisperse uranium oxide particles prepared using an aerosol generation technique developed at ITU, which is capable of producing particles of well-characterized size and isotopic composition was exploited. The evidence of a straightforward correlation between the particle volume and the mass of uranium was demonstrated in this study. Experimental results have shown that the uranium mass per particle can be measured via the ID-TIMS method to a relative expanded uncertainty of about 10% (coverage factor k=2). The availability of reliable and validated methods for the characterization of uranium particles is considered to be essential for the establishment of SI-traceable measurement results. It is therefore expected that the method developed in this study is valuable for the certification of particulate materials in which the isotopic composition and the content of uranium must be accurately known. PMID:23021805

Kraiem, M; Richter, S; Erdmann, N; Kühn, H; Hedberg, M; Aregbe, Y



Thermal conductivity and sound attenuation in dilute atomic Fermi gases  

SciTech Connect

We compute the thermal conductivity and sound attenuation length of a dilute atomic Fermi gas in the framework of kinetic theory. Above the critical temperature for superfluidity, T{sub c}, the quasiparticles are fermions, whereas below T{sub c}, the dominant excitations are phonons. We calculate the thermal conductivity in both cases. We find that at unitarity the thermal conductivity {kappa} in the normal phase scales as {kappa}{proportional_to}T{sup 3/2}. In the superfluid phase we find {kappa}{proportional_to}T{sup 2}. At high temperature the Prandtl number, the ratio of the momentum and thermal diffusion constants, is 2/3. The ratio increases as the temperature is lowered. As a consequence we expect sound attenuation in the normal phase just above T{sub c} to be dominated by shear viscosity. We comment on the possibility of extracting the shear viscosity of the dilute Fermi gas at unitarity using measurements of the sound absorption length.

Braby, Matt; Chao Jingyi; Schaefer, Thomas [Physics Department, North Carolina State University, Raleigh, North Carolina 27695 (United States)



Stable isotope dilution analysis of hydrologic samples by inductively coupled plasma mass spectrometry  

USGS Publications Warehouse

Inductively coupled plasma mass spectrometry is employed in the determination of Ni, Cu, Sr, Cd, Ba, Ti, and Pb in nonsaline, natural water samples by stable isotope dilution analysis. Hydrologic samples were directly analyzed without any unusual pretreatment. Interference effects related to overlapping isobars, formation of metal oxide and multiply charged ions, and matrix composition were identified and suitable methods of correction evaluated. A comparability study snowed that single-element isotope dilution analysis was only marginally better than sequential multielement isotope dilution analysis. Accuracy and precision of the single-element method were determined on the basis of results obtained for standard reference materials. The instrumental technique was shown to be ideally suited for programs associated with certification of standard reference materials.

Garbarino, J. R.; Taylor, H. E.



Determination of Key Intermediates in Cholesterol and Bile Acid Biosynthesis by Stable Isotope Dilution Mass Spectrometry  

PubMed Central

For more than a decade, we have developed stable isotope dilution mass spectrometry methods to quantify key intermediates in cholesterol and bile acid biosynthesis, mevalonate and oxysterols, respectively. The methods are more sensitive and reproducible than conventional radioisotope (RI), gas-chromatography (GC) or high-performance liquid chromatography (HPLC) methods, so that they are applicable not only to samples from experimental animals but also to small amounts of human specimens. In this paper, we review the development of stable isotope dilution mass spectrometry for quantifying mevalonate and oxysterols in biological materials, and demonstrate the usefulness of this technique.

Yoshida, Tadashi; Honda, Akira; Miyazaki, Hiroshi; Matsuzaki, Yasushi



Determination of germanium by isotope dilution-hydride generation inductively coupled plasma mass spectrometry  

Microsoft Academic Search

Inorganic germanium in aqueous solution is determined by a combination of isotope dilution, hydride generation, and inductively-coupled plasma mass spectrometry (ID-HG-ICP-MS). Samples (5–20 ml) are spiked with an enriched stable isotope (70Ge). Germanic acid is reduced by sodium borohydride to germane (GeH4), stripped in He gas and collected on a liquid nitrogen trap. The hydrides are subsequently evaporated from the

Richard A. Mortlock; Philip. N. Froelich



Isotopic Thermal-Diffusion Factor for Krypton  

Microsoft Academic Search

The isotopic thermal-diffusion factor ?0 for krypton has been determined over a temperature range of 242° to 643°K. An artificial mixture of krypton isotopes containing about 14% 82Kr and 10% 86Kr was utilized in this study in conjunction with a 10-tube swing separator, ?0 being obtained from the concentration changes in these two isotopes only. A least-squares fitting procedure yields

R. Paul; W. W. Watson



Putting a spin on LA-ICP-MS analysis combined to isotope dilution.  


The determination of Zn, Sr, Ba, and Pb in solid samples has been achieved by laser ablation inductively coupled plasma isotope dilution mass spectrometry using a spinning platform. The fast rotation of a sample and an isotopically enriched spike placed close together on a sample holder allowed performing the isotope dilution directly inside the ablation cell. The proportion of spike versus sample of the aerosol mixture obtained has been determined online by isotope dilution in order to correct for differences in ablation rate although both materials were placed on the axis of rotation of the motor. Homogeneous, time-stable, and reusable samples were prepared by lithium borate fusion. A unique isotopically enriched spike glass was used to analyze four Standard Reference Materials of different matrix (after a simple polishing): two sediments Standard Reference Material (SRM) 1944 and SRM 2702 and two soils SRM 2586 and SRM 2711a. The proposed method yielded mass fractions with a deviation from the certified value usually lower than 12% and a precision of less than 9% RSD (except for Zn in SRM 2586 and 2711a). Although direct spiking of the solid before fusion could presumably provide better isotopic mixing, the presented methodology allows the reuse of the spike glass (thus, decreasing drastically the cost of the analysis) and is relatively faster because the spike does not need to be weighted, added, and evaporated each time. These results demonstrate the potential of this newly developed method for fast analysis of solid samples using isotope dilution at a low cost. PMID:23307123

Claverie, Fanny; Malherbe, Julien; Bier, Naomi; Molloy, John L; Long, Stephen E



User's manual for the ARMLID (Argonne metallic lithium\\/isotopic dilution) tritium assay system  

Microsoft Academic Search

The Argonne Metallic Lithium - Isotopic Dilution (ARMLID) system described in this report, originally developed at ANL for other purposes, was recently redeployed to measure the tritium production rate (TPR) in a series of US\\/Japanese collaborative fusion blanket integral experiments, involving large assemblies of fusion breeder blanket materials that were irradiated with a fusion neutron source at FNS\\/JAERI, Japan. Whereas

K. G. Porges; M. M. Bretscher; E. F. Bennett; G. DiIorio; R. F. Mattas; E. F. Lewandowski



User`s manual for the ARMLID (Argonne metallic lithium\\/isotopic dilution) tritium assay system  

Microsoft Academic Search

The Argonne Metallic Lithium - Isotopic Dilution (ARMLID) system described in this report, originally developed at ANL for other purposes, was recently redeployed to measure the tritium production rate (TPR) in a series of US\\/Japanese collaborative fusion blanket integral experiments, involving large assemblies of fusion breeder blanket materials that were irradiated with a fusion neutron source at FNS\\/JAERI, Japan. Whereas

K. G. Porges; M. M. Bretscher; E. F. Bennett; G. DiIorio; R. F. Mattas; E. F. Lewandowski



Determination of methylmercury in fish tissues by isotope dilution SPME-GC-ICP-MS  

Microsoft Academic Search

A method is described for the accurate and precise determination of monomethylmercury (MMHg) by species specific isotope dilution (ID) calibration using solid phase microextraction (SPME) in combination with gas Chromatographic (GC) separation and inductively coupled plasma mass spectrometric (ICP-MS) detection. Samples were digested with methanolic potassium hydroxide, derivatized in aqueous solution with sodium tetrapropylborate and headspace sampled with a polydimethylsiloxane

Lu Yang; Zoltán Mester; Ralph E. Sturgeon



Substoichiometric determination of heavy rare earths by isotopic dilution analysis.  


A substoichiometric method for the determination of heavy rare earths (holmium, thulium) has been developed. After the addition of a substoichiometric amount of EDTA to the test sample of rare earth labelled with its radioactive isotopes, the negatively charged complex formed was separated by passage through a column of Dowex 50 x 8. Interfering metals can be removed by preliminary cupferron and diethylammonium diethyldithiocarbamate extraction. Concentrations of rare earth down to 4 x 10(-7)g 5 ml have been determined. PMID:18960041

Prásilová, J



Development of isotope dilution gamma-ray spectrometry for plutonium analysis  

SciTech Connect

We are studying the feasibility of determining the plutonium concentration and isotopic distribution of highly radioactive, spent-fuel dissolver solutions by employing high-resolution gamma-ray spectrometry. The study involves gamma-ray plutonium isotopic analysis for both dissolver and spiked dissolver solution samples, after plutonium is eluted through an ion-exchange column and absorbed in a small resin bead bag. The spike is well characterized, dry plutonium containing {approximately}98% of {sup 239}Pu. By using measured isotopic information, the concentration of elemental plutonium in the dissolver solution can be determined. Both the plutonium concentration and the isotopic composition of the dissolver solution obtained from this study agree well with values obtained by traditional isotope dilution mass spectrometry (IDMS). Because it is rapid, easy to operate and maintain, and costs less, this new technique could be an alternative method to IDMS for input accountability and verification measurements in reprocessing plants. 7 refs., 4 figs., 4 tabs.

Li, T.K.; Parker, J.L. (Los Alamos National Lab., NM (United States)); Kuno, Y.; Sato, S.; Kurosawa, A.; Akiyama, T. (Power Reactor and Nuclear Fuel Development Corp., Tokai, Ibaraki (Japan))



An isotopic dilution approach for 1,3-butadiene tailpipe emissions and ambient air monitoring.  


An isotopic dilution approach for 1,3-butadiene analysis in gaseous samples is presented. The methodology is based on active sampling on sorbent tubes and subsequent analysis by thermal desorption into a gas chromatography/mass spectrometry system. By adding a perdeuterated internal standard onto the sorbent tubes before sampling, and using mass spectrometric detection, the methodology gives high accuracy for this unstable analyte. The method has been used to monitor 1,3-butadiene ambient air concentrations in a residential area in proximity to a heavy-traffic roadway over a one-week period, for comparison with other traffic-related pollutants analysed by standard procedures. It has also been used to determine tailpipe emissions of two vehicles by standard emission testing procedures in a dynamometer. These vehicles were chosen as examples of low- and high-end emission rate vehicles, i.e., an old no-catalytic converter Otto engine and a new direct-injection diesel engine with catalytic converter. Exhaust gas emissions were 0.052 and 35.85 mg/km, reflecting differences in fuel, engine design, age, and presence (or not) of a catalytic abatement system. The ambient air results showed a weekly average concentration of 1,3-butadiene of 0.53 microg/m(3). PMID:14966846

Riservato, Manuela; Rolla, Antonio; Davoli, Enrico



Development of stable isotope dilution assays for the quantitation of amadori compounds in foods.  


During thermal processing of foods, reducing carbohydrates and amino acids may form 1-amino-1-desoxyketoses named Amadori rearrangement products after the Italian chemist Mario Amadori. Although these compounds are transient intermediates of the Maillard reaction, they are often used as suitable markers to measure the extent of a thermal food processing, such as for spray-dried milk or dried fruits. Several methods are already available in the literature for their quantitation, but measurements are often done with external calibration without addressing losses during the workup procedure. To cope with this challenge, stable isotope dilution assays in combination with LC-MS/MS were developed for the glucose-derived Amadori products of the seven amino acids valine, leucine, isoleucine, phenylalanine, tyrosine, methionine, and histidine using the respective synthesized [(13)C6]-labeled isotopologues as internal standards. The quantitation of the analytes added to a model matrix showed a very good sensitivity with the lowest limits of detection for the Amadori compound of phenylalanine of 0.1 ?g/kg starch and 0.2 ?g/kg oil, respectively. Also, the standard deviation measured in, for example, wheat beer was only ±2% for this analyte. Application of the method to several foods showed the highest concentrations of the Amadori product of valine in unroasted cocoa (342 mg/kg) as well as in dried bell pepper (3460 mg/kg). In agreement with literature data, drying of foods led to the formation of Amadori products, whereas they were degraded during roasting of, for example, coffee or cocoa. The study presents for the first time results on concentrations of the Amadori compounds of tyrosine and histidine in foods. PMID:24865106

Meitinger, Michael; Hartmann, Sandra; Schieberle, Peter



Two-dimensional infrared spectroscopy of isotope-diluted low density amorphous ice.  


We present two-dimensional (2D) infrared (IR) spectra of isotope diluted ice in its low density amorphous form. Amorphous ice, which is structurally more similar to liquid water than to crystalline ice, provides higher resolution spectra of the hydrogen bond potentials because all motion is frozen. In the case of OD vibration of HOD in H2O, diagonal and off-diagonal (intermode) anharmonicity as well as the relaxation rate of the first excited state increase with hydrogen bond strength in a consistent way. For the OH vibration of HOD in D2O, additional more specific couplings need to be taken into account to explain the 2D IR response, that is, a Fermi resonance with the HOD bend vibration and couplings to phonon modes that lead to quantum beating. The lifetime of the fist excited state, 240 fs, is the shortest ever reported for any phase of isotope diluted water. PMID:23909621

Shalit, Andrey; Perakis, Fivos; Hamm, Peter



Reverse isotope dilution method for determining benzene and metabolites in tissues  

SciTech Connect

A method utilizing reverse isotope dilution for the analysis of benzene and its organic soluble metabolites in tissues of rats and mice is presented. Tissues from rats and mice that had been exposed to radiolabeled benzene were extracted with ethyl acetate containing known, excess quantities of unlabeled benzene and metabolites. Butylated hydroxytoluene was added as an antioxidant. The ethyl acetate extracts were analyzed with semipreparative reversed-phase HPLC. Isolated peaks were collected and analyzed for radioactivity (by liquid scintillation spectrometry) and for mass (by UV absorption). The total amount of each compound present was calculated from the mass dilution of the radiolabeled isotope. This method has the advantages of high sensitivity, because of the high specific activity of benzene, and relative stability of the analyses, because of the addition of large amounts of unlabeled carrier analogue.

Bechtold, W.E.; Sabourin, P.J.; Henderson, R.F.



Isotope dilution GC\\/MS determination of anandamide and other fatty acylethanolamides in rat blood plasma  

Microsoft Academic Search

Anandamide and allied fatty acylethanolamides (AEs) may act as signalling molecules in brain and peripheral tissues. In the present study, we describe an electron-impact gas chromatography\\/mass spectrometry (GC\\/MS) method based on isotope dilution, which may be used for the identification and quantification of anandamide and other AEs in biological matrices. The calibration curves for standard AEs were linear over the

Andrea Giuffrida; Daniele Piomelli



Evidence for dilution of deep, confined ground water by vertical recharge of isotopically heavy Pleistocene water  

Microsoft Academic Search

New analyses of the isotopic composition of water, 14-dating of dissolved inorganic carbon, and order-of-magnitude Darcy calculations suggest that a dilute body of water, trending north-south in the Cambrian-Ordovician aquifer of Iowa, was emplaced as vertical recharge of Pleistocene-age water from the base of the Des Moines lobe of late Wisconsin time. The recharge occurred through more than 300 m

D. I. Siegel



15 N isotope dilution techniques to study soil nitrogen transformations and plant uptake  

Microsoft Academic Search

The use of15N as a tracer in soil\\/plant research is examined. The limitations of the so-called Ndff approach are discussed to show the need to consider not just the fate of the added label but also the path that was followed and the rate of the transformation. The development of15N isotope dilution techniques to determine gross rates of nitrogen transformation

D. Barraclough



Isotope dilution liquid chromatography-tandem mass spectrometry for quantitative amino acid analysis.  


The role of amino acid analysis in bioanalysis has changed from a qualitative to a quantitative technique. With the discovery of both electrospray ionization and matrix-assisted laser desorption ionization in the early 1990s, the use of amino acid analysis for qualitative analysis of proteins and peptides has been replaced by mass spectrometry. Accurate measurement of the relative molecular masses of proteins and peptides, peptide mapping, and sequencing by tandem mass spectrometry provide significantly better qualitative information than can be achieved from amino acid analysis. At NIST, amino acid analysis is used to assign concentration values to protein and peptide standard reference materials (SRMs) which, subsequently, will be used in the calibration of a wide variety of protein and peptide assays, such as those used in clinical diagnostics. It is critical that the amino acid analysis method used at NIST for SRM measurement deliver the highest accuracy and precision possible. Therefore, we have developed an amino acid analysis method that uses isotope dilution LC-MS/MS - the analytical technique routinely used at NIST to certify analyte concentrations in SRMs for a wide variety of analytes. Amino acid analysis by isotope dilution LC-MS/MS was first used to measure the concentration of bovine serum albumin in NIST SRM 927d ("bovine serum albumin, 7% solution"). We have recently refined our isotope dilution LC-MS/MS amino acid analysis method to certify the concentration of 17 amino acids in NIST SRM 2389a ("amino acids in 0.1 mol/L hydrochloric acid"). We present here our most recent method for the quantification of amino acids using isotope dilution LC-MS/MS. PMID:22125133

Bunk, David M; Lowenthal, Mark S



Determination of perchlorate in infant formula by isotope dilution ion chromatography/tandem mass spectrometry  

PubMed Central

A sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in infant formula. The perchlorate was extracted from infant formula by using 20 ml of methanol and 5 ml of 1% acetic acid. All samples were spiked with 18O4 isotope-labelled perchlorate internal standard prior to extraction. After purification on a graphitised carbon solid-phase extraction column, the extracts were injected into an ion chromatography system equipped with an Ionpac AS20 column for separation of perchlorate from other anions. The presence of perchlorate in samples was quantified by isotope dilution mass spectrometry. Analysis of both perchlorate and its isotope-labelled internal standard was carried out on a Waters Quattro Ultima triple quadrupole mass spectrometer operating in a multiple reaction monitoring (MRM) negative ionisation mode. The method was validated for linearity and range, accuracy, precision, sensitivity, and matrix effects. The limit of quantification (LOQ) was 0.4 ?g 1?1 for liquid infant formula and 0.95 ?g kg?1 for powdered infant formula. The recovery ranged from 94% to 110% with an average of 98%. This method was used to analyse 39 infant formula, and perchlorate concentrations ranging from

Wang, Z.; Lau, B.P.-Y.; Tague, B.; Sparling, M.; Forsyth, D.



Direct determination of urinary iodine by inductively coupled plasma mass spectrometry using isotope dilution with iodine-129  

Microsoft Academic Search

An inductively coupled mass spectrometric method was developed for the direct determination of iodine in urine. The application of isotope dilution analysis with added 129I offers new possibilities for automatic and accurate determinations. The sample preparation con- sists of dilution with an ammonia solution containing 129 I. The validation was made by comparison with the results obtained in another laboratory

Max Haldimann; Bernhard Zimmerli; Claudine Als; Hans Gerber


Automated isotope dilution liquid chromatography-tandem mass spectrometry with on-line dilution and solid phase extraction for the measurement of cortisol in human serum sample.  


A candidate reference measurement procedure involving automated isotope dilution coupled with liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) with on-line dilution and solid phase extraction (SPE) has been developed and critically evaluated. We constructed the LC-MS/MS with on-line dilution and SPE system. An isotopically labelled internal standard, cortisol-d4, was added to serum sample. After equilibration, the methanol was added to the sample, and deproteination was performed. Then, the sample was applied to the LC-MS/MS system. The limit of detection (LOD) and limit of quantification (LOQ) were 0.2 and 1ngg(-1), respectively. Excellent precision was obtained with within-day variation (RSD) of 1.9% for ID-LC-MS/MS analysis (n=6). This method, which demonstrates simple, easy, good accuracy, high precision, and is free from interferences from structural analogues, qualifies as a reference measurement procedure. PMID:24769301

Kawaguchi, Migaku; Eyama, Sakae; Takatsu, Akiko



Assessment of vitamin A status in rats by isotope dilution: A simplified model  

SciTech Connect

Isotope-dilution analysis of vitamin A status requires giving a known quantity of labeled vitamin A to the subject and measuring the ratio of labeled to unlabeled retinol in the blood after a period for equilibration. To calculate total body stores from the isotopic ratio of plasma retinol, several assumptions must be made. In considering new ways of better calculating liver vitamin A stores from isotope-dilution data, the authors used the data of Green et al. to estimate loss of vitamin A tracer as a function of time and of vitamin A status. This correction markedly improves the correlation between calculated and analyzed liver vitamin A stores and also quantitively explains the hyperbolic relationship between fraction of tracer dose recovered in liver and mass of liver vitamin A stores. Agreement of this model with experimental data suggests that efficiency of absorption and storage of vitamin A is not affected by vitamin A status. This model can be used to estimate both the amount of tracer needed for a given lower limit of detection and an optimum sampling time.

Furr, H.C.; Cooper, D.A.; Olson, J.A. (Iowa State Univ., Ames (United States))



Evaluation of an isotope dilution liquid chromatography tandem mass spectrometry method for pharmaceuticals in fish.  


An isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was successfully developed and applied for analysis of 15 pharmaceuticals and 2 pharmaceutically active metabolites in fish tissues. This method relied on electrospray ionization (ESI), for which the influence of sample matrix on analyte ionization efficiencies remains a persistent challenge to environmental analysis. Statistically derived method detection limits (MDLs) for most analytes ranged from 1 to 10 ng/g, independent of sample matrix, and were as low as 0.04 ng/g for the most sensitive compounds in fillet tissue. MDLs for fish fillets were determined for both 10 ?L and 100 ?L injection volumes; however, results showed that detection limits did not scale linearly with injection volume. Direct comparison of spike recoveries from fish liver demonstrated that isotope dilution was superior to matrix-matched calibration in compensating for matrix interference. Spike recoveries for the isotope dilution approach generally ranged from 91 to 112%, independent of tissue (i.e., fillet or liver). The developed method was applied to examine target analytes in brown trout (Salmo trutta), collected upstream and downstream from a municipal effluent discharge to East Canyon Creek, Park City, UT, USA. Though no pharmaceuticals were detected in fish samples from the upstream location, 3 and 10 compounds (out of 17 target analytes) were detected in fish fillet and liver samples, respectively, from the downstream sampling site. Pharmaceuticals in fish fillets were observed at concentrations ranging from 0.14 to 12 ng/g, while levels were markedly higher in liver tissues (range: 0.27-600 ng/g). PMID:22840821

Du, B; Perez-Hurtado, P; Brooks, B W; Chambliss, C K



Use of isotope dilution method to predict bioavailability of organic pollutants in historically contaminated sediments.  


Many cases of severe environmental contamination arise from historical episodes, where recalcitrant contaminants have resided in the environment for a prolonged time, leading to potentially decreased bioavailability. Use of bioavailable concentrations over bulk chemical levels improves risk assessment and may play a critical role in determining the need for remediation or assessing the effectiveness of risk mitigation operations. In this study, we applied the principle of isotope dilution to quantify bioaccessibility of legacy contaminants DDT and PCBs in marine sediments from a Superfund site. After addition of (13)C or deuterated analogues to a sediment sample, the isotope dilution reached a steady state within 24 h of mixing. At the steady state, the accessible fraction (E) derived by the isotope dilution method (IDM) ranged from 0.28 to 0.89 and was substantially smaller than 1 for most compounds, indicating reduced availability of the extensively aged residues. A strong linear relationship (R(2) = 0.86) was found between E and the sum of rapid (Fr) and slow (Fs) desorption fractions determined by sequential Tenax desorption. The IDM-derived accessible concentration (Ce) was further shown to correlate closely with tissue residue in the marine benthic polychaete Neanthes arenaceodentata exposed in the same sediments. As shown in this study, the IDM approach involves only a few simple steps and may be readily adopted in laboratories equipped with mass spectrometers. This novel method is expected to be especially useful for historically contaminated sediments or soils, for which contaminant bioavailability may have changed significantly due to aging and other sequestration processes. PMID:24946234

Jia, Fang; Bao, Lian-Jun; Crago, Jordan; Schlenk, Daniel; Gan, Jay



Isotopic Dilution GC/MS Method for Methionine Determination in Biological Media  

NASA Astrophysics Data System (ADS)

The isotopic dilution mass spectrometry technique is the method of choice for sensitive and accurate determination of analytes in biological samples. The aim of this work was to establish a sensitive analytical method for the determination of methionine in different biological media. Quantitation of methionine from the resultant tracer spectrum requires deconvolution of the enrichment of the isotopomers. Deconvolution of the ion abundance ratios to yield tracer-to-tracee ratio for the isotopomer was done using Brauman's least squares approach. Comparison with regression curve calculation method is presented. The method was applied for amino-acids determination in beef, pork and fish meat.

Horj, Elena; Iordache, Andreea; Culea, Monica



Reference Soret coefficients of natural isotopes and diluted alloys of tin  

NASA Astrophysics Data System (ADS)

Measurements of Soret coefficients of tin alloys have been performed in the MFA-067 experiment of the automatic retrievable satellite EURECA. They complete the set of measurements performed in tin dilute alloys in microgravity manned laboratories. They allow also for an accurate determination of the isotopic thermomigration and for a better evaluation of the accuracy of microgravity measurements of the thermodiffusion factors. These data are compared to nonequilibrium condensed matter theories. A reasonable agreement has been obtained with the revised Enskog theory, and no electronic contribution could be identified.

van Vaerenbergh, S.; Garandet, J. P.; Praizey, J. P.; Legros, J. C.



Low level mercury speciation in freshwaters by isotope dilution GC-ICP-MS  

PubMed Central

Atmospheric deposition of anthropogenic Hg has led to increased Hg concentrations in many ecosystems. Modeling is an effective method for predicting the complex dynamics of Hg fate and transport in watersheds; such models require accurate concentrations for water column methylmercury, CH3Hg+, as input parameters, yet these concentrations are very difficult to measure precisely as they are so low. We developed a method for aqueous CH3Hg+ quantification in Lake Champlain VT, where ambient CH3Hg+ concentrations are < 0.04 ng l-1. The analysis utilized species specific isotope dilution, purge and trap, gas chromatography ICP-MS and provided instrument detection limits of ca 0.2 fM (0.04 pg l-1) and method detection limits of 15 fM (0.003 ng l-1) for CH3Hg+ which are amongst the lowest reported. Artifactual methylation of inorganic Hg2+ was shown to be minor and the precision of the isotope dilution method was generally < 5% relative standard deviation; much lower than would have been the case for an external calibration approach. The method is accurate even at low concentrations of ca. 0.025 ng l-1. This combination of precision, accuracy and low detection allow for quantification of significant differences in CH3Hg+ concentration between bays and over time within bays of Lake Champlain where mean CH3Hg+ concentrations differ by only 0.006 ng l-1 at concentrations as low as 0.014 ng l-1.

Jackson, Brian; Taylor, Vivien; Baker, R. Arthur; Miller, Eric



An isotope dilution-precipitation process for removing radioactive cesium from wastewater.  


A novel isotope dilution-precipitation method has been developed to remove cesium-137 from radioactive wastewater. The process involves adding stable cesium chloride to wastewater in order to raise the total cesium concentration, which then allows both the stable and radioactive cesium ions to be precipitated together using sodium tetraphenylborate. This process was investigated utilizing laboratory solutions to determine stable cesium dose rates, mixing times, effects of pH, and filtration requirements. Once optimized, the process was then tested on synthetic wastewater and aqueous low-level waste. Experiments showed the reaction to be very quick and stable in the pH range tested, 2.5-11.5. The wastewater may need to be filtered using a 0.45-?m filter, though ferric sulfate has been shown to promote coagulation and settling, thereby eliminating the necessity for filtration. This investigation showed that this isotope dilution-precipitation process can remove Cs-37 levels below the U.S. Department of Energy's (DOE) Derived Concentration Standard (DCS) of 3.0 × 10(-6) ?Ci/mL using a single dosage, potentially allowing the wastewater to be discharged directly to sanitary sewers. PMID:23116720

Rogers, Harold; Bowers, John; Gates-Anderson, Dianne



Accurate determination and certification of bromine in plastic by isotope dilution inductively coupled plasma mass spectrometry.  


The accurate analytical method of bromine (Br) in plastic was developed by an isotope dilution inductively coupled plasma mass spectrometry (ID-ICPMS). The figures of merit of microwave acid digestion procedures using polytetrafluoroethylene (PTFE) or quartz vessels were studied and the latter one was suitable for Br analysis since its material was free from Br contamination. The sample dilution procedures using Milli-Q water or ammonium (NH3) solution were also studied to remove memory effect for ICPMS measurement. Although severe memory effect was observed on Milli-Q water dilution, NH3 solution could remove it successfully. The accuracy of the ID-ICPMS was validated by a certified reference material (CRM) as well as the comparison with the analytical result obtained by an instrumental neutron activation analysis (INAA) as different analytical method. From these results, the ID-ICPMS developed in the present study could be evaluated as accurate analytical method of Br in plastic materials and it could apply to certification of Br in candidate plastic CRM with respect to such regulations related to RoHS (restriction of the use of hazardous substances in electrical and electronics equipment) directive. PMID:25000854

Ohata, Masaki; Miura, Tsutomu



Potential phytoavailability of anthropogenic cobalt in soils as measured by isotope dilution techniques.  


Isotope dilution is a useful technique to determine the potential phytoavailability of an element in soil. This method involves equilibrating an isotope with soil and then sampling the labile metal pool by analysis of the soil solution (E value) or plants growing in the soil (L value). The work reported here was conducted to evaluate the distribution coefficient (Kd), and the potential phytoavailability (E value) of cobalt (Co) in eight soils subjected to the atmospheric deposition of anthropogenic Co. Multiple regression analyses demonstrated that the K(d) of isotopically exchangeable Co in these soils was best modelled with two parameters: soil pH and organic carbon (OC) content (log Kd=0.85(pH)+1.1(logOC)-5.0, R2=0.94, p<0.01). Cobalt E values ranged from 1.5 to 37% of total soil Co concentrations. No evidence was obtained to suggest that Co(III), if present, was isotopically exchangeable in these soils and it was concluded that the Co E values consisted solely of Co(II). Cobalt L values, measured with Triticum aestivum L. (46 days), of two of these soils (varying in soil pH, e.g. 5.0 and 7.2) were statistically (p<0.05) different to E values. However, when changes of bulk soil pH on Co E values were considered, the two values were statistically (p<0.05) similar indicating that processes affecting soil pH during plant growth can alter isotopically exchangeable concentrations of Co. PMID:18762325

Bakkaus, Estelle; Collins, Richard N; Morel, Jean-Louis; Gouget, Barbara



Transport and Thermal Properties of Tl and Its Dilute Alloys  

Microsoft Academic Search

About thallium and its dilute alloys with indium and tin, some physical quantities were measured as functions of concentration. The heat of transition of pure thallium was also measured. In Tl-In system at 25°C the Hall coefficient decreases monotonically with increasing concentration of indium. The heat of transition at 235°C of the transformation from hexagonal close-packed to body-centred cubic structure

Ikuyo Shiozaki; Takao Sato



Determination of part-per-trillion levels of atmosphere dimethyl sulfide by isotope dilution gas chromatography/mass spectrometry  

NASA Astrophysics Data System (ADS)

Stable isotopic dilution was applied to the determination of dimethyl sulfide (DMS) in ambient air at the low part-per-trillion by volume (pptrv) levels. Perdeuterated DMS was used as an internal standard in the gas chromatography/mass spectrometry determination. The isotopically labelled internal standard provided insensitivity to possible losses of DMS in sampling and analysis. The lower limit of detection (LLD) was 1 pptrv with a sample acquisition time of 2 min.

Thornton, Donald C.; Bandy, Alan R.; Ridgeway, Robert G.; Driedger, Arthur R., III; Lalevic, Marija



Quantitation of vitamin B6 in biological samples by isotope dilution mass spectrometry  

SciTech Connect

Methods have been developed for the simultaneous quantitative analysis of vitamin B6 forms in biological samples by isotope dilution mass spectrometry using deuterated forms of pyridoxine, pyridoxal, pyridoxamine, and pyridoxic acid. The biological fluid or tissue sample was homogenized and then treated with a cocktail containing appropriate amounts of each deuterated vitamer, as well as the deuterated, phosphorylated vitamer forms. The individual vitamers were isolated from the homogenate by a complex high-performance liquid chromatographic procedure that provided separate fractions for each of the six vitamers found in biological samples. Aldehydic B6 vitamers were reduced to the alcohol form prior to acetylation and analysis by gas chromatography/mass spectrometry (GC/MS). The three resulting vitamers were analyzed by electron ionization GC/MS using a silicone capillary column. The methods have been applied to analysis of vitamin B6 in liver, milk, urine, and feces at levels as low as 0.02 nmol/ml.

Hachey, D.L.; Coburn, S.P.; Brown, L.T.; Erbelding, W.F.; DeMark, B.; Klein, P.D.



Quantitation of vitamin B6 in biological samples by isotope dilution mass spectrometry.  


Methods have been developed for the simultaneous quantitative analysis of vitamin B6 forms in biological samples by isotope dilution mass spectrometry using deuterated forms of pyridoxine, pyridoxal, pyridoxamine, and pyridoxic acid. The biological fluid or tissue sample was homogenized and then treated with a cocktail containing appropriate amounts of each deuterated vitamer, as well as the deuterated, phosphorylated vitamer forms. The individual vitamers were isolated from the homogenate by a complex high-performance liquid chromatographic procedure that provided separate fractions for each of the six vitamers found in biological samples. Aldehydic B6 vitamers were reduced to the alcohol form prior to acetylation and analysis by gas chromatography/mass spectrometry (GC/MS). The three resulting vitamers were analyzed by electron ionization GC/MS using a silicone capillary column. The methods have been applied to analysis of vitamin B6 in liver, milk, urine, and feces at levels as low as 0.02 nmol/ml. PMID:4091275

Hachey, D L; Coburn, S P; Brown, L T; Erbelding, W F; DeMark, B; Klein, P D



Determination of Cholesterol Oxidation Products in Human Plasma by Isotope Dilution-Mass Spectrometry  

Microsoft Academic Search

A method based on isotope dilution-mass spectrometry was developed for the determination of nine cholesterol oxidation products in human plasma. The cholesterol oxidation products determined were cholest-5-ene-3 ?,7 ?-diol, cholest-5-ene-3 ?,7?-diol (7?- and 7?-hydroxycholesterol, respectively), 3?-hydroxycholest-5-en-7-one (7-oxocholesterol), 5,6?-epoxy-5?-cholestan-3?-ol (cholesterol-5?,6?-epoxide), 5,6?-epoxy- 5?-cholestan-3?-ol (cholesterol-5?,6?-epoxide), cholestane-3?,5?,6?-triol, cholest-5-ene-3?,24-diol (24-hydroxycholesterol), cholest-5-ene-3?,25-diol (25-hydroxycholesterol), and cholest-5-ene-3?,27-diol (27-hydroxycholesterol). A corresponding deuterium-labeled internal standard, containing 3 to 6 deuterium

S. Dzeletovic; O. Breuer; E. Lund; U. Diczfalusy



Quantification of four artificial sweeteners in Finnish surface waters with isotope-dilution mass spectrometry.  


The artificial sweeteners sucralose (SCL), acesulfame (ACS), saccharin (SAC), and cyclamate (CYC) have been detected in environmental waters in Europe and North America. Higher environmental levels are expected in view of the increasing consumption of these food additives. In this study, an isotope-dilution mass spectrometry (IDMS) LC-MS/MS method was developed and validated for quantifying the four artificial sweeteners in boreal lakes (n = 3) and rivers (n = 12). The highest concentrations of ACS, SAC, CYC and SCL were 9,600, 490, 210 and 1000 ng/L, respectively. ACS and SAC were detected in all studied samples, and CYC and SCL in 98% and 56% of the samples. Seasonal trends of ACS and SAC were observed in some rivers. ACS and SCL concentrations in rivers correlated linearly with population equivalents of the wastewater treatment plants in the catchment areas, whereas SAC and CYC concentrations depend more on the source. PMID:24100049

Perkola, Noora; Sainio, Pirjo



Application of stable isotopes in environmental tracer studies – Measurement of monomethylmercury (CH3Hg+) by isotope dilution ICP-MS and detection of species transformation  

Microsoft Academic Search

The monovalent cation monomethylmercury (CH3Hg+) was determined in certified reference materials by isotope dilution GC\\/ICP-MS and good agreement between measured and certified\\u000a values has been found. The use of enriched stable isotopes with subsequent detection by ICP-MS is a powerful tracer technique\\u000a to study dynamic environmental processes. For the first time, it was possible to monitor opposite processes like Hg2+

H. Hintelmann; R. D. Evans



Low-level mercury speciation in freshwaters by isotope dilution GC-ICP-MS.  


Atmospheric deposition of anthropogenic Hg has led to increased Hg concentrations in many ecosystems. Modeling is an effective method for predicting the complex dynamics of Hg transport in watersheds. Such models require accurate concentrations of water column methylmercury, CH3Hg+, for input parameters, yet these concentrations are very difficult to measure precisely because they are so low. We developed a method for aqueous CH3Hg+ quantification in Lake Champlain, VT, where ambient CH3Hg+ concentrations are < 0.04 ng L(-1). The analysis utilized species-specific isotope dilution, purge and trap gas chromatography inductively coupled plasma mass spectrometry and provided instrument detection limits of about 0.3 fM (0.06 pg L(-1)) and method detection limits of 15 fM (0.003 ng L(-1)) for CH3Hg+, which are among the lowest reported. Artifactual methylation of inorganic Hg(2+) was shown to be minor, and the precision of the isotope dilution method was generally <5% relative standard deviation, which is much lower than would have been the case for an external calibration approach. The method is accurate even at low concentrations of 0.025 ng L(-1). This combination of precision, accuracy, and low detection allows for quantification of significant differences in CH3Hg+ concentration between bays and over time within bays of Lake Champlain, where mean CH3Hg+ concentrations differ by only 0.006 ng L(-1) at concentrations as low as 0.014 ng L(-1). PMID:19452902

Jackson, Brian; Taylor, Vivien; Baker, R Arthur; Miller, Eric



An isotope-dilution standard GC/MS/MS method for steroid hormones in water  

USGS Publications Warehouse

An isotope-dilution quantification method was developed for 20 natural and synthetic steroid hormones and additional compounds in filtered and unfiltered water. Deuterium- or carbon-13-labeled isotope-dilution standards (IDSs) are added to the water sample, which is passed through an octadecylsilyl solid-phase extraction (SPE) disk. Following extract cleanup using Florisil SPE, method compounds are converted to trimethylsilyl derivatives and analyzed by gas chromatography with tandem mass spectrometry. Validation matrices included reagent water, wastewater-affected surface water, and primary (no biological treatment) and secondary wastewater effluent. Overall method recovery for all analytes in these matrices averaged 100%; with overall relative standard deviation of 28%. Mean recoveries of the 20 individual analytes for spiked reagent-water samples prepared along with field samples analyzed in 2009–2010 ranged from 84–104%, with relative standard deviations of 6–36%. Detection levels estimated using ASTM International’s D6091–07 procedure range from 0.4 to 4 ng/L for 17 analytes. Higher censoring levels of 100 ng/L for bisphenol A and 200 ng/L for cholesterol and 3-beta-coprostanol are used to prevent bias and false positives associated with the presence of these analytes in blanks. Absolute method recoveries of the IDSs provide sample-specific performance information and guide data reporting. Careful selection of labeled compounds for use as IDSs is important because both inexact IDS-analyte matches and deuterium label loss affect an IDS’s ability to emulate analyte performance. Six IDS compounds initially tested and applied in this method exhibited deuterium loss and are not used in the final method.

Foreman, William T.; Gray, James L.; ReVello, Rhiannon C.; Lindley, Chris E.; Losche, Scott A.




EPA Science Inventory

It has been fifty years since Kirkham and Bartholmew (1954) presented the conceptual framework and derived the mathematical equations that formed the basis of the now commonly employed method of 15N isotope dilution. Although many advances in methodology and analysis have been ma...


Determination of B in body fluids by isotope dilution inductively coupled mass spectrometry with direct injection nebulization  

Microsoft Academic Search

The determination of B in small volumes of undigested blood plasma and urine by isotope dilution and high efficiency direct injection nebulization (DIN) inductively coupled plasma mass spectrometry (ICP-MS) is proposed. The C interference over 11B was removed by precipitating the samples proteins. Samples aliquots of 1 ml were spiked with an enriched 10B solution and shaken during 1 h

Ana Cláudia S Bellato; Maria Fernanda Giné; Amauri A Menegário



Convenient synthesis of stable deuterium-labeled alkylpyrazines for use in stable isotope dilution assays.  


Stable isotope dilution assays (SIDA) provide for accurate and precise quantitation of aroma components, such as alkylpyrazines, which are often present in low concentrations in complex food matrices. The unavailability of labeled standards is the main limitation to the widespread use of SIDA. This study describes the chlorination of several alkylpyrazines to form the corresponding chloroalkylpyrazine compounds, which are efficient starting materials for the synthesis of deuterium-labeled alkylpyrazines, namely [²H?]-2-methylpyrazine (d-1), [²H?]-2-ethylpyrazine (d-2), [²H?]-2,3(or 6)-dimethylpyrazine (d-3A, d-3B), [²H?]-2,[²H?]-6-dimethylpyrazine (d-3C), [²H?]-2,[²H?]-6-diethylpyrazine (d-4), [²H?]-2-ethyl-3(or 6)-methylpyrazine (d-5A, d-5B), 2,[²H?]-3,5-trimethylpyrazine (d-6), [²H?]-2-ethyl-3,6-dimethylpyrazine (d-7), [²H?]-2-ethyl-3,5-dimethylpyrazine (d-8), and 2,3-diethyl-[²H?]-5-methylpyrazine (d-9), which were obtained in good yields (57-100%) and high purities (86-98%). These stable isotopes were used as internal standards in SIDA to accurately and precisely determine selected alkylpyrazines in commercial peanut butter, cocoa powder, and instant coffee. 2,3-Diethyl-5-methylpyrazine (p-9) and 2-ethyl-3,5-dimethylpyrazine (p-8), despite their low abundance, had the highest odor-active values among the 13 pyrazines quantified in all products due to their very low odor thresholds. PMID:23528050

Fang, Mingchih; Cadwallader, Keith R



Absolute quantification of peptides by isotope dilution liquid chromatography-inductively coupled plasma mass spectrometry and gas chromatography\\/mass spectrometry  

Microsoft Academic Search

Absolute quantitation of peptides\\/proteins in dilute calibration solutions used in various diagnostic settings is a major challenge. Here we report the absolute quantitation of peptides by non-species-specific isotope dilution liquid chromatography-inductively coupled plasma mass spectrometry (ID LC-ICPMS) based on stoichiometric Eu tagging. The method was validated by species-specific isotope dilution gas chromatography\\/mass spectrometry (GC\\/MS) analysis of constituent amino acids of

R. a b c Liu; X. b Hou; Y. b Lv; M. a McCooeye; L. a Yang; Z.a Mester



Measurement of methylglyoxal by stable isotopic dilution analysis LC-MS/MS with corroborative prediction in physiological samples.  


This protocol describes a method for the detection and quantification of methylglyoxal (MG), the major physiological substrate of the cytosolic glyoxalase system. Accumulation of MG, also called dicarbonyl stress, is implicated in tissue damage in aging and disease. Measurement of MG is important in physiological studies, in the development of glyoxalase 1 (Glo1) inducer and inhibitor therapeutics, and in the characterization of medical products, especially dialysis fluids, and of thermally processed foods and beverages. MG can be derivatized with 1,2-diaminobenzene (DB), resulting in an adduct that can be detected using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Quantification is achieved by stable isotopic dilution analysis with [(13)C3]MG. Pre-analytic processing at ambient temperature, under acidic conditions with peroxidase inhibition, avoids artifactual overestimation of MG. Estimates obtained from physiological samples can be validated by kinetic modeling of in situ rates of protein glycation by MG for confirmation of the results. This procedure was developed for the analysis of cultured cells, plasma and animal tissue samples, and it can also be used to analyze plant material. Experimental measurement requires 4.5 h for sample batch pre-analytic processing and 30 min per sample for LC-MS/MS analysis. PMID:25058644

Rabbani, Naila; Thornalley, Paul J



Apolipoprotein A-I assayed in human serum by isotope dilution as a potential standard for immunoassay  

SciTech Connect

We measured the amount of apoA-I in serum by isotope dilution, finding 1.33 mg/ml (standard deviation 0.177) in six normolipidemic, healthy subjects. We developed this method by adapting published techniques to purify apoA-I from 3 ml of serum in two steps: density gradient ultracentrifugation and high performance liquid chromatography gel filtration. The 125I-labeled apoA-I tracer was first screened, by incubation with serum, to select labeled apoA-I which retained the ability to exchange with native apoA-I and bind to HDL. A known amount of 125I-labeled apoA-I-labeled HDL was added to unknown serum samples; apoA-I was reisolated from the serum and its specific radioactivity was used to calculate the dilution of the added, labeled apoA-I by the unlabeled apoA-I in the unknown serum. By not relying on immunochemical techniques, the isotope dilution assay provided results that are independent of the expression of individual apoA-I antigenic sites. Therefore, sera that have been assayed by isotope dilution can serve as standards to evaluate the accuracy of immunoassays for serum apoA-I and provide primary standards for such immunoassays.

Weech, P.K.; Jewer, D.; Marcel, Y.L.



The measurement of free thyroxine by isotope dilution tandem mass spectrometry  

PubMed Central

Background Most clinical chemistry laboratories measure free thyroxine (FT4) by an analogue (direct) method. Nevertheless, the validity of analogue FT4 immunoassays has been questioned and patient’s results using this approach frequently do not fit in with the clinical presentation. Because of these problems we routinely send out all direct free T4’s that are < 2.5th percentile and many that are > 97.5th percentile for measurement by equilibrium dialysis, the gold standard method. In approximately half of these cases, the FT4 by equilibrium dialysis was normal. We developed a rapid, reliable free T4 method employing isotope dilution tandem mass spectrometry and compared our results with both the analogue (direct) free T4 and equilibrium dialysis procedures. Methods An API-4000 tandem mass spectrometer (Sciex, Toronto, Canada) equipped with TurboIonSpray and Agilent HPLC system was used employing isotope dilution with deuterium labeled internal standard (IS=L-thyroxine-d2). Serum was filtered through the Centrifree YM-30 ultrafiltration device by centrifugation, IS added to the ultrafiltrate, and 400 ?L injected onto a C-18 column. After washing, the switch valve is activated and a methanol gradient allows for elution of both T4 and the IS into the LC/MS/MS system. Quantitation was by MRM analysis in the negative mode. Equilibrium dialysis was performed by the Nichols method and analogue free T4 results were obtained on the Dade Dimension RxL. Results The within-day and between-day CV’s were < 7.1% at all concentrations tested. The results correlated well with equilibrium dialysis (Eq Dial=0.971 MS+0.041, n =68, Syx=1.381, r =0.954). A poor correlation was found with the analogue (direct) free T4 method (IA=0.326 MS+6.27, n =154, Syx=1.96, r =0.459). Conclusions Samples can be processed in batches of 30. The free T4 tandem MS method has a rapid turn-around-time vs the equilibrium dialysis procedure, with a chromatographic run time of 8 min per sample.

Soldin, Steven J.; Soukhova, Nadia; Janicic, Natasa; Jonklaas, Jacqueline; Soldin, Offie P.



Determination of total mercury in biological tissue by isotope dilution ICPMS after UV photochemical vapor generation.  


A method is developed for the determination of trace mercury in biological samples using photo chemical vapor generation (PVG) and isotope dilution inductively coupled plasma mass spectrometry (ID ICPMS) detection. Biological tissues were solubilized in formic acid. Subsequently, the sample solutions were exposed to an ultraviolet (UV) source for the reduction of mercury into vapor species prior to ICPMS measurements. The formic acid served not only as a tissue solubilizer in the sample preparation procedure, but also as a photochemical reductant for mercury in the PVG process. The problem arising from the opaque formic acid digested solution was efficiently solved by using ID method. The optimum conditions for sample treatment and PVG were investigated. A limit of detection (LOD) of 0.5 pg g(-1), based on an external calibration, provided 350-fold improvement over that obtained by utilizing conventional pneumatic nebulization sample introduction. Method validation was demonstrated by the determination of total mercury in several biological tissue certified reference materials (CRMs). The results were in good agreement with the certified values. PMID:24209355

Liu, Rui; Xu, Mo; Shi, Zeming; Zhang, Jiayun; Gao, Ying; Yang, Lu



Precise determination of seawater calcium using isotope dilution inductively coupled plasma mass spectrometry.  


We describe a method for rapid, precise and accurate determination of calcium ion (Ca(2+)) concentration in seawater using isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). A 10 ?L aliquot of seawater was spiked with an appropriate (43)Ca enriched solution for (44)Ca/(43)Ca ID-ICP-MS analyses, using an Element XR (Thermo Fisher Scientific), operated at low resolution in E-scan acquisition mode. A standard-sample bracketing technique was applied to correct for potential mass discrimination and ratio drift at every 5 samples. A precision of better than 0.05% for within-run and 0.10% for duplicate measurements of the IAPSO seawater standard was achieved using 10 ?L solutions with a measuring time less than 3 minutes. Depth profiles of seawater samples collected from the Arctic Ocean basin were processed and compared with results obtained by the classic ethylene glycol tetra-acetic acid (EGTA) titration. Our new ID-ICP-MS data agreed closely with the conventional EGTA data, with the latter consistently displaying 1.5% excess Ca(2+) values, possibly due to a contribution of interference from Mg(2+) and Sr(2+) in the EGTA titration. The newly obtained Sr/Ca profiles reveal sensitive water mass mixing in the upper oceanic column to reflect ice melting in the Arctic region. This novel technique provides a tool for seawater Ca(2+) determination with small sample size, high throughput, excellent internal precision and external reproducibility. PMID:24434804

Liu, Hou-Chun; You, Chen-Feng; Cai, Wei-Jun; Chung, Chuan-Hsiung; Huang, Kuo-Fang; Chen, Bao-Shan; Li, Yen



Cadmium measurements in coral skeleton using isotope dilution-inductively coupled plasma-mass spectrometry  

NASA Astrophysics Data System (ADS)

Here a method for the precise analysis of Cd/Ca in coral skeleton using inductively coupled plasma-mass spectrometry (ICP-MS) is presented. Isotope dilution and gravimetric standards with internal standardization were used for Cd and Ca determination, respectively. Separation of alkaline earth metals from Cd using ion chromatography reduced the high total dissolved solids while maintaining a strong Cd signal. Repeated Cd/Ca measurements of a coral standard yielded a precision of ±2.2% (one standard deviation as a fraction of signal). Analyses of reference materials (BCR-1, BHVO-1, W-2, GSR-3, GSR-6, CACB-1, JCp-1, and JCt-1) fell within established ranges, with a precision comparable to other ICP-MS measurements. Advantages of this approach over existing methods for corals are as follows: (1) reduced introduction of high-concentration elements into the mass spectrometer, (2) sample requirements as low as 15 mg (i.e., ?1 pmol Cd/sample), and (3) determination of multiple element ratios on the same sample aliquot with a precision of ±7% or better.

Matthews, Kathryn A.; McDonough, William F.; Grottoli, AndréA. G.



Daily cortisol production rate in man determined by stable isotope dilution/mass spectrometry  

SciTech Connect

Growth retardation as well as the development of Cushingoid features in adrenally insufficient patients treated with the currently accepted replacement dose of cortisol (33-41 mumol/day.m2; 12-15 mg/ prompted us to reevaluate the cortisol production rate (FPR) in normal subjects and patients with Cushing's syndrome, using a recently developed thermospray liquid chromatography-mass spectrometry method. The stable isotope (9,12,12-2H3)cortisol was infused continuously for 31 h at about 5% of the anticipated FPR. Blood samples were obtained at 20-min intervals for 24 h, spun, and pooled in 4-h groups. Tracer dilution in plasma was determined by liquid chromatography/mass spectrometry. The method was validated with controlled infusions in 6 patients with adrenal insufficiency. Results from 12 normal volunteers revealed a FPR of 27.3 +/- 7.5 mumol/day (9.9 +/- 2.7 mg/day) or 15.7 mumol/day.m2; 5.7 mg/m2. day. A previously unreported circadian variation in FPR was observed. Patients with Cushing's syndrome demonstrated unequivocal elevation of FPR and cortisol concentration correlated during each sample period in normal volunteers, indicating that cortisol secretion, rather than metabolism, is mainly responsible for changes in plasma cortisol. Our data suggest that the FPR in normal subjects may be lower than previously believed.

Esteban, N.V.; Loughlin, T.; Yergey, A.L.; Zawadzki, J.K.; Booth, J.D.; Winterer, J.C.; Loriaux, D.L. (National Institute of Child Health and Human Development, Bethesda, MD (USA))



[Determination of indicator toxaphene in soil by isotope dilution-gas chromatography-tandem mass spectrometry].  


Although toxaphene is now banned in use, the analysis of toxaphene has attracted increasing interest due to its persistence and widespread atmospheric transport in the environment. A new method based on isotope dilution-gas chromatography-tandem mass spectrometry (ID-GC-MS/MS) has been developed for the determination of three toxaphene specific congeners comprised of Parlar No. 26 (P26), Parlar No. 50 (P50) and Parlar No. 62 (P62) in soil. (13)C10-labeled indicator toxaphene solution was added to the sample prior to pretreatment. Then the sample was extracted using pressurized liquid extraction (PLE) followed by purification on multilayer acidic silica column and neutral silica column. The eluent was concentrated under gentle nitrogen gas flow and spiked with the injection of internal standard of (13)C10-chlordane. Identification and quantification of the analytes were carried out in the multiple reaction monitoring (MRM) mode after the GC separation. The linear range was 20-800 microg/L for three congeners, limits of detection (LOD) ranged from 3.0 to 6.0 pg. The five point calibration curves showed a good linearity for all the congeners (R2 > 0.99). The relative standard deviations (RSDs) were below 11% for and the spiked recoveries were in the range of 55%-110%. The developed analytical method is suitable for the determination of toxaphene specific congeners in soil. PMID:20812620

Zhang, Bing; Wu, Jiajia; Liu, Guorui; Gao, Lirong; Zheng, Minghui



Measurement of trimethylamine-N-oxide by stable isotope dilution liquid chromatography tandem mass spectrometry.  


Trimethylamine-N-oxide (TMAO) levels in blood predict future risk for major adverse cardiac events including myocardial infarction, stroke, and death. Thus, the rapid determination of circulating TMAO concentration is of clinical interest. Here we report a method to measure TMAO in biological matrices by stable isotope dilution liquid chromatography tandem mass spectrometry (LC/MS/MS) with lower and upper limits of quantification of 0.05 and >200?M, respectively. Spike and recovery studies demonstrate an accuracy at low (0.5?M), mid (5?M), and high (100?M) levels of 98.2, 97.3, and 101.6%, respectively. Additional assay performance metrics include intraday and interday coefficients of variance of <6.4 and <9.9%, respectively, across the range of TMAO levels. Stability studies reveal that TMAO in plasma is stable both during storage at -80°C for 5years and to multiple freeze thaw cycles. Fasting plasma normal range studies among apparently healthy subjects (n=349) show a range of 0.73-126?M, median (interquartile range) levels of 3.45 (2.25-5.79)?M, and increasing values with age. The LC/MS/MS-based assay reported should be of value for further studies evaluating TMAO as a risk marker and for examining the effect of dietary, pharmacologic, and environmental factors on TMAO levels. PMID:24704102

Wang, Zeneng; Levison, Bruce S; Hazen, Jennie E; Donahue, Lillian; Li, Xin-Min; Hazen, Stanley L



Boundary-layer isotope dilution/mass balance methods for measurement of nocturnal methane emissions from grazing sheep  

NASA Astrophysics Data System (ADS)

Following advances with methods for 13C/ 12C isotopic analysis of methane in small (?4 L) air samples, new isotope dilution techniques are proposed for measurement of methane emissions at the paddock scale from grazing ruminant animals. These techniques combine measurement of the isotopic ?13CH 4 composition of air samples with a non-intrusive mass balance method applied in the nocturnal boundary layer. Flux estimates from trials using the isotope dilution techniques are compared with estimates based on scaling up individual animal emission measurements using a rumen gas tracer technique. The methane flux assessed by the latter technique ranged from 35 to 70 mg (CH 4) m -2 d -1 with a stocking density between 10 and 20 sheep ha -1. The isotope dilution based nocturnal boundary-layer estimates generally agreed to better than a factor of 2 and usually to within 20% of the average of individual animal emission rate per unit area of paddock. Both static and advecting mass balance methods are developed. In the advecting case, the upwind/downwind contrast in ?13C was typically 0.2-0.5‰. Care was necessary with air sampling to avoid error in this small contrast contributing to error in the flux. Agreement between concentration- and isotope-based nocturnal boundary layer methods and the sheep breath measurements indicated that sample representativeness was generally good. Factors which affect the accuracy of the method are examined and include variability in nocturnal mixing height, the assumed ?13CH 4 composition of the source sheep breath and diurnal patterns in sheep emission. This paper establishes new techniques useful in the paddock to landscape scale although widespread application awaits further development of technology for rapid and repeatable field analysis of ?13CH 4 in small samples.

Harvey, M. J.; Brailsford, G. W.; Bromley, A. M.; Lassey, K. R.; Mei, Z.; Kristament, I. S.; Reisinger, A. R.; Walker, C. F.; Kelliher, F. M.


Quantifying gross fluxes of nitrous oxide and dinitrogen gas using a novel isotope pool dilution technique  

NASA Astrophysics Data System (ADS)

One of the existing challenges in trace gas biogeochemistry lies in understanding the environmental controls on the net and gross fluxes of soil-derived compounds. This is because gross production and consumption fluxes of these gases often occur simultaneously or in close spatial proximity, making it difficult to make inferences about the effects of environmental variables (e.g. temperature, soil water content, porosity, redox, etc.) on gross fluxes based on bulk concentration measurements alone. One novel approach for quantifying gross fluxes of N2O and N2 is 'stable isotope pool dilution;' a technique that has been successfully applied to study bidirectional fluxes of other biogenic compounds, such as CH4 and halocarbons. To evaluate the efficacy of this method for quantifying gross N2O and N2 fluxes, we conducted a combined field and laboratory test of the pool dilution technique along side conventional measures of nitrification and denitrification. Experiments were conducted in a N-rich managed peatland pasture in the Sacramento-San Joaquin Delta, California, USA. Field and laboratory measurements were performed in a broad range of microforms and microtopes spanning a range of hydrologic and environmental conditions. Field experiments focussed on gross fluxes of N2O and N2 in upper soil horizons; the soil layers that exchange most rapidly with the atmosphere. Laboratory experiments indicated that 15N pool dilution compares favourably with more conventional measures of N2O and N2 flux, such as acetylene inhibition or the 15NO3- pulse-trace approach. Gross N2O fluxes greatly exceeded N2 fluxes by as much as an order of magnitude or more, and averaged 6.1 ± 2.2 mg N m-2 d-1, with a range from 0.06 to 63.13 mg N m-2 d-1. N2O:N2 emissions ratios generally exceeded 1 except along slopes, with an overall range of 0.2 to 30.9. NH4+ concentrations and denitrifying enzyme activity were the best predictors of gross N2O fluxes in the field (r2 = 0.65). Net N2O production rates explained 53 percent of the variability in gross N2 fluxes, whereas N2O:N2 ratios were best predicted by the combination of water-filled pore space and mineral N concentration (r2 = 0.44). This research highlights the potential of the pool dilution approach for quantifying gross fluxes of N2O and N2 from surface soils under both field and laboratory conditions. Future experiments will couple these measures of soil surface fluxes with push-pull methods for determining gross N2O and N2 fluxes at depth, and natural abundance isotopomer measurements to determine sources of N2O.

Arn Teh, Yit; Yang, Wendy; Silver, Whendee L.



Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.  


This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. PMID:24874385

Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L



Biological nitrogen fixation in maize ( Zea mays L.) by 15 N isotope-dilution and identification of associated culturable diazotrophs  

Microsoft Academic Search

The nitrogen-fixing capacity of a range of commercial cultivars of maize (Zea mays L.) was evaluated by the 15N isotope-dilution method. Biological nitrogen fixation (BNF) expressed as percent nitrogen derived from air (Ndfa) ranged\\u000a from 12 to 33 regardless of nitrogen fertilization. BNF was not affected by mineral nitrogen fertilization except on cultivar\\u000a Topacio and PAU-871 cultivars. Subsequently, culturable bacterial

Adriana Montañez; Cecilia Abreu; Paul R. Gill; Gudni Hardarson; Margarita Sicardi



Performance of Sorghum Grown on a Salt Affected Soil Manured with Dhaincha Plant Residues Using a N Isotopic Dilution Technique  

Microsoft Academic Search

A field experiment was conducted on a salt-affected soil to determine the effect of application of three types of Dhaincha (Sesbania aculeata Pers.) residues (R, roots; L, shoots; L+R, shoots plus roots) on the performance of sorghum (Sorghum bicolor L.) using the indirect N isotopic dilution technique. Results indicated that sesbania residues (L and L+R), used as green manures, significantly

F. Kurdali; F. Al-Ain; M. Al-Shammaa; A. K. Razzouk



Isotope-dilution ICP–MS for trace element determination and speciation: from a reference method to a routine method?  

Microsoft Academic Search

This critical review discusses the conditions under which inductively coupled plasma–isotope dilution mass spectrometry (ICP–IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP–IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP–IDMS suffer both

Klaus G. Heumann



Pilot Study for the Standardization of Insulin Immunoassays with Isotope Dilution-Liquid Chromatography\\/Tandem Mass Spectrometry  

Microsoft Academic Search

Background: An international working group convened by the American Diabetes Association (ADA) called for a reference measurement procedure for use in a true- ness-based standardization project of insulin immuno- assays. In view of this demand, we conducted a pilot study to investigate the feasibility of such a standard- ization project with our isotope dilution-liquid chro- matography\\/tandem mass spectrometry (ID-LC\\/tandem MS)

Diego Rodriguez-Cabaleiro; Katleen Van Uytfanghe; Veronique Stove; Tom Fiers; Linda M. Thienpont



Ultratrace-level radium-226 determination in seawater samples by isotope dilution inductively coupled plasma mass spectrometry  

Microsoft Academic Search

An improved and novel sample preparation method for 226Ra determination in liquid samples by isotope dilution inductively coupled plasma sector field mass spectrometry using laboratory-prepared\\u000a 228Ra tracer has been developed. The procedure involves a selective preconcentration achieved by applying laboratory-prepared\\u000a MnO2 resin followed by cation exchange chromatographic separation. In order to completely eliminate possible molecular interferences,\\u000a medium mass resolution (R?=?4,000)

Zsolt Varga



Lead speciation in rainwater by isotope dilution-high performance liquid chromatography-inductively coupled plasma-mass spectrometry  

Microsoft Academic Search

A new method for lead speciation in rainwater by isotope dilution analysis (IDA) using directly coupled high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) is described and demonstrated. Samples containing trimethyllead (TML) chloride and triethyllead (TEL) chloride in the presence of large amounts of inorganic lead have been analysed by HPLC-ICP-MS using reverse phase ion-pairing chromatography. The detection limit for

Les Ebdon; Steve J. Hill; Cristina Rivas



Isotope-dilution ICP-MS for trace element determination and speciation: from a reference method to a routine method?  


This critical review discusses the conditions under which inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP-IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP-IDMS suffer both from lack of commercially available isotope-labeled spike compounds for species-specific isotope dilution and from the more complicated system set-up required for species-unspecific ICP-IDMS analysis. Coupling of gas or liquid chromatography with species-specific ICP-IDMS, however, enables validation of analytical methods involving species transformations which cannot easily be performed by other methods. The potential and limitations of ICP-IDMS are demonstrated by recently published results and by some unpublished investigations by our group. It has been shown that possible loss of silicon as volatile SiF4 during decomposition of a sample by use of hydrofluoric acid has no effect on trace silicon determination if the isotope-dilution step occurs during digestion in a closed system. For powder samples, laser ablation ICP-IDMS can be applied with an accuracy comparable with that only available from matrix-matched standardization, whereas the accuracy of electrothermal vaporization ICP-IDMS was strongly dependent on the element determined. The significance of easy synthesis of isotope-labeled spike compounds for species-specific ICP-IDMS is demonstrated for monomethylmercury and Cr(VI). Isotope-exchange reactions between different element species can prevent the successful application of ICP-IDMS, as is shown for iodinated hydrocarbons. It is also shown for monomethylmercury that species transformations during sample-pretreatment steps can be followed by species-specific ICP-IDMS without loss of accuracy. A relatively simple and time-efficient procedure for determination of monomethylmercury in environmental and biological samples is discussed. The method, which entails a rapid microwave-assisted isotope dilution step and in-situ extraction of the derivatized species, has good potential for routine application in the future. PMID:14647946

Heumann, Klaus G



Cellular Lipid Extraction for Targeted Stable Isotope Dilution Liquid Chromatography-Mass Spectrometry Analysis  

PubMed Central

The metabolism of fatty acids, such as arachidonic acid (AA) and linoleic acid (LA), results in the formation of oxidized bioactive lipids, including numerous stereoisomers1,2. These metabolites can be formed from free or esterified fatty acids. Many of these oxidized metabolites have biological activity and have been implicated in various diseases including cardiovascular and neurodegenerative diseases, asthma, and cancer3-7. Oxidized bioactive lipids can be formed enzymatically or by reactive oxygen species (ROS). Enzymes that metabolize fatty acids include cyclooxygenase (COX), lipoxygenase (LO), and cytochromes P450 (CYPs)1,8. Enzymatic metabolism results in enantioselective formation whereas ROS oxidation results in the racemic formation of products. While this protocol focuses primarily on the analysis of AA- and some LA-derived bioactive metabolites; it could be easily applied to metabolites of other fatty acids. Bioactive lipids are extracted from cell lysate or media using liquid-liquid (l-l) extraction. At the beginning of the l-l extraction process, stable isotope internal standards are added to account for errors during sample preparation. Stable isotope dilution (SID) also accounts for any differences, such as ion suppression, that metabolites may experience during the mass spectrometry (MS) analysis9. After the extraction, derivatization with an electron capture (EC) reagent, pentafluorylbenzyl bromide (PFB) is employed to increase detection sensitivity10,11. Multiple reaction monitoring (MRM) is used to increase the selectivity of the MS analysis. Before MS analysis, lipids are separated using chiral normal phase high performance liquid chromatography (HPLC). The HPLC conditions are optimized to separate the enantiomers and various stereoisomers of the monitored lipids12. This specific LC-MS method monitors prostaglandins (PGs), isoprostanes (isoPs), hydroxyeicosatetraenoic acids (HETEs), hydroxyoctadecadienoic acids (HODEs), oxoeicosatetraenoic acids (oxoETEs) and oxooctadecadienoic acids (oxoODEs); however, the HPLC and MS parameters can be optimized to include any fatty acid metabolites13. Most of the currently available bioanalytical methods do not take into account the separate quantification of enantiomers. This is extremely important when trying to deduce whether or not the metabolites were formed enzymatically or by ROS. Additionally, the ratios of the enantiomers may provide evidence for a specific enzymatic pathway of formation. The use of SID allows for accurate quantification of metabolites and accounts for any sample loss during preparation as well as the differences experienced during ionization. Using the PFB electron capture reagent increases the sensitivity of detection by two orders of magnitude over conventional APCI methods. Overall, this method, SID-LC-EC-atmospheric pressure chemical ionization APCI-MRM/MS, is one of the most sensitive, selective, and accurate methods of quantification for bioactive lipids.

Gelhaus, Stacy L.; Mesaros, A. Clementina; Blair, Ian A.



Evaluation of the agronomic effectiveness of natural and partially acidulated phosphate rocks in several soils using 32 P isotopic dilution techniques  

Microsoft Academic Search

The agronomic effectiveness of two natural phosphate rocks (PRs) from North Carolina (USA) and Togo and their 50% partially acidulated products (PAPRs) was evaluated in two greenhouse experiments using32P isotopic dilution techniques, namely L and AL values.

N. Kato; F. Zapata; H. Axmann



Speciation and isotope dilution analysis of gadolinium-based contrast agents in wastewater.  


The fate of Gadolinium (Gd)-based contrast agents for magnetic resonance imaging (MRI) during sewage treatment was investigated. The total concentration of Gd in influent and effluent 2 and 24 h composite samples was determined by means of isotope dilution analysis. The balancing of Gd input and output of a sewage plant over seven days indicated that approximately 10% of the Gd is removed during treatment. Batch experiments simulating the aeration tank of a sewage treatment plant confirmed the Gd complex removal during activated sludge treatment. For speciation analysis of the Gd complexes in wastewater samples, high performance liquid chromatography (HPLC) was hyphenated to inductively coupled plasma sector field mass spectrometry (ICP-SFMS). Separation of the five predominantly used contrast agents was carried out on a new hydrophilic interaction liquid chromatography stationary phase in less than 15 min. A limit of detection (LOD) of 0.13 ?g/L and a limit of quantification of 0.43 ?g/L could be achieved for the Gd chelates without having to apply enrichment techniques. Speciation analysis of the 24 h composite samples revealed that 80% of the Gd complexes are present as Gd-BT-DO3A in the sampled treatment plant. The day-of-week dependent variation of the complex load followed the variation of the total Gd load, indicating a similar behavior. The analysis of sewage sludge did not prove the presence of anthropogenic Gd. However, in the effluent of the chamber filter press, which was used for sludge dewatering, two of the contrast agents and three other unknown Gd species were observed. This indicates that species transformation took place during anaerobic sludge treatment. PMID:23062026

Telgmann, Lena; Wehe, Christoph A; Birka, Marvin; Künnemeyer, Jens; Nowak, Sascha; Sperling, Michael; Karst, Uwe



Quantitative determination of free and total bisphenol A in human urine using labeled BPA glucuronide and isotope dilution mass spectrometry.  


Bisphenol A (BPA) is a widely used industrial chemical in the manufacturing of polycarbonate plastic bottles, food and beverage can linings, thermal receipts, and dental sealants. Animal and human studies suggest that BPA may disrupt normal hormonal function and hence, potentially, have negative effects on the human health. While total BPA is frequently reported, it is recognized that free BPA is the biologically active form and is rarely reported in the literature. The objective of this study was to develop a sensitive and improved method for the measurement of free and total BPA in human urine. Use of a labeled conjugated BPA (bisphenol A-d6 ?-D-glucuronide) allowed for the optimization of the enzymatic reaction and permitted an accurate determination of the conjugated BPA concentration in urine samples. In addition, a (13)C12-BPA internal standard was used to account for the analytical recoveries and performance of the isotope dilution method. Solid-phase extraction (SPE) combined with derivatization and analysis using a triple quadrupole GC-EI/MS/MS system achieved very low method detection limit of 0.027 ng/mL. BPA concentrations were measured in urine samples collected during the second and third trimesters of pregnancy in 36 Canadian women. Total maternal BPA concentrations in urine samples ranged from not detected to 9.40 ng/mL (median, 1.21 ng/mL), and free BPA concentrations ranged from not detected to 0.950 ng/mL (median, 0.185 ng/mL). Eighty-six percent of the women had detectable levels of conjugated BPA, whereas only 22 % had detectable levels of free BPA in their urine. BPA levels measured in this study agreed well with data reported internationally. PMID:24817354

Kubwabo, Cariton; Kosarac, Ivana; Lalonde, Kaela; Foster, Warren G



Determination of lead in urine and whole blood by stable isotope dilution gas chromatography-mass spectrometry.  


A stable isotope dilution gas chromatography-mass spectrometry (GC-MS) method is described for the determination of lead (Pb) in urine and whole blood. The use of lithium bis(trifluoroethyl)dithiocarbamate Pb(FDEDTC) as a chelating agent showed strong memory effect, restricting the range of Pb isotope ratios that can be measured in unknown samples. To overcome this carryover problem, we further derivatized the Pb(FDEDTC)2 chelate with 4-fluorophenyl magnesium bromide to form Pb(FC6H4)4. The sequential analyses of solutions of natural Pb and enriched 204Pb with Pb(FC6H4)4 chelate by GC-MS demonstrated no observable memory effect. Precision and accuracy of Pb isotope ratio measurements with Pb(FC6H4)4 were established, and the isotope dilution GC-MS method was validated by determining Pb concentrations in urine standards from the National Institute of Standards and Technology, urine and blood reference materials from the New York State Department of Health, and blood Pb survey samples from the College of American Pathologists. PMID:8044988

Aggarwal, S K; Kinter, M; Herold, D A



Determination of trace level cadmium in SRM 3280 Multivitamin/Multielement Tablets via isotope dilution inductively coupled plasma mass spectrometry.  


Cadmium was quantified at 80.15±0.86 ng/g (mean±95% expanded uncertainty) in NIST SRM 3280 Multivitamin/Multielement Tablets, using isotope dilution mass spectrometry. The method described utilized various precipitation and solid-phase extraction separation methodologies to isolate Cd from Sn and Mo, present respectively, at 11.1±0.9 mg/kg and 70.7±4.5 mg/kg in the tablet matrix. This allowed for measurement of (111)Cd/(113)Cd and (111)Cd/(114)Cd isotope ratios using both quadrupole collision cell technology inductively coupled plasma mass spectrometry (Q-CCT-ICP-MS) and sector field (SF)-ICP-MS equipped with a desolvating nebulizer system to mitigate the MoO(+) and MoOH(+) molecular ion interferences that typically affect the envelope of Cd isotopes. PMID:24148367

Christopher, Steven J; Thompson, Robert Q



Analysis of ochratoxin A in grapes, musts and wines by LC-MS/MS: first comparison of stable isotope dilution assay and diastereomeric dilution assay methods.  


Ochratoxin A (OTA) exhibits potent nephrotoxic, carcinogenic and teratogenic effects and its maximum level in wines has been set to 2 ?g L(-1) by regulation. Consequently, the analytical procedures for OTA determination in wines have to be both very sensitive and reliable. In this paper, we compared two quantification methods: the stable isotope dilution assay (SIDA) and the diastereomeric dilution assay (DIDA). For this purpose, non-natural analogues of OTA were synthesized: the labeled OTA (OTA-d4) as a diastereomeric mixture for the SIDA and one non-natural OTA's diastereomer (OTA-dia) for the DIDA. To quantify OTA in red grapes, musts or wines, the sample preparation was optimized using immunoaffinity column extraction and the analysis was performed by LC-MS/MS in Multiple Reaction Monitoring mode. A validation procedure in agreement with the International Organization of Vine and Wine recommendations was conducted. It appeared that SIDA quantification exhibited excellent sensitivity (LOD<1 ng L(-1)), accuracy (recovery=98%), repeatability (RSD<3%) and intermediate reproducibility (RSD<4%) compared to quantification by DIDA. Indeed, DIDA method did not provide satisfactory results demonstrating that immunoaffinity extraction is exclusively selective for the natural OTA and not for its diastereomer, which therefore cannot be considered as a good internal standard for this particular method. PMID:24626401

Roland, Aurélie; Bros, Pauline; Bouisseau, Anaïs; Cavelier, Florine; Schneider, Rémi



Trace determination of uranium, thorium, calcium, and other heavy metals in high-purity refractory metal silicides, niobium, and silicon dioxide with isotope dilution mass spectrometry  

SciTech Connect

A method for the determination of trace impurities (U, Th, Ca, Fe, Cr, Ni, Cu, and Cd) in silicides of refractory metals, in niobium, and in silicon dioxide with isotope dilution mass spectrometry (IDMS) has been developed. This method enables uranium and thorium analyses down to the lowest picogram per gram level with high precision and accuracy, which is especially important for the characterization of microelectronic devices. The other elements can be determined down to the low nanogram per gram level or - depending on the blank values - in some cases less. Selective chromatographic, extractive, and electrolytic procedures for the trace-matrix-separation were combined with positive thermal ionization mass spectrometry. Different samples of high-purity materials (metal and silicide powders, compact silicide, and silicon dioxide powder) for advanced technologies were analyzed.

Herzner, P.; Heumann, K.G. (Universitaet Regensburg (Germany))




SciTech Connect

DOE has initiated numerous activities to focus on identifying material management strategies to disposition various excess fissile materials. In particular the INEEL has stored 1,700 Kg of offspec HEU at INTEC in CPP-651 vault facility. Currently, the proposed strategies for dispositioning are (a) aqueous dissolution and down blending to LEU via facilities at SRS followed by shipment of the liquid LEU to NFS for fabrication into LWR fuel for the TVA reactors and (b) dilution of the HEU to 0.9% for discard as a waste stream that would no longer have a criticality or proliferation risk without being processed through some type of enrichment system. Dispositioning this inventory as a waste stream via aqueous processing at SRS has been determined to be too costly. Thus, dry blending is the only proposed disposal process for the uranium oxide materials in the CPP-651 vault. Isotopic dilution of HEU to typically less than 20% by dry blending is the key to solving the dispositioning issue (i.e., proliferation) posed by HEU stored at INEEL. RM-2 mill is a technology developed and successfully tested for producing ultra-fine particles by dry grinding. Grinding action in RM-2 mill produces a two million-fold increase in the number of particles being blended in a centrifugal field. In a previous study, the concept of achieving complete and adequate blending and mixing (i.e., no methods were identified to easily separate and concentrate one titanium compound from the other) in remarkably short processing times was successfully tested with surrogate materials (titanium dioxide and titanium mono-oxide) with different particle sizes, hardness and densities. In the current project, the RM-2 milling technology was thoroughly tested with mixtures of natural uranium oxide (NU) and depleted uranium oxide (DU) stock to prove its performance. The effects of mill operating and design variables on the blending of NU/DU oxides were evaluated. First, NU and DU both made of the same oxide, UO{sub 3}, was used in the testing. Next, NU made up of UO{sub 3} and DU made up of UO{sub 2} was used in the test work. In every test, the blend achieved was characterized by spatial sampling of the ground product and analyzing for {sup 235}U concentration. The test work proved that these uranium oxide materials can be blended successfully. The spatial concentration was found to be uniform. Next, sintered thorium oxide pellets were used as surrogate for light water breeder reactor pellets (LWBR). To simulate LWBR pellet dispositioning, the thorium oxide pellets were first ground to a powder form and then the powder was blended with NU. In these tests also the concentration of {sup 235}U and {sup 232}Th in blended products fell within established limits proving the success of RM-2 milling technology. RM-2 milling technology is applicable to any dry radioactive waste, especially brittle solids that can be ground up and mixed with the non-radioactive stock.

Raj K. Rajamani; Sanjeeva Latchireddi; Vikas Devrani; Harappan Sethi; Roger Henry; Nate Chipman



Thermal conductivity of isotopically enriched 71GaAs crystal  

NASA Astrophysics Data System (ADS)

A gallium arsenide bulk crystal highly enriched with gallium isotope 71Ga to 99.40 at% has been grown using the seedless horizontal Bridgman method. The crystal has a total impurity concentration of about 2 × 1017 atoms cm-3 and a high electrical resistivity rho(300 K) ~ 103-108 Omega cm. Thermal conductivity measurements have been made from 90 K to 300 K of the enriched 71GaAs sample and three different natGaAs samples with a natural isotope composition of gallium. The 71GaAs has a higher value of thermal conductivity due to reduced isotope scattering of phonons: the observed isotope effect amounts to 5% at room temperature, increasing to 13% with a temperature decrease down to 100 K.

Inyushkin, A. V.; Taldenkov, A. N.; Yakubovsky, A. Yu; Markov, A. V.; Moreno-Garsia, L.; Sharonov, B. N.



Determination of picomolar iron in seawater by double Mg(OH) 2 precipitation isotope dilution high-resolution ICPMS  

Microsoft Academic Search

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)2 co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 ?l 4% nitric acid (HNO3) solution followed by HR-ICPMS measurement. The high pre-concentration ratio (?500:1) achieved by the

Jingfeng Wu



Species-specific isotope dilution with permeation tubes for determination of gaseous mercury species.  


Instrumentation and methodology for determination of the gaseous mercury species Hg0, (CH3)2Hg, and CH3Hg+ has been developed. The method is based on continuous addition of gaseous isotopically enriched Hg species (tracers) at the point of sample acquisition, in combination with reduced pressure sampling on Carbotrap adsorbent tubes. Permeation tubes are used for generation of the tracers. Collected species are thermally desorbed and purged through an aqueous sodium tetraethylborate solution for derivatization of CH3Hg+. The purged gas is dried with a Nafion membrane, and the Hg species are subsequently collected on a smaller Tenax TA adsorbent tube. Species are then thermally desorbed from the Tenax TA and introduced into a gas chromatograph connected to an inductively coupled plasma mass spectrometer for separation and detection. To be able to add tracers during field sampling, we developed a portable device, supplying the permeation tubes with a thermostated and mass flow-controlled air stream of 5.0 +/- 0.1 degrees C and 50.0 mL min(-1), respectively. Typical permeation rates obtained during a period of more than 6 weeks were 12.93 +/- 0.56, 0.42 +/- 0.01, and 0.49 +/- 0.03 (mean +/- standard deviation) pg of Hg min(-1) for a set of 199Hg0, (CH3)2 198Hg, and CH3 200Hg+ tubes, respectively. Methodological detection limits (3sigma) were determined to 700 pg of Hg m(-3) for Hg0 and 50 pg of Hg m(-3) for (CH3)2Hg and CH3Hg+. The collection efficiencies for sampled volumes of 400 L of synthetic air on the Carbotrap tubes used in this study were 13 +/- 2, 102 +/- 2, and 99 +/- 4% for Hg0, (CH3)2Hg, and CH3Hg+, respectively. Desorption efficiencies for the above species and tubes were 98 +/- 2, 98 +/- 1, and 90 +/- 4%, respectively. Fractions (20-40%) of the added (CH3)2 198Hg and CH3 200Hg+ tracers were found to be transformed during the analytical processing of collected air samples. Determined concentrations in the research laboratory air, corrected for species transformations, were 3-53, 8-11, and 1-2 ng of Hg m(-3) for Hg0, (CH3)2Hg, and CH3Hg+, respectively. Concentrations in the ambient air were determined to be 2.1-2.6 ng m(-3) for Hg0 and below the detection limit for (CH3)2Hg and CH3Hg+. PMID:14710842

Larsson, T; Frech, W



Experimental Study of Isotope Scaling of Ion Thermal Transport  

NASA Astrophysics Data System (ADS)

The wide divergence between most theoretical predictions of isotopic mass scaling of transport and tokamak experimental results motivated a basic physics experiment in the Columbia Linear Machine [

R. Scarmozzino, A. K. Sen, and G. A. Navratil, Phys. Rev. Lett. 57, 1729 (1986)
]. The experiments on ion thermal conductivity due to ion temperature gradient-driven slab modes are performed using two different gases: hydrogen and deuterium. The results indicate inverse dependence of ion thermal conductivity on the isotope mass close to K?˜A-0.5i. This is similar to the tokamak results, but in stark contradiction to most present theoretical models.

Sokolov, V.; Sen, A. K.



Thermal effects on rare earth element and strontium isotope chemistry in single conodont elements  

Microsoft Academic Search

A low-blank, high sensitivity isotope dilution, ICP-MS analytical technique has been used to obtain REE abundance data from single conodont elements weighing as little as 5 ?g. Sr isotopes can also be measured from the column eluants enabling Sr isotope ratios and REE abundance to be determined from the same dissolution. Results are comparable to published analyses comprising tens to

H. A. Armstrong; D. G. Pearson; M. Griselin



Quantification of cyclic dipeptides from cultures of Lactobacillus brevis R2? by HRGC/MS using stable isotope dilution assay.  


Lactic acid bacteria (LAB) play an important role as natural preservatives in fermented food and beverage systems, reducing the application of chemical additives. Thus, investigating their antifungal compounds, such as cyclic dipeptides, has gained prominence. Previous research has primarily focussed on isolation of these compounds. However, their precise quantification will provide further information regarding their antifungal performance in a complex system. To address this, deuterated labelled standards of the cyclic dipeptides cyclo(Leu-Pro), cyclo(Pro-Pro), cyclo(Met-Pro) and cyclo(Phe-Pro) were synthesized, and stable isotope dilution assays were developed, enabling an accurate quantification of cyclo(Leu-Pro), cyclo(Pro-Pro), cyclo(Met-Pro) and cyclo(Phe-Pro) in MRS-broth and wort. Quantitative results showed that, in the Lactobacillus brevis R2? fermented MRS-broth, the concentrations of cyclo(Leu-Pro), cyclo(Pro-Pro) and cyclo(Phe-Pro) were significantly higher (P?isotope dilution assays in LAB cultures both in vitro and in a food system. PMID:24477717

Axel, Claudia; Zannini, Emanuele; Arendt, Elke K; Waters, Deborah M; Czerny, Michael



Trace analysis of acidic pharmaceutical residues in waters with isotope dilution gas chromatography-mass spectrometry via methylation derivatization.  


Acidic pharmaceutical residues are pollutants of emerging concern and are generally monitored by HPLC-MS/MS. However, due to the limited separation efficiency of HPLC column and lack of suitable mass transition for confirmation analysis, some interference may not be separated completely and differentiated from ibuprofen, which may cause the results with interference, especially in sample with complex matrix. The objective of this study is to develop a sensitive and reliable method for the determination of acidic pharmaceutical residues in water samples by GC-MS with better resolution by using methylation derivatization and isotope dilution techniques. TMSDM, a mild reagent, was used as the derivatization reagent coupling with the isotope dilution technique, for the first time, to improve the precision and accuracy of the analytical method to determine the pharmaceutical residues in water. The MDLs for the five acidic organic compounds: ibuprofen, gemfibrozil, naproxen, ketoprofen and diclofenac were from 0.7 to 1.1 ng/L, with recoveries ranging from 93 to 110%. Alternative to the HPLC-MS/MS method, the developed GC-MS protocols provides an additional option for the analysis of acidic pharmaceutical residues in water, with better separation efficiency in reducing interferences from complicated sample matrix, for determination of ibuprofen residues. PMID:21872014

Hu, Ruikang; Yang, Zhaoguang; Zhang, Lifeng



Quantification of immunoreactive viral influenza proteins by immunoaffinity capture and isotope-dilution liquid chromatography-tandem mass spectrometry.  


An immunocapture isotope dilution mass spectrometry (IC-IDMS) method was developed to quantify antibody-bound influenza hemagglutinins (HA) in trivalent influenza vaccines (TIV). Currently, regulatory potency requirements for TIV require HA quantification based on the single radial immunodiffusion (SRID) assay, which is time-consuming, laborious, and requires production of large quantities of reagents globally. In IC-IDMS, antiserum to the HA of interest captured viral proteins that were in the correct conformation to be recognized by the antibodies. The captured proteins were digested, and evolutionarily conserved tryptic peptides were quantified using isotope-dilution liquid chromatography-tandem mass spectrometry. IC-IDMS relies on antibody-antigen binding similar to SRID but incorporates the accuracy and precision of IDMS. Polyclonal antibodies (pAb-H3) prepared by injection of sheep with purified H3 HA captured 82.9% (55.26 fmol/?L) of the total H3 HA (66.69 fmol/?L) from the commercial TIV and 93.6% (57.23 fmol/?L) of the total H3 HA (61.14 fmol/?L) in purified virus. While other HA (H1, B), neuraminidase (N1, N2, NB), viral matrix proteins, and nucleoproteins were also captured by this antiserum, our results were not affected due to the specificity of the mass spectrometer. IC-IDMS is an accurate, precise, sensitive, and selective method to measure antibody-bound HA in purified virus and commercial vaccines. PMID:21591780

Pierce, Carrie L; Williams, Tracie L; Moura, Hercules; Pirkle, James L; Cox, Nancy J; Stevens, James; Donis, Ruben O; Barr, John R



Quantitation of odor-active compounds in rye flour and rye sourdough using stable isotope dilution assays.  


Application of the aroma extract dilution analysis on a flavor distillate prepared from freshly ground rye flour (type 1150) revealed 1-octen-3-one (mushroom-like), methional (cooked potato), and (E)-2-nonenal (fatty, green) with the highest flavor dilution (FD) factors among the 26 odor-active volatiles identified. Quantitative measurements performed by stable isotope dilution assays and a comparison to the odor thresholds of selected odorants in starch suggested methional, (E)-2-nonenal, and hexanal as contributors to the flour aroma, because their concentrations exceeded their odor thresholds by factors >100. Application of the same approach on a rye sourdough prepared from the same batch of flour revealed 3-methylbutanal, vanillin, 3-methylbutanoic acid, methional, (E,E)-2,4-decadienal, 2,3-butanedione, and acetic acid as important odorants; their concentrations exceeded their odor thresholds in water and starch by factors >100. A comparison of the concentrations of 20 odorants in rye flour and the sourdough made therefrom indicated that flour, besides the fermentation process, is an important source of aroma compounds in dough. However, 3-methylbutanol, acetic acid, and 2,3-butanedione were much increased during fermentation, whereas (E,E)-2,4-decadienal and 2-methylbutanal were decreased. Similar results were obtained for five different flours and sourdoughs, respectively, although the amounts of some odorants in the flour and the sourdough differed significantly within batches. PMID:12207478

Kirchhoff, Eva; Schieberle, Peter



Chemical and isotopic characteristics of thermal fluids in the Long Valley caldera lateral flow system, California  

SciTech Connect

Chemical and isotopic data of thermal waters in Long Valley caldera have been used to identify both the origins and characteristics of the fluids and to evaluate mixing and boiling processes occurring within the lateral flow system of the caldera. Recharge to the Long Valley geothermal system occurs in the western part of the caldera with the water being heated at depth and flowing laterally eastward in the subsurface. The lateral flow system was recently intersected by the Shady Rest Continental Scientific Drilling Program (CSDP) corehole at 335 m (1100 ft) with fluids in this 202/sup 0/C zone being more concentrated than non-boiled fluids to the east. As the Na-K-HCO/sub 3/-Cl thermal fluids flow eastward, they are increasingly mixed with isotopically depleted, dilute groundwaters similar to cold waters east of Lake Crowley. Near surface boiling of Casa Diablo well fluids at 100/sup 0/C forms waters with the compositions of Colton and Casa Diablo hot springs. Waters to the east of the Casa Diablo area are mixtures of meteoric water and boiled thermal fluids with a composition close to that of Colton Hot Spring. There is no correlation between /sup 3/H and /sup 36/Cl in thermal fluids or between these components and conservative species, and it appears that cold fluids involved in mixing must be relatively old waters, low in both meteoric /sup 3/H and /sup 36/Cl.

Shevenell, L.; Goff, F.; Grigsby, C.O.; Janik, C.J.; Trujillo, P.E. Jr.; Counce, D.



Thermal Neutron Capture Cross Sections Of The Palladium Isotopes  

Microsoft Academic Search

We have measured precise thermal neutron capture gamma-ray cross sections cry for all stable Palladium isotopes with the guided thermal neutron beam from the Budapest Reactor. The data were compared with other data from the literature and have been evaluated into the Evaluated Gamma-ray Activation File (EGAF). Total radiative neutron capture cross-sections sigmagamma can be deduced from the sum of

R. B. Firestone; M. Krtiáka; D. P. McNabb; B. Sleaford; U. Agvaanluvsan; T. Belgya; Zs. Révay



Thermal Neutron Capture Cross Sections of The Palladium Isotopes  

Microsoft Academic Search

We have measured precise thermal neutron capture γ-ray cross sections Ï{sub γ} for all stable Palladium isotopes with the guided thermal neutron beam from the Budapest Reactor. The data were compared with other data from the literature and have been evaluated into the Evaluated Gamma-ray Activation File (EGAF)[1]. Total radiative neutron capture cross-sections Ïâ can be deduced from the sum

R B Firestone; M Krticka; D P McNabb; B Sleaford; U Agvaanluvsan; T Belgya; Z Revay



Direct ?-flow injection isotope dilution ICP-MS for the determination of heavy metals in oil samples.  


The determination of trace elements in oil samples and their products is of high interest as their presence significantly affects refinery processes and the environment by possible impact of their combustion products. In this context, inductively coupled plasma mass spectrometry (ICP-MS) plays an important role due to its outstanding analytical properties in the quantification of trace elements. In this work, we present the accurate and precise determination of selected heavy metals in oil samples by making use of the combination of ?-flow direct injection and isotope dilution ICP-MS (ICP-IDMS). Spike solutions of (62)Ni, (97)Mo, (117)Sn and (206)Pb were prepared in an organic solvent, mixed directly with the diluted oil samples and tested to be fit for purpose for the intended ID approach. The analysis of real samples revealed strong matrix effects affecting the ICP-MS sensitivity, but not the isotope ratio measurements, so that accurate results are obtained by ICP-IDMS. Typical relative standard deviations were about 15% for peak area and peak height measurements, whereas the isotope ratios were not significantly affected (RSD < 2%). The developed method was validated by the analysis of a metallo-organic multi-element standard (SCP-21, typically applied as a calibration standard) and the standard reference material SRM1084a (wear metals in lubricating oil). The obtained results were in excellent agreement with the certified values (recoveries between 98% and 102%), so the proposed methodology of combining ?-flow direct injection and ICP-IDMS can be regarded as a new tool for the matrix-independent, multi-element and reliable determination of trace elements in oil and related organic liquids. PMID:21983977

Bettmer, Jörg; Heilmann, Jens; Kutscher, Daniel J; Sanz-Medel, Alfredo; Heumann, Klaus G



The longevity of the South Pacific isotopic and thermal anomaly  

USGS Publications Warehouse

The South Pacific is anomalous in terms of the Sr, Nd, and Pb isotope ratios of its hot spot basalts, a thermally enhanced lithosphere, and possibly a hotter mantle. We have studied the Sr, Nd, and Pb isotope characteristics of 12 Cretaceous seamounts in the Magellans, Marshall and Wake seamount groups (western Pacific Ocean) that originated in this South Pacific Isotopic and Thermal Anomaly (SOPITA). The range and values of isotope ratios of the Cretaceous seamount data are similar to those of the island chains of Samoa, Tahiti, Marquesas and Cook/Austral in the SOPITA. These define two major mantle components suggesting that isotopically extreme lavas have been produced at SOPITA for at least 120 Ma. Shallow bathymetry, and weakened lithosphere beneath some of the seamounts studied suggests that at least some of the thermal effects prevailed during the Cretaceous as well. These data, in the context of published data, suggest: 1. (1)|SOPITA is a long-lived feature, and enhanced heat transfer into the lithosphere and isotopically anomalous mantle appear to be an intrinsic characteristic of the anomaly. 2. (2)|The less pronounced depth anomaly during northwesterly plate motion suggests that some of the expressions of SOPITA may be controlled by the direction of plate motion. Motion parallel to the alignment of SOPITA hot spots focusses the heat (and chemical input into the lithosphere) on a smaller cross section than oblique motion. 3. (3)|The lithosphere in the eastern and central SOPITA appears to have lost its original depleted mantle characteristics, probably due to enhanced plume/lithosphere interaction, and it is dominated by isotopic compositions derived from plume materials. 4. (4)|We speculate (following D.L. Anderson) that the origin of the SOPITA, and possibly the DUPAL anomaly is largely due to focussed subduction through long periods of the geological history of the earth, creating a heterogeneous distribution of recycled components in the lower mantle. ?? 1991.

Staudigel, H.; Park, K. -H.; Pringle, M.; Rubenstone, J. L.; Smith, W. H. F.; Zindler, A.



Investigation of at-vent dynamics and dilution using thermal infrared radiometers at Masaya volcano, Nicaragua  

NASA Astrophysics Data System (ADS)

In order to develop a detailed understanding of the dynamics of gas puffing (gas release as a series of distinct pulses) and more sustained degassing (steady plumes of gas) during persistent volcanic degassing, measurements of gas mass flux are required in the vicinity of the volcanic vent. Masaya volcano (Nicaragua), a persistently degassing system, is an ideal location for measuring the dynamics of releases of volcanic gas in the first few seconds of their propagation. We carried out two field experiments during February 2002 and March 2003, during which thermal infrared thermometers were targeted into the degassing vent at Masaya to record thermal variations related to variations in the at-vent gas emission over short (on the order of seconds) time scales. The thermometers recorded an oscillating signal as gas puffs passed through the field of view, detailing variations in the degassing process developing over time scales of seconds. These data were processed to extract puff frequencies, amplitudes, durations, emission velocities and volumes. These data showed that, over time periods of hours, the total gas flux was stable with little variation in the puffing frequency. However, between the 2002 and 2003 data set we noted an increase in mean plume temperature, puffing frequency, puff emission velocity and puff volume, as well as a decrease in mean puff duration. These changes were consistent with a thermal data-derived increase in emitted gas flux from 4.2 × 10 7 m 3 d - 1 to 6.4 × 10 7 m 3 d - 1 between the two campaigns. Turbulent gas puffs entrain surrounding air, and quantifying the magnitude of air entrainment, or dilution, represents a major challenge for the measurement of total volcanic gas emissions. Our observations of small gas puffs suggest that they behave as turbulent buoyant thermals, and we use equations for mass, momentum and buoyancy, coupled with the standard entrainment assumption for turbulent buoyant flows, to estimate the gas puff dilution. The theoretically calculated dilution of 0.09 and 0.24 between emission and detection yields total SO 2 mass fluxes of 209 t d - 1 and 864 t d - 1 for 2002 and 2003, respectively. This compares well with UV-spectrometer SO 2 fluxes of 470 and 680 t d - 1 for February 2002 and March 2003, respectively.

Branan, Yvonne K.; Harris, Andrew; Watson, I. Matthew; Phillips, J. C.; Horton, Keith; Williams-Jones, Glyn; Garbeil, Harold



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


Trace levels (pg kg(-1)) of 241Am in sediments were determined by isotope dilution high resolution inductively coupled plasma mass spectrometry (ID HR ICP-MS) using a microconcentric nebulizer. 241Am was isolated from major elements like Ca and Fe by different selective precipitations. In further steps. Am was first separated from other transuranic elements and purified by anion exchange and extraction chromatography prior to the mass spectrometric measurements. The ID HR ICP-MS results are compared with isotope dilution alpha spectrometry. PMID:11393755

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



Nd isotopic composition of water masses and dilution of the Mediterranean outflow along the southwest European margin  

NASA Astrophysics Data System (ADS)

Nd isotopic compositions (?Nd) of seawater profiles and deep-sea corals collected off the coast of Iberia and from the Bay of Biscay were measured (1) to constrain the Nd isotopic composition of water masses along the southwest European margin, (2) to track the Mediterranean Outflow Water (MOW) during its northward propagation, and (3) to establish hydrological changes during the last 1500 years. The Eastern North Atlantic Central Water (ENACW) is characterized by Nd isotopic composition of around -12.0. Mediterranean Sea Water (MSW) is collected from 800 and 1200 m depth and is characterized by ?Nd values ranging from -10.9, off the coast of Iberia, to -11.6 in the Bay of Biscay. These ?Nd results suggest a strong dilution of the pure MOW at the Strait of Gibraltar (?Nd -9.4) of approximately 40% and 30% along its northward circulation pathway essentially with a contribution from ENACW. At around 2000 m depth, ?Nd water profiles display the occurrence of a nonradiogenic water mass (?Nd -13), originating from the Labrador Sea (Labrador Sea Water). Fossil deep-sea corals, dated between 84 and 1500 years, display Nd isotopic compositions that vary moderately from present-day seawater values, suggesting a weaker influence of MOW in the formation of MSW during the Dark Ages and the Little Ice Age. These recent cold events seem to be associated with a reduction in the northward penetration of MSW, which may result from a greater eastward extension of the middepth subpolar gyre and/or a reduction of MSW formation, likely tied to a variation in deep Mediterranean water production.

Copard, K.; Colin, C.; Frank, N.; Jeandel, C.; Montero-Serrano, J.-C.; Reverdin, G.; Ferron, B.



Contents of selected B vitamins in NIST SRM 3280 multivitamin/multielement tablets by liquid chromatography isotope dilution mass spectrometry.  


There is increased interest in accurately assessing the total dietary intake of vitamins from all sources, including foods and dietary supplements. Consequently, a Dietary Supplement Ingredient Database (DSID), based upon analytical values, is being established by USDA with support of the Office of Dietary Supplements (ODS), NIH. The DSID necessitated the development of a new SRM, 3280--Multivitamin/Multimineral Tablets, by the National Institute of Standards and Technology (NIST), with support from the ODS. As a continuation of a long-term project to develop and validate new methods of determining water-soluble B vitamins in foods and dietary supplements, and as part of a collaborative effort with NIST to characterize SRM 3280, values for the vitamin contents of SRM 3280 have been generated by a liquid chromatographic isotope dilution mass spectrometric (LC/IDMS) method. Isotope-labeled ((13)C and/or (2)H) B vitamins (B1-thiamine, B6-pyridoxine, B3-nicotinamide, and B5-pantothenic acid) were obtained from commercial sources, with the support of the ODS/NIH. Our LC/IDMS method uses a C18 reversed phase column, an Agilent 1100 HPLC system, and a Quattro Micro triple-quad mass spectrometer (MS). B vitamin determination was achieved using a gradient LC profile combined with MS/MS detection in multiple reaction monitoring mode. Stock solutions of the isotope-labeled vitamins were calibrated against USP standard solutions. The SRM tablets, with added amounts of the four isotope-labeled B vitamins, were extracted and the vitamins simultaneously determined in a single LC run, in contrast with the single-component determinations performed via IDMS. Unknown vitamin concentrations were calculated by comparing the ratios of the integrated LC peaks at the different masses of the unlabeled and labeled vitamins. PMID:17646973

Chen, Pei; Ozcan, Mustafa; Wolf, Wayne R



Liquid chromatography, chemical oxidation, and online carbon isotope dilution mass spectrometry as a universal quantification system for nonvolatile organic compounds.  


A procedure for the universal detection and quantification of polar organic compounds separated by liquid chromatography (LC) based on postcolumn carbon isotope dilution mass spectrometry (IDMS) was developed. The eluent from the LC column is mixed online with a continuous flow of (13)C-enriched sodium bicarbonate, and the sodium persulfate oxidation reaction in acidic media is employed to achieve isotope equilibration. All carbon-containing compounds eluting from the column are oxidized to (12)CO(2) and (13)CO(2), respectively, and the carbon dioxide is separated from the aqueous phase using a gas-permeable membrane. The gaseous carbon dioxide is then carried to the mass spectrometer for isotope ratio measurements. Different water-soluble organic compounds were evaluated using a flow injection configuration to assess the efficiency of the oxidation process. Most water-soluble organic compounds tested showed quantitative oxidation. However, chemical structures involving conjugated C?N double bounds and guanidinium-like structures were found to be resistant to the oxidation and were further studied. For this purpose, (13)C(1)-labeled creatine (with the isotopic label in the guanidinium group) was employed as model compound. Specific conditions for the quantitative oxidation of these compounds required lower flow rates and the addition of metallic catalysts. This novel approach was tested as a universal detection and quantification system for LC. A simple standard mixture of four amino acids was separated under 100% aqueous conditions and quantified without the need for specific standards with good accuracy and precision using potassium hydrogen phthalate as internal standard. The main field of application of the developed method is for the purity assessment of organic standards with direct traceability to the International System of Units (SI). PMID:23252800

Díaz, Sergio Cueto; Encinar, Jorge Ruiz; Sanz-Medel, Alfredo; Alonso, J Ignacio García



Measurement of dialkyl phosphate metabolites of organophosphorus pesticides in human urine using lyophilization with gas chromatography-tandem mass spectrometry and isotope dilution quantification  

Microsoft Academic Search

Urinary dialkylphosphate (DAP) metabolites have been used to estimate human exposure to organophosphorus pesticides. We developed a method for quantifying the six DAP urinary metabolites of at least 28 organophosphorus pesticides using lyophilization and chemical derivatization followed by analysis using isotope-dilution gas chromatography–tandem mass spectrometry (GC–MS\\/MS). Urine samples were spiked with stable isotope analogues of the DAPs and the water

Roberto Bravo; Lisa M Caltabiano; Gayanga Weerasekera; Ralph D Whitehead; Carolina Fernandez; Larry L Needham; Asa Bradman; Dana B Barr



Determination of serum uric acid using high-performance liquid chromatography (HPLC)\\/isotope dilution mass spectrometry (IDMS) as a candidate reference method  

Microsoft Academic Search

Uric acid is an important diagnostic marker of catabolism of the purine nucleosides, and accurate measurements of serum uric acid are necessary for proper diagnosis of gout or renal disease appearance. A candidate reference method involving isotope dilution coupled with liquid chromatography\\/mass spectrometry (LC\\/MS) has been described. An isotopically labeled internal standard, [1,3-15N2] uric acid, was added to serum, followed

Xinhua Dai; Xiang Fang; Chunmei Zhang; Ruifeng Xu; Bei Xu



Determination of Methylmercury, Ethylmercury, and Inorganic Mercury in Mouse Tissues, Following Administration of Thimerosal, by Species-Specific Isotope Dilution GC?Inductively Coupled Plasma-MS  

Microsoft Academic Search

Isotopically enriched HgO standards were used to syn- thesize CH3200Hg+ and C2H5199Hg+ using Grignard re- agents. These species were employed for isotope dilution GC-ICPMS to study uptake and biotransformation of ethylmercury in mice treated with thimerosal, (sodium ethylmercurithiosalicylate) 10 mg L-1 in drinking water ad libitum for 1, 2.5, 6, or 14 days. Prior to analysis, samples were spiked with

Johanna Qvarnstro; Lars Lambertsson; Said Havarinasab; Per Hultman; Wolfgang Frech



Method for Processing alpha Spectra Adapted for Measuring Plutonium, Americium and Curium by Isotopic Dilution.  

National Technical Information Service (NTIS)

With this method, results to within 1% can be achieved rapidly and without calibration for ratios such as lesser energy peaks/higher energy peaks within the range 0.5 and 1000. It can also be used, in certain conditions, for measuring isotopic ratios such...

F. Amoudry M. Silly



Simultaneous determination of alachlor, metolachlor, atrazine, and simazine in water and soil by isotope dilution gas chromatography/mass spectrometry  

SciTech Connect

A multiresidue method was developed for the simultaneous determination of low parts per billion (ppb) concentrations of the herbicides alachlor, metolachlor, atrazine, and simazine in water and soil using isotope dilution gas chromatography/mass spectrometry (GC/MS). Known amounts of /sup 15/N,/sup 13/C-alachlor and /sup 2/H/sub 5/-atrazine were added to each sample as internal standards. The samples were then prepared by a solid phase extraction with no further cleanup. A high resolution GC/low resolution MS system with data acquisition in selected ion monitoring mode was used to quantitate herbicides in the extract. The limit of detection was 0.05 ppb for water and 0.5 ppb for soil. Accuracy greater than 80% and precision better than 4% was demonstrated with spiked samples.

Huang, L.Q.



An isotope-dilution, GC-MS assay for formate and its application to human and animal metabolism.  


Formate, a crucial component of one-carbon metabolism, is increasingly recognized as an important intermediate in production and transport of one-carbon units. Unlike tetrahydrofolate-linked intermediates, it is not restricted to the intracellular milieu so that circulating levels of formate can provide insight into cellular events. We report a novel isotope-dilution, GC-MS assay employing derivatization by 2,3,4,5,6-pentafluorobenzyl bromide for the determination of formate in biological samples. This assay is robust and sensitive; it may be applied to the measurement of formate in serum, plasma and urine. We demonstrate how this method may be applied by providing the first characterization of formate levels in a human population; formate levels were higher in males than in females. We also show how this procedure may be applied for the measurement of in vivo kinetics of endogenous formate production in experimental animals. PMID:24748098

Lamarre, Simon G; MacMillan, Luke; Morrow, Gregory P; Randell, Edward; Pongnopparat, Theerawat; Brosnan, Margaret E; Brosnan, John T



Short communication: milk output in llamas (Lama glama) in relation to energy intake and water turnover measured by an isotope dilution technique.  


Despite the fact that llamas have become increasingly popular as companion and farm animals in both Europe and North America, scientific knowledge on their nutrient requirements is scarce. Compared with other livestock species, relatively little is known especially about the nutrient and energy requirements for lactating llamas. Therefore, we aimed to measure milk output in llama dams using an isotope dilution technique and relate it to energy intakes at different stages of lactation. We also validated the dilution technique by measuring total water turnover (TWT) directly and comparing it with values estimated by the isotope dilution technique. Our study involved 5 lactating llama dams and their suckling young. Milk output and TWT were measured at 4 stages of lactation (wk 3, 10, 18, and 26 postpartum). The method involved the application of the stable hydrogen isotope deuterium ((2)H) to the lactating dam. Drinking water intake and TWT decreased significantly with lactation stage, whether estimated by the isotope dilution technique or calculated from drinking water and water ingested from feeds. In contrast, lactation stage had no effect on dry matter intake, metabolizable energy (ME) intake, or the milk water fraction (i.e., the ratio between milk water excreted and TWT). The ratios between TWT measured and TWT estimated (by isotope dilution) did not differ with lactation stage and were close to 100% in all measurement weeks, indicating that the D(2)O dilution technique estimated TWT with high accuracy and only small variations. Calculating the required ME intakes for lactation from milk output data and gross energy content of milk revealed that, with increasing lactation stage, ME requirements per day for lactation decreased but remained constant per kilogram of milk output. Total measured ME intakes at different stages of lactation were similar to calculated ME intakes from published recommendation models for llamas. PMID:23332845

Riek, A; Klinkert, A; Gerken, M; Hummel, J; Moors, E; Südekum, K-H



Effect of dilute gelatine on the ultrasonic thermally assisted synthesis of nano hydroxyapatite.  


A series of nano hydroxyapatite-gelatine composites with different dilute solutions of gelatine concentrations were synthesized by a thermally assisted low-power ultrasonic irradiation method. The gelatine hydroxyapatite, (Gel-HAP) nanoparticles were prepared using Ca(NO(3))(2) and KH(2)PO(4) in the presence of gelatine in an aqueous solution. The synthesised products were heat treated between 100 and 400°C. The effect of the addition of gelatine on the nucleation and growth of synthesised nano HAP was investigated. Characterisation was performed using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectroscopy (FT-IR). The characterisation results indicate that gelatine has been appended to the nano HAP forming regular spherical shaped crystals of nano sized Gel-HAP. PMID:21168355

Brundavanam, Ravi Krishna; Jiang, Zhong-Tao; Chapman, Peter; Le, Xuan-Thi; Mondinos, Nicholas; Fawcett, Derek; Poinern, Gérrard Eddy Jai



Mass Independent Fractionation of Cadmium Isotopes During Thermal Ionization  

NASA Astrophysics Data System (ADS)

We have previously reported that Cd isotopes exhibit anomalous, non-mass dependent fractionation of odd versus even isotopes when measured by TIMS using silica gel-phosphoric acid activator. The deviation from mass dependent fractionation (MDF) on the odd masses 111 and 113 varies by fractions of a per-cent between runs. The effects cannot be explained by isobaric interferences, but seem, instead, to reflect mass independent fractionation (MIF) of Cd isotopes, much like that recently documented for Hg isotopes in natural systems (Bergquist and Blum, 2007). The absence of comparable Cd isotope anomalies in the ICP torch, and during extreme in-vacuo volatilization of Cd metal (Wombacher et al., 2004) conclusively implicates the silica gel activator in the process. So far, MIF has been documented for Cd, Zn and Pb isotopes when measured using the silica gel technique (Thirlwall, 2000; Schmitt et al., 2006; Manhes and Göpel, 2007). These MIF effects on Cd isotopes might perhaps be related to the non-mass dependence of nuclear volume with mass number, as described by Bigeleisen (1996) - also known as the "nuclear field shift". The MIF caused by the nuclear field shift results is a departure from MDF broadly characterized by a odd-even staggering with mass number. These effects have been quantified by Schauble (2007) who showed that the magnitude of the non-mass dependence for Hg and Tl isotopes lies in the ppm range for some simple reactions. Such MIF effects would appear, overall, far too small to account for our data, which require MIF offsets on the odd masses 111 and 113 approaching a per-cent. Moreover, an in-depth examination along the lines of Fujii et al. (2006) predicts tell-tale offsets for the even-even isotope pairs 114Cd/112Cd and 116Cd/112Cd as well, based upon the theory and the respective nuclear radii, but such accompanying offsets are unequivocally absent in our data. The odd-even isotope effects seen in our runs using silica gel activator are better explained by appealing to the nuclear spin (and magnetic moment) of odd nuclei alone. The "magnetic isotope effect" is a consequence of hyperfine coupling, in which an electron interacts with a nucleus of non-zero magnetic moment - i.e. one that has an odd number of nucleons (Turro, 1983; Buchachenko, 1995, 2001). This is purely a kinetic phenomenon in which the life-time, and thus the outcome, of reaction transition states is altered by the hyperfine splitting present in atoms with odd nuclei. The mechanism by which silica gel activator enhances the thermal ionization of elements such as Cd, Pb and Zn has been outlined by Kessinger and Delmore (2002). The first step involves the in-situ reduction of Cd2+ ions to Cd metal in the molten silica gel-phosphoric acid glass. It is most likely in this step - whereby two electrons are added - that a suitably long-lived transition state exists, during which the magnetic isotope effect enhances (or inhibits) reduction of masses 111 and 113 to metal species compared to those of even isotopes of Cd. The resulting "odd" and "even" populations of Cd-metal in the molten silica gel then cannot be related simply in terms of MDF. Overall, the magnetic isotope effect provides the best explanation of the MIF effects observed for Pb, Cd and Zn during thermal ionization with silica gel activator, and, probably, why the measured fractionation is always biased towards light isotopes.

Abouchami, W.; Galer, S. J.; Feldmann, H.; Schmitt, A. D.



Daily cortisol production rate in man determined by stable isotope dilution\\/mass spectrometry  

Microsoft Academic Search

Growth retardation as well as the development of Cushingoid features in adrenally insufficient patients treated with the currently accepted replacement dose of cortisol (33-41 mumol\\/day.m2; 12-15 mg\\/ prompted us to reevaluate the cortisol production rate (FPR) in normal subjects and patients with Cushing's syndrome, using a recently developed thermospray liquid chromatography-mass spectrometry method. The stable isotope (9,12,12-2H3)cortisol was infused continuously

N. V. Esteban; T. Loughlin; A. L. Yergey; J. K. Zawadzki; J. D. Booth; J. C. Winterer; D. L. Loriaux



Determination of atmospheric carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry  

SciTech Connect

A gas chromatography/mass spectrometry (GB/MS) method for determining atmospheric carbonyl sulfide (OCS) with a precision better than 2% is reported. High precision and insensitivity to sample loss and changes in detector response were achieved by using isotopically labeled OCS as an internal standard. Tenax, Molecular Sieve 5A, Carbosieve B, and Carbosieve S were evaluated for collecting atmospheric OCS. Molecular Sieve 5A provided the best trapping and recovery efficiencies.

Lewin, E.E.; Taggart, R.L.; Lalevic, M.; Bandy, A.R.



Determination of volatile elements in biological materials by isotopic dilution ETV-ICP-MS after dissolution with tetramethylammonium hydroxide or acid digestion  

Microsoft Academic Search

Isotopic dilution for the determination of Ag, Cd, Hg, Pb and Tl in biological materials by ETV-ICP-MS is proposed. The sample was simply dissolved with tetramethylammonium hydroxide (TMAH) or acid digested in a microwave furnace, with an on line matrix separation. When the dissolution was employed, Ir was used as a chemical modifier for Hg and Pb and Pd was

Dirce Pozebon; Valderi L. Dressler; Adilson J. Curtius



Determination of atrazine, lindane, pentachlorophenol, and diazinon in water and soil by isotope dilution gas chromatography/mass spectrometry  

SciTech Connect

This paper describes an isotope dilution GC/MS technique for the analysis of low-parts-per-billion concentrations of atrazine, lindane, pentachlorophenol, and diazinon in water and soil. Known amounts of stable-labeled isotopes such as atrazine-d/sub 5/, lindane-d/sub 6/, pentachlorophenol-/sup 13/C/sub 6/, and diazinon-d/sub 10/ are spiked into each sample prior to extraction. Water samples are extracted with methylene chloride; soil samples are extracted with acetone/hexane. Analysis is performed by high-resolution GC/MS with the mass spectrometer operated in the selected ion monitoring mode. Accuracy greater than 86% and precision better than 8% were demonstrated by use of spiked samples. This technique has been used successfully in the analysis of over 300 water and 300 soil samples. Detection limits of 0.1-1.0 ppb were achieved for the test compounds by selected ion monitoring GC/MS. 8 references, 2 figures, 4 tables.

Lopez-Avila, V.; Hirata, P.; Kraska, S.; Flanagan, M.; Taylor, J.H. Jr.; Hern, S.C.



Analysis of N-nitrosamines in water by isotope dilution gas chromatography-electron ionisation tandem mass spectrometry.  


A method has been developed for the determination of eight N-nitrosamines in drinking water and treated municipal effluent. The method uses solid phase extraction (SPE), gas chromatography (GC) and analysis by tandem mass spectrometry (MS-MS) with electron ionization (EI). The target compounds are N-nitrosodimethylamine (NDMA), N-nitrosomethyethylamine (NMEA), N-nitrosodiethylamine NDEA), N-nitrosodipropylamine (NDPA), N-nitrosodi-n-butylamine (NDBuA), N-nitrosodiphenylamine (NDPhA), N-nitrosopyrrolidine (NPyr), N-nitrosopiperidine (NPip), N-nitrosomorpholine (NMorph). The use of direct isotope analogues for isotope dilution analysis of all analytes ensures accurate quantification, accounting for analytical variabilities that may occur during sample processing, extraction and instrumental analysis. Method detection levels (MDLs) were determined to describe analyte concentrations sufficient to provide a signal with 99% certainty of detection. The established MDLs for all analytes were 0.4-4 ng L(-1) in a variety of aqueous matrices. Sample matrices were observed to have only a minor impact on MDLs and the method validation confirmed satisfactory method stability over intra-day and inter-day analyses of tap water and tertiary treated effluent samples. PMID:22967534

McDonald, James A; Harden, Nick B; Nghiem, Long D; Khan, Stuart J



Thermal conductivity of isotopically enriched 71GaAs crystal  

Microsoft Academic Search

A gallium arsenide bulk crystal highly enriched with gallium isotope 71Ga to 99.40 at% has been grown using the seedless horizontal Bridgman method. The crystal has a total impurity concentration of about 2 × 1017 atoms cm-3 and a high electrical resistivity rho(300 K) ~ 103-108 Omega cm. Thermal conductivity measurements have been made from 90 K to 300 K

A. V. Inyushkin; A. N. Taldenkov; A. Yu Yakubovsky; A. V. Markov; L. Moreno-Garsia; B. N. Sharonov



Evaluation of matrix effect in isotope dilution mass spectrometry based on quantitative analysis of chloramphenicol residues in milk powder.  


In the present study, we developed a comprehensive strategy to evaluate matrix effect (ME) and its impact on the results of isotope dilution mass spectrometry (IDMS) in analysis of chloramphenicol (CAP) residues in milk powder. Stable isotope-labeled internal standards do not always compensate ME, which brings the variation of the ratio (the peak area of analyte/the peak area of isotope). In our investigation, impact factors of this variation were studied in the extraction solution of milk powder using three mass spectrometers coupled with different ion source designs, and deuterium-labeled chloramphenicol (D5-CAP) was used as the internal standard. ME from mobile phases, sample solvents, pre-treatment methods, sample origins and instruments was evaluated, and its impact on the results of IDMS was assessed using the IDMS correction factor (?). Our data showed that the impact of ME of mobile phase on the correction factor was significantly greater than that of sample solvent. Significant ion suppression and enhancement effects were observed in different pre-treated sample solutions. The IDMS correction factor in liquid-liquid extraction (LLE) and molecular imprinted polymer (MIP) extract with different instruments was greater or less 1.0, and the IDMS correction factor in hydrophilic lipophilic balance (HLB) and mix-mode cation exchange (MCX) extract with different instruments was all close to 1.0. To the instrument coupled with different ion source design, the impact of ME on IDMS quantitative results was significantly different, exhibiting a large deviation of 11.5%. Taken together, appropriate chromatographic conditions, pre-treatment methods and instruments were crucial to overcome ME and obtain reliable results, when IDMS methods were used in the quantitative analysis of trace target in complex sample matrix. PMID:24356223

Li, Xiu Qin; Yang, Zong; Zhang, Qing He; Li, Hong Mei



Determination of zinc in plant samples by isotope dilution inductively coupled plasma mass spectrometry.  


Determination of zinc involved spiking with (68)Zn enriched solution, digestion by HNO(3)+H(2)O(2) in microwave decomposition unit, off-line separation of zinc on Chelex-100 column and measurement of ((64)Zn+(66)Zn)/(68)Zn isotope ratio on ICP-MS spectrometer with a quadrupole mass filter. After optimization of standard operation procedure (details are given) the method was validated. LOD was found to be 0.3 mug g(-1) for the procedure without zinc separation and 3.6 mug g(-1) for the procedure involving zinc separation, respectively. The accuracy of results was proved by analyses of several CRM and a primary solution of zinc, the concentration of which was verified by gravimetry and complexometric titration. Barium is the only element causing serious interferences and it must be removed from samples. The uncertainty budget is given together with the scheme of combined uncertainty calculation. The main uncertainty components are contamination during zinc separation and uncertainty of isotopic composition of natural zinc. PMID:18968316

Mestek, O; Komínková, J; Koplík, R; Suchánek, M



Isotopic fractionation of the major elements of molten basalt by chemical and thermal diffusion  

Microsoft Academic Search

Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter ?i defined as the fractionation in per mil per 100°C

Frank M. Richter; E. Bruce Watson; Ruslan Mendybaev; Nicolas Dauphas; Bastian Georg; James Watkins; John Valley



Phonon-isotope scattering and thermal conductivity in materials with a large isotope effect: A first-principles study  

NASA Astrophysics Data System (ADS)

The interplay between phonon-isotope and phonon-phonon scattering in determining lattice thermal conductivities in semiconductors and insulators is examined using an ab initio Boltzmann transport equation approach. We identify materials with large enhancements to their thermal conductivities with isotopic purification, known as the isotope effect, and we focus in particular on results for beryllium-VI compounds and cubic germanium carbide. We find that germanium carbide and beryllium selenide have very large room temperature isotope effects of 450%, far larger than in any other material. Thus, isotopic purification in these materials gives surprisingly high intrinsic room temperature thermal conductivities, over 1500 Wm-1 K-1 for germanium carbide and over 600 Wm-1 K-1 for beryllium selenide, well above those of the best metals. In compound semiconductors, a large mass ratio of the constituent atoms and large isotope mixture for the heavier atom gives enhanced isotope scattering. A frequency gap between acoustic and optic phonons (also due to a large mass ratio) and bunching of the acoustic phonon branches give weak anharmonic scattering. Combined, weak anharmonic phonon scattering and strong isotope scattering give a large isotope effect in the materials examined here. The physical insights discussed in this work will help guide the efficient manipulation of thermal transport properties of compound semiconductors through isotopic modification.

Lindsay, L.; Broido, D. A.; Reinecke, T. L.



Effects of conventional heating on the stability of major olive oil phenolic compounds by tandem mass spectrometry and isotope dilution assay.  


The quality of olive oils is sensorially tested by accurate and well established methods. It enables the classification of the pressed oils into the classes of extra virgin oil, virgin oil and lampant oil. Nonetheless, it would be convenient to have analytical methods for screening oils or supporting sensorial analysis using a reliable independent approach based on exploitation of mass spectrometric methodologies. A number of methods have been proposed to evaluate deficiencies of extra virgin olive oils resulting from inappropriate technological treatments, such as high or low temperature deodoration, and home cooking processes. The quality and nutraceutical value of extra virgin olive oil (EVOO) can be related to the antioxidant property of its phenolic compounds. Olive oil is a source of at least 30 phenolic compounds, such as oleuropein, oleocanthal, hydroxytyrosol, and tyrosol, all acting as strong antioxidants, radical scavengers and NSAI-like drugs. We now report the efficacy of MRM tandem mass spectrometry, assisted by the isotope dilution assay, in the evaluation of the thermal stability of selected active principles of extra virgin olive oil. PMID:21124271

Attya, Mohamed; Benabdelkamel, Hicham; Perri, Enzo; Russo, Anna; Sindona, Giovanni



Comparison of isotope dilution with bioelectrical impedance analysis among HIV-infected and HIV-uninfected pregnant women in Tanzania  

PubMed Central

Background Bioelectrical impedance analysis (BIA) is a simple tool to assess total body water (TBW), from which body composition can be estimated using statistical equations. However, standard BIA equations have not been sufficiently validated during pregnancy, in HIV infection, or in sub-Saharan Africa. We therefore compared TBW estimates from multifrequency BIA with those from the reference method deuterium isotope dilution (Deut) in a cohort of 30 HIV-uninfected and 30 HIV-infected pregnant women from Tanzania. Methods We enrolled pregnant women presenting for routine antenatal care and collected data on pregnancy outcomes. At each trimester of gestation and once at 10-wk post-partum, we measured maternal anthropometry, TBWBIA, and TBWDeut. Results TBWBIA was highly correlated at each time point with TBWDeut among HIV-infected (all P ?0.001) and HIV-uninfected women (all P <0.0001). During pregnancy, mean TBWBIA progressively underestimated TBWDeut in the overall cohort; trimester-specific differences (mean ±SD) were ?1.02 ±2.36 kg, ?1.47 ±2.43 kg, and ?2.42 ±2.63 kg, respectively. The difference at 10-wk postpartum was small (?0.24 ±2.07 kg). In Bland-Altman and regression models, TBWBIA was subject to a systematic predictive bias at each antenatal and postnatal time point (all P ?0.038). Among HIV-positive women, TBWDeut measured during the first (P =0.02) and second trimester (P =0.03) was positively related to birthweight. Conclusions The validity of current BIA equations to assess TBW during pregnancy and in the postpartum period among women from sub-Saharan Africa remains uncertain. Deuterium dilution may assess aspects of maternal body composition relevant for pregnancy outcomes among HIV-infected women.

Kupka, R.; Manji, K.P.; Wroe, E.; Aboud, S.; Bosch, R.J.; Fawzi, W.W.; Kurpad, A.V.; Duggan, C.



Thermal neutron capture cross sections of the palladium isotopes  

SciTech Connect

Precise thermal neutron capture {gamma}-ray cross sections {sigma}{sub {gamma}} were measured for all elements with Z=1-83,90, and 92, for He and Pm, at the Budapest Reactor. These data were evaluated with additional information from the literature to generate the Evaluated Gamma-ray Activation File (EGAF). Isotopic radiative neutron cross sections can be deduced from the total transition cross section feeding the ground state, {sigma}{sub 0}={sigma}{sigma}{sub {gamma}}(GS) if the decay scheme is complete. The EGAF file contains partial {gamma}-ray cross sections for all stable palladium isotopes. None of these decay schemes are complete, although in each case transitions de-exciting low-lying levels are known. We have performed Monte Carlo simulations of the palladium thermal neutron capture decay schemes using the computer code DICEBOX. The simulated populations of low low-lying levels are normalized to the measured {sigma}{sub {gamma}} values from EGAF and the total radiative neutron cross section {sigma}{sub 0} is obtained. The {sigma}{sub 0} values derived for the palladium isotopes agree well with previous measurements and were in several cases more precise. Complementary use of {gamma}-ray cross-section data and Monte Carlo calculations has proven effective in determining both the palladium total radiative cross sections and new nuclear structure information.

Krticka, M. [Charles University in Prague, Faculty of Mathematics and Physics, V Holesovickach 2, CZ-180 00 Prague 8 (Czech Republic); North Carolina State University, Raleigh, NC 27695 (United States); Firestone, R. B. [Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); McNabb, D. P.; Sleaford, B.; Agvaanluvsan, U. [Lawrence Livermore National Laboratory, L-414, 7000 East Avenue, Livermore, CA 94551 (United States); Belgya, T.; Revay, Z. S. [Institute of Isotope and Surface Chemistry, H-1525, Budapest (Hungary)



Validation of a gas chromatography-mass spectrometry isotope dilution method for the determination of 2-butoxyethanol and other common glycol ethers in consumer products.  


A gas chromatography-mass spectrometry isotope dilution (GC-MS ID) method was developed and tested for the determination of 14 common glycol ethers in consumer products. Stable isotope labelled standards, 2-methoxyethanol-D(7) and 2-butoxyethanol-(13)C(2) (CDN isotopes) were employed to enhance the accuracy and precision of the glycol ethers determination. A 1000-fold sample dilution with methanol was applied to avoid column overload and contamination. At this dilution matrix effects were in most cases negligible and did not interfere with the analysis. The instrument detection limit (IDL) for analysed compounds varied from 0.01 to 1 ?g/mL; while the estimated limit of quantification (LoQ) varied between different glycol ethers from 0.02 to 3.4 ?g/mL. Calibration was tested in the range of 0.1-200 ?g/mL and showed that the linear fit is upheld from 0.1 to 10 ?g/mL, and extends beyond this range for some of the analytes. Recoveries of glycol ethers from products with different matrices were similar. The recoveries varied from 87% to 116% between the analysed compounds, while measurements precision varied between 2% and 14%. The method is applicable to products with glycol ether concentrations above 0.002-0.2% (w/w). The concentration range can be extended below the specified limits by decreasing the dilution factor; however, with lower dilution the sample matrix effect is expected to be stronger. Products with very high concentrations of glycol ether (>20%) may need to be further diluted prior to injection to avoid column overload. The method can be used for testing liquid and aerosol products designed for household use, such as cleaners, paints, solvents and paint stripers, for compliance and enforcement of regulations which limit glycol ethers content. PMID:20855078

Tokarczyk, Ryszard; Jiang, Ying; Poole, Gary; Turle, Richard



Diagnosis of inborn errors of metabolism using filter paper urine, urease treatment, isotope dilution and gas chromatography-mass spectrometry.  


This review will be concerned primarily with a practical yet comprehensive diagnostic procedure for the diagnosis or even mass screening of a variety of metabolic disorders. This rapid, highly sensitive procedure offers possibilities for clinical chemistry laboratories to extend their diagnostic capacity to new areas of metabolic disorders. The diagnostic procedure consists of the use of urine or filter paper urine, preincubation of urine with urease, stable isotope dilution, and gas chromatography-mass spectrometry. Sample preparation from urine or filter paper urine, creatinine determination, stable isotope-labeled compounds used, and GC-MS measurement conditions are described. Not only organic acids or polar ones but also amino acids, sugars, polyols, purines, pyrimidines and other compounds are simultaneously analyzed and quantified. In this review, a pilot study for screening of 22 target diseases in newborns we are conducting in Japan is described. A neonate with presymptomatic propionic acidemia was detected among 10,000 neonates in the pilot study. The metabolic profiles of patients with ornithine carbamoyl transferase deficiency, fructose-1,6-bisphosphatase deficiency or succinic semialdehyde dehydrogenase deficiency obtained by this method are presented as examples. They were compared to those obtained by the conventional solvent extraction methods or by the tandem mass spectrometric method currently done with dried filter blood spots. The highly sensitive, specific and comprehensive features of our procedure are also demonstrated by its use in establishing the chemical diagnosis of pyrimidine degradation defects in order to prevent side effects of pyrimidine analogs such as 5-flurouracil, and the differential diagnosis of three types of homocystinuria, orotic aciduria, uraciluria and other urea cycle disorders. Evaluation of the effects of liver transplantation or nutritional conditions such as folate deficiency in patients with inborn errors of metabolism is also described. PMID:11482733

Kuhara, T



Assessment of the amount of body water in the Red Knot (Calidris canutus): an evaluation of the principle of isotope dilution with H, O, and O as measured with laser spectrometry and isotope ratio mass spectrometry  

Microsoft Academic Search

We have used the isotope dilution technique to study changes in the body composition of a migratory shorebird species (Red Knot, Calidris canutus) through an assessment of the amount of body water in it. Birds were quantitatively injected with a dose of water with elevated concentrations of H, O, and O. Thereafter, blood samples were taken and distilled. The resulting

Erik R. T. Kerstel; Theunis A. J. Piersma; G. Jim Gessaman; Anne Dekinga; Harro A. J. Meijer; G. Henk Visser



Solvent extraction\\/anion exchange separation and determination of PGEs (Os, Ir, Pt, Pd, Ru) and Re–Os isotopes in geological samples by isotope dilution ICP-MS  

Microsoft Academic Search

A method is described that allows the separation of Re, Os, Pt, Pd, Ir and Ru for determination by isotope dilution via inductively coupled mass spectrometry (ICP-MS) at pg levels, from the same sample aliquot. Samples are digested in Carius tubes, enabling effective attack of PGEs in a wide range of geological materials, including pure chromite separates. Os is isolated

D. G Pearson; S. J Woodland



Improved approach for analyzing bromophenols in seafood using stable isotope dilution analysis in combination with SPME.  


An analytical method for the measurement of five naturally occurring bromophenols of sensory relevance in seafood (barramundi and prawns) is presented. The method combines simultaneous distillation-extraction followed by alkaline back extraction of a hexane extract and subsequent acetylation of the bromophenols. Analysis of the bromophenol acetates was accomplished by headspace solid phase microextraction and gas chromatography-mass spectrometry using selected ion monitoring. The addition of (13)C 6 bromophenol stable isotope internal standards for each of the five congeners studied permitted the accurate quantitation of 2-bromophenol, 4-bromophenol, 2,6-dibromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol down to a limit of quantification of 0.05 ng/g of fish flesh. The method indicated acceptable precision and repeatability and excellent linearity over the typical concentration range of these compounds in seafood (0.5-50 ng/g). The analytical method was applied to determine the concentration of bromophenols in a range of farmed and wild barramundi and prawns and was also used to monitor bromophenol uptake in a pilot feeding trial. PMID:18754626

Fuller, Steve C; Frank, Damian C; Fitzhenry, Matthew J; Smyth, Heather E; Poole, Sue E



Application of isotope dilution mass spectrometry: determination of ochratoxin A in the Canadian Total Diet Study  

PubMed Central

Analytical methods are generally developed and optimized for specific commodities. Total Diet Studies, representing typical food products ‘as consumed’, pose an analytical challenge since every food product is different. In order to address this technical challenge, a selective and sensitive analytical method was developed suitable for the quantitation of ochratoxin A (OTA) in Canadian Total Diet Study composites. The method uses an acidified solvent extraction, an immunoaffinity column (IAC) for clean-up, liquid chromatography-tandem mass spectrometry (LC-MS/MS) for identification and quantification, and a uniformly stable isotope-labelled OTA (U-[13C20]-OTA) as an internal recovery standard. Results are corrected for this standard. The method is accurate (101% average recovery) and precise (5.5% relative standard deviation (RSD)) based on 17 duplicate analysis of various food products over 2 years. A total of 140 diet composites were analysed for OTA as part of the Canadian Total Diet Study. Samples were collected at retail level from two Canadian cities, Quebec City and Calgary, in 2008 and 2009, respectively. The results indicate that 73% (102/140) of the samples had detectable levels of OTA, with some of the highest levels of OTA contamination found in the Canadian bread supply.

Tam, J.; Pantazopoulos, P.; Scott, P.M.; Moisey, J.; Dabeka, R.W.; Richard, I.D.K.



Online determination of copper in aluminum alloy by microchip solvent extraction using isotope dilution ICP-MS method.  


Isotope dilution mass spectroscopy (IDMS)/ICP-MS combined with microchip solvent extraction was successfully applied for the online determination of copper in an aluminum alloy. The microchip solvent extraction was developed for the separation of Cu from major element, and optimal pH range was wider than that of the batchwise extraction method. The dimensions of the microchip were 30 mm x 70 mm and that of micro-channel on the microchip was 180 microm wide and 40 microm deep. The copper complex with 8-hydroxyquinoline was extracted into o-xylene at pH 5.5 and back extracted with 0.1 mol l(-1) nitric acid at flow rate of 20 microl min(-1). The total extraction efficiency (water/organic solvent/nitric acid) was around 40%. IDMS/ICP-MS was coupled with solvent extraction for precise determination of Cu. The extraction and back-extraction on the microchip took about 1s and the total measurement time for the IDMS/ICP-MS was about 40s/sample. The blank value of this method was 0.1 ng g(-1). The proposed method was used for the determination of Cu in Al standard materials (JSAC 0121-C, The Japan Society for Analytical Chemistry and 7074 Al alloy, Nippon Light Metal Co. Ltd.). The obtained analytical results are in good agreement with the certified values. PMID:19615499

Kagawa, Tsuyoshi; Ohno, Masashi; Seki, Tatsuya; Chikama, Katsumi



Sensitive isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry method for the determination of acrylamide in chocolate.  


Isotope dilution liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-MS/MS) was applied to the quantification of acrylamide in chocolate matrixes (dark chocolate, milk chocolate, chocolate with nuts, chocolate with almonds, and chocolate with wheat best element). The method included defatting with petroleum ether, extracting with aqueous solution of 2 mol l(-1) sodium chloride and clean-up by solid-phase (SPE) with OASIS HLB 6 cm3 cartridges. Acrylamide was detected with an Atlantis dC18 5 microm 210 x 1.5 mm column using 10% methanol/0.1% formic acid in water as the mobile phase. The analytical method was in-house validated and good results were obtained with respect to repeatability (RSD < 3.5%) and recovery (86-93%), which fulfilled the requirements defined by European Union legislation. The acrylamide levels in chocolate were 23-537 microg kg(-1). Therefore, the method was successfully used for the quantitative analysis of acrlyamide in various chocolate products. PMID:16517524

Ren, Yiping; Zhang, Yu; Jiao, Jingjing; Cai, Zengxuan; Zhang, Ying



Quantification of recombinant human erythropoietin by amino acid analysis using isotope dilution liquid chromatography-tandem mass spectrometry.  


Herein, we describe an accurate method for protein quantification based on conventional acid hydrolysis and an isotope dilution-ultra performance liquid chromatography-tandem mass spectrometry method. The analyte protein, recombinant human erythropoietin (rhEPO), was effectively hydrolyzed by incubation with 8 mol/L hydrochloric acid at 130 °C for 48 h, in which at least 1 ?mol/kg of rhEPO was treated to avoid possible degradation of released amino acids during hydrolysis. Prior to hydrolysis, sample solution was subjected to ultrafiltration to eliminate potential interfering substances. In a reversed-phase column, the analytes (phenylalanine, proline, and valine) were separated within 3 min using gradient elution comprising 20 % (v/v) acetonitrile and 10 mmol/L ammonium acetate, both containing 0.3 % (v/v) trifluoroacetic acid. The optimized hydrolysis and analytical conditions in our study were strictly validated in terms of accuracy and precision, and were suitable for the accurate quantification of rhEPO. Certified rhEPO was analyzed using a conventional biochemical assay kit as an additional working calibrant for the quantification of EPO and improved the accuracy. The optimized protocol is suitable for the accurate quantification of rhEPO and satisfactorily serves as a reference analytical procedure for the certification of rhEPO and similar proteins. PMID:24842400

Yim, Jung-Hyuk; Yoon, Ina; Yang, Hyo-Jin; Kim, Sook-Kyung; Park, Sang-Ryoul; Lee, Yong-Moon; Jeong, Ji-Seon



Radioimmunoassay and liquid-chromatographic analysis for free cortisol in urine compared with isotope dilution-mass spectrometry  

SciTech Connect

Three different routine methods for analysis for urinary cortisol with those by a highly specific reference method based on isotope dilution-mass spectrometry (I) were compared. A ''high-performance'' liquid-chromatographic method (II) gave the most comparable results (regression coefficient 0.86, intercept 9 nmol/L). For some urines much lower values were obtained by I than by II. Two radioimmunoassay (III) methods, one involving direct assay and one involving extraction, gave less-accurate results (regression coefficients of 1.87 and 1.52 and intercepts of 86 and 12 nmol/L, respectively), although values obtained by III and by I correlated well (r = 0.95-0.99), indicating a relation between the free cortisol and the compounds interfering in III. The apparent accuracy for the extraction method was improved by using as calibration standards urine samples previously assayed by I (regression coefficient 0.90, intercept 6 nmol/L). All four methods investigated showed a statistically significant sex-related difference in 24-h urinary cortisol excretion; evidently such a finding should be a prerequisite in any such method proposed for routine use.

Lantto, O.



Quality evaluation of olive oil by statistical analysis of multicomponent stable isotope dilution assay data of aroma active compounds.  


An instrumental method for the evaluation of olive oil quality was developed. Twenty-one relevant aroma active compounds were quantified in 95 olive oil samples of different quality by headspace solid phase microextraction (HS-SPME) and dynamic headspace coupled to GC-MS. On the basis of these stable isotope dilution assay results, statistical evaluation by partial least-squares discriminant analysis (PLS-DA) was performed. Important variables were the odor activity values of ethyl isobutanoate, ethyl 2-methylbutanoate, 3-methylbutanol, butyric acid, E,E-2,4-decadienal, hexanoic acid, guaiacol, 2-phenylethanol, and the sum of the odor activity values of Z-3-hexenal, E-2-hexenal, Z-3-hexenyl acetate, and Z-3-hexenol. Classification performed with these variables predicted 88% of the olive oils' quality correctly. Additionally, the aroma compounds, which are characteristic for some off-flavors, were dissolved in refined plant oil. Sensory evaluation of these models demonstrated that the off-flavors rancid, fusty, and vinegary could be successfully simulated by a limited number of odorants. PMID:22117816

Dierkes, Georg; Bongartz, Annette; Guth, Helmut; Hayen, Heiko



Ultratrace-level radium-226 determination in seawater samples by isotope dilution inductively coupled plasma mass spectrometry.  


An improved and novel sample preparation method for 226Ra determination in liquid samples by isotope dilution inductively coupled plasma sector field mass spectrometry using laboratory-prepared 228Ra tracer has been developed. The procedure involves a selective preconcentration achieved by applying laboratory-prepared MnO2 resin followed by cation exchange chromatographic separation. In order to completely eliminate possible molecular interferences, medium mass resolution (R = 4,000) combined with chemical separation was found to be a good compromise that enhanced the reliability of the method. The detection limit of 0.084 fg g(-1) (3.1 mBq kg(-1)) achieved is comparable to that of the emanation method or alpha spectrometry and is suitable for low-level environmental measurements. The chemical recovery of the sample preparation method ranged from 72 to 94%. The proposed method enables a rapid, accurate and less labor-intensive approach to routine environmental 226Ra determination than the radioanalytical techniques conventionally applied. PMID:17593357

Varga, Zsolt



Quantitative determination of 2-methoxy-3-isobutylpyrazine in red wines and grapes of Bordeaux using a stable isotope dilution assay.  


Quantitative analysis of 2-methoxy-3-isobutylpyrazine (MIBP) in grapes and wines was developed, using a stable isotope dilution assay. This was applied to red grapes and wines from the Bordeaux region. The grapes and the wines of the 1995 and 1996 vintages came from the three most frequently used varieties of the region, Merlot, Cabernet Franc and Cabernet Sauvignon. The wines made from Cabernet Sauvignon grapes exhibited levels of MIBP (mean concentration, 12 ng l-1 for 1996 vintage and 13 ng l-1 for 1995 vintage) close to or higher than its odour threshold in wines (10 ng l-1) and slightly higher than the amounts found in the Merlot wines (mean concentration, 8 ng l-1 for 1996 vintage and 4 ng l-1 for 1995 vintage), especially those of the 1996 vintage. The variation in the levels of MIBP in grape samples and in their corresponding wines was monitored at four different stages towards the end of maturation. MIBP was present in all grapes and wines analysed, even in surmaturation. A linear trend was observed between grapes and wines of the three cultivars during maturation. PMID:10371049

Kotseridis, Y; Baumes, R L; Bertrand, A; Skouroumounis, G K



Quantitative determination of beta-ionone in red wines and grapes of Bordeaux using a stable isotope dilution assay.  


Quantitative analysis of beta-ionone has been developed, using a stable isotope dilution assay. This was applied to red wines from different cultivars and regions. The Burgundy Pinot noir wines exhibited the highest levels of beta-ionone. The variation in the levels of beta-ionone in grape samples and in their corresponding wines, of Merlot, Cabernet Sauvignon and Cabernet franc from Bordeaux regions was monitored at four different stages towards the end of maturation: the levels of beta-ionone were almost similar, exhibiting only a slight decrease during maturation. beta-Ionone occurred in all the grapes and wines samples analysed at levels higher than, or close to its odour threshold which was determined in a model wine solution and was found to be of 90 ng l-1. In a previously supplemented model wine solution with beta-ionone (250 ng l-1), the odour threshold was found to be of 980 ng l-1 (total levels). PMID:10427760

Kotseridis, Y; Baumes, R L; Bertrand, A; Skouroumounis, G K



Quantitative determination of four nitrofuran metabolites in meat by isotope dilution liquid chromatography-electrospray ionisation-tandem mass spectrometry.  


A confirmatory method based on isotope dilution liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been developed for the low-level determination of residues of four nitrofuran veterinary drugs in meat, e.g., furazolidone, furaltadone, nitrofurantoin, and nitrofurazone. The procedure entails an acid-catalysed release of protein-bound metabolites, followed by their in situ conversion into the 2-nitrobenzaldehyde (NBA) imine-type derivatives. Liquid-liquid extraction and clean-up on a polymeric solid phase extraction cartridge are then performed before LC-MS/MS analysis by positive electrospray ionisation (ESI) applying multiple reaction monitoring of three transition reactions for each compound. Reliable quantitation is obtained by using one deuterated analogue per analyte (d4-NBA derivative) as internal standard (IS). Validation of the method in chicken meat was conducted following the European Union (EU) criteria for the analysis of veterinary drug residues in foods. The decision limits (CCalpha) were 0.11-0.21 microg/kg, and the detection capabilities (CCbeta) 0.19-0.36 microg/kg, thus below the minimum required performance limit (MRPL) set at 1 microg/kg by the EU. The method is robust and suitable for routine quality control operations, and more than 200 sample injections were performed without excessive pollution of the mass spectrometer or loss of LC column performance. PMID:15844512

Mottier, Pascal; Khong, Seu-Ping; Gremaud, Eric; Richoz, Janique; Delatour, Thierry; Goldmann, Till; Guy, Philippe A



Parkinson-dementia complex and development of a new stable isotope dilution assay for BMAA detection in tissue  

SciTech Connect

{beta}-Methylamino-L-alanine (BMAA) has been proposed as a global contributor to neurodegenerative diseases, including Parkinson-dementia complex (PDC) of Guam and Alzheimer's disease (AD). The literature on the effects of BMAA is conflicting with some but not all in vitro data supporting a neurotoxic action, and experimental animal data failing to replicate the pattern of neurodegeneration of these human diseases, even at very high exposures. Recently, BMAA has been reported in human brain from individuals afflicted with PDC or AD. Some of the BMAA in human tissue reportedly is freely extractable (free) while some is protein-associated and liberated by techniques that hydrolyze the peptide bond. The latter is especially intriguing since BMAA is a non-proteinogenic amino acid that has no known tRNA. We attempted to replicate these findings with techniques similar to those used by others; despite more than adequate sensitivity, we were unable to detect free BMAA. Recently, using a novel stable isotope dilution assay, we again were unable to detect free or protein-associated BMAA in human cerebrum. Here we review the development of our new assay for tissue detection of BMAA and show that we are able to detect free BMAA in liver but not cerebrum, nor do we detect any protein-associated BMAA in mice fed this amino acid. These studies demonstrate the importance of a sensitive and specific assay for tissue BMAA and seriously challenge the proposal that BMAA is accumulating in human brain.

Snyder, Laura R. [Department of Chemistry, University of Washington, Seattle, WA (United States); Cruz-Aguado, Reyniel [Department of Ophthalmology and Visual Sciences, University of British Columbia, Vancouver, BC (Canada); Sadilek, Martin [Department of Chemistry, University of Washington, Seattle, WA (United States); Galasko, Douglas [Department of Neurosciences, University of California at San Diego, San Diego, CA (United States); Shaw, Christopher A. [Department of Ophthalmology and Visual Sciences, University of British Columbia, Vancouver, BC (Canada); Montine, Thomas J. [Department of Pathology, University of Washington, Seattle, WA 98104 (United States)], E-mail:



Survey of Natural Cadmium Isotope Fractionation by Double Spike Thermal Ionisation Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Wombacher et al. (2003) have shown recently that natural Cd isotope fractionations in terrestrial materials are extremely limited (~100 ppm/amu or less). Thus, excellent external precision is absolutely paramount if Cd isotope fractionations are to be adequately quantified. Here we present a new high-precision double spike (DS) technique for Cd isotopes in which the Cd is measured by thermal ionisation mass spectrometry (TIMS, ThermoElectron Triton), which draws on the pioneering work of Rosman et al. (1980). We observe pronounced anomalous odd-even isotope mass bias during TIMS measurement of Cd with silica gel activator, and avoid such effects by utilizing even isotopes of Cd only. The double spike and its composition were carefully optimized (cf. Galer, 1999), and the "natural" Cd isotope fractionation is expressed as the relative deviations in ^{112}Cd/^{110}Cd (in parts per 104) from our JMC Cd shelf standard. The external reproducibility for 100 ng loads of double-spiked JMC Cd shelf is ± 0.14 ?^{112/110}Cd (2SD, N=57) -- i.e. ±7 ppm/amu -- which is a factor of 4 to 10 times better than that reported in published studies using MC-ICP-MS techniques (e.g. Wombacher et al., 2003; Cloquet et al., 2005). The DS-TIMS method offers further benefits in terms of superior sensitivity, while Cd abundances are obtained as a biproduct by isotope dilution. We have analyzed ?^{112/110}Cd in over sixty samples from different terrestrial reservoirs and environments in order to delimit the extent of natural isotope fractionation of Cd. Most samples were duplicated or triplicated. To facilitate inter-lab comparison, our measured ?^{112/110}Cd for the standards "Münster Cd" and BAM-1012 averaged +21.46 and -7.42, respectively. On the whole, our study confirms the conclusions of Wombacher et al. (2003) that Cd isotope variations in terrestrial materials are limited -- nearly all samples fall within the range -1.0 to +1.0 in ?^{112/110}Cd. Nevertheless, we are able for the first time to resolve clearly differences far outside of analytical error. Analyses of 31 hydrogenous Fe-Mn deposits (and phosphorites) worldwide range from -0.6 to +2.0; those from the Indian and Circum- Antarctic Oceans lie at ~0, whíle Pacific and Atlantic samples generally having positive values. We suggest these differences reflect different rates of vertical inorganic scavenging and remineralization. Oceanic basalts (MORB, Hawaii) and continental loess samples generally have negative ?^{112/110}Cd (-1.2 to -0.5) which may imply that the bulk silicate Earth has a mildly negative value relative to our Cd standard. Major sphalerite deposits worldwide are clustered between -1.0 and 0 suggesting that the mechanisms of ore deposit formation do not result in large isotopic fractionations of Cd. Ocean floor hydrothermal sulphide and Fe-Mn deposits mostly cluster around -0.5, but a few of the sulphides exhibit large variations -- as fractionated as -3.0 to +1.0. Overall, natural variations in ?^{112/110}Cd appear to be quite limited -- and are now resolvable -- but are dwarfed by the extreme Cd isotope fractionations found in meteorites (Rosman et al., 1980; Wombacher et al., 2003) and anthropogenic Cd (Cloquet et al., 2005). References: Cloquet C. et al. (2005), Geostand. Geoanal. Res. 1, 95-106; Galer S.J.G. (1999), Chem. Geol. 157, 255-274; Rosman K.J.R. et al. (1980), Geochem. J. 14, 269-277; Wombacher F. et al. (2003), Geochim. Cosmochim. Acta 67, 4639-4654.

Schmitt, A.; Galer, S. J.; Abouchami, W.



Potassium-Argon Ages of the Dartmoor and Shap Granites using the Total Volume and Isotopic Dilution Techniques of Argon Measurement  

Microsoft Academic Search

EARLY in 1960, J. L. Kulp and others reported potassium-argon and rubidium-strontium ages for a number of granites from Great Britain and Eire1. The argon measurements were made at the Lamont Geological Observatory by the isotopic dilution technique, and the rubidium-strontium determinations were made at Oxford and Harwell. Some of the rocks examined, including the Shap and Dartmoor granites, had

M. H. Dodson; J. A. Miller; D. York



Quantification of carcinogenic 4- to 6-ring polycyclic aromatic hydrocarbons in human urine by solid-phase microextraction gas chromatography–isotope dilution mass spectrometry  

Microsoft Academic Search

Polycyclic aromatic hydrocarbons (PAHs) are pollutants found in living and working environments. The aim of this study was\\u000a to develop a solid-phase microextraction (SPME) gas chromatography (GC)–isotope dilution mass spectrometry method for the\\u000a quantification of 10 four- to six-ring PAHs in urine samples. Seven of the selected PAHs have been classified as carcinogenic.\\u000a Under the final conditions, analytes were sampled

Laura Campo; Silvia Fustinoni; PierAlberto Bertazzi


Quantification of ochratoxin A in foods by a stable isotope dilution assay using high-performance liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

A stable isotope dilution assay (SIDA) was developed for quantification of the mycotoxin ochratoxin A (OTA) by using [2H5]-OTA as internal standard. The synthesis of labelled OTA was accomplished by acid hydrolysis of unlabelled OTA and subsequent coupling one of the products, ochratoxin ?, to [2H5]-l-phenylalanine. The mycotoxin was quantified in foods by LC-tandem MS after extraction with buffers containing

Michael Lindenmeier; Peter Schieberle; Michael Rychlik



Application of isotope dilution to the determination of methylmercury in fish tissue by solid-phase microextraction gas chromatography-mass spectrometry  

Microsoft Academic Search

Species-specific isotope dilution (ID) calibration using solid-phase microextraction (SPME) in combination with gas chromatography-mass spectrometry (GC-MS) for separation and detection of methylmercury (MeHg) in fish tissue is described. Samples were digested with methanolic potassium hydroxide. Analytes were propylated and headspace sampled with a polydimethylsiloxane-coated SPME fused-silica fiber. ID analysis was performed using a laboratory-synthesized 198Hg-enriched methylmercury (Me198Hg) spike. Using selective

Lu Yang; Vanessa Colombini; Paulette Maxwell; Zoltán Mester; Ralph E. Sturgeon



Isotope dilution determination of polycyclic aromatic hydrocarbons in olive pomace oil by gas chromatography-mass spectrometry.  


A gas chromatographic (GC) method with mass spectrometry detection (MS) for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in olive pomace oil has been developed. The oil was diluted with n-pentane and extracted by liquid-liquid partition with dimethyl sulphoxide (DMSO). After water addition and back-extraction with cyclohexane, a thin-layer chromatography on silica gel was performed as a further purification step. The PAHs spot was scraped off from the plate and the final extract was concentrated and analysed by GC-MS in full scan mode. The eight PAHs under investigation were determined in the presence of the corresponding labelled compounds added as internal standards to the sample at the beginning of the analytical process. The identified PAHs were then quantified by the isotope dilution methodology assuring the compensation of the concentration of each analyte for any variation in the sample preparation. The method precision was satisfactory with relative standard deviation (R.S.D.) values in the range 3.6-12.7% for all PAHs. The average recovery rates ranged from 69.0 to 97.5%. Accuracy was also calculated for benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene by analysing a certified reference material (CRM 458, coconut oil) with adequate results. All response curves exhibited a linear fit from 0.1 to 10 microg ml(-1) and the determination coefficients R2 were better than 0.9942. The limits of detection (0.1-0.4 microg kg(-1)) were acceptable when compared with the maximum permitted limit of 2 microg kg(-1) for each of the eight considered PAHs and 5 microg kg(-1) for the sum of the eight PAHs established by the Italian legislation. Measurement uncertainty was finally calculated identifying and quantifying the uncertainty components of the analytical process. The relative expanded uncertainties (Uc), expressed as percent values were in the range 8.5-11.4% thus appropriate for residues quantification in the range of concentrations considered in the present study. PMID:15679162

Diletti, Gianfranco; Scortichini, Giampiero; Scarpone, Rossana; Gatti, Giuseppe; Torreti, Luigi; Migliorati, Giacomo



A stable isotope dilution LC-ESI-MS/MS method for the quantification of pyridoxal-5'-phosphate in whole blood.  


Vitamin B6 is a cofactor in numerous biologic processes that include gluconeogenesis, neurotransmitter synthesis and amino acid metabolism. The aim of this study was to develop a method to measure the concentration of the biologically active form of vitamin B6 (pyridoxal-5'-phosphate, PLP) in whole blood with stable isotope dilution LC-ESI-MS/MS and compare this new procedure with an established HPLC method based on derivatization of pyridoxal-5'-phosphate. 50 ?l of stable isotope (PLP-d3) was added to 250 ?l of sample, followed by deproteinization with 10% trichloroacetic acid. After centrifugation, 20 ?l of the supernatant was injected into the LC-ESI-MS/MS. Reversed phase chromatography was performed on a UPLC system, using a Waters™ Symmetry C18 column, with a gradient of 0.1% formic acid in methanol. PLP was measured on a tandem MS with a mass transition of 247.8>149.8 in the positive ion mode with a collision energy of 14 eV. The chromatographic run lasted 4 min. The method was linear from 4 to 8000 nmol/l. The intra-day and inter-day precision ranged between 1.7-2.8% and 3.0-4.1%, respectively. The mean absolute matrix-effect was 99.3% [97-102%]. The relative matrix-effect was 98.8%. The mean recovery was 98% [89-103%]. The lower limit of quantification was 4 nmol/l. The comparison of the LC-ESI-MS/MS method with our current HPLC method yielded the following equation: LC-ESI-MS/MS=1.11 [confidence interval, CI: 1.03-1.20] × HPLC+4.6 [CI: -1.3 to 11.0] (r²=0.94). This LC-ESI-MS/MS based method is characterized by simple sample processing and a short run time. The comparison with the current HPLC method is excellent although a significant proportional bias was detected. To conclude, the LC-ESI-MS/MS method is an appropriate method to determine PLP in whole blood. PMID:22857864

van Zelst, Bertrand D; de Jonge, Robert



Viscosity and Thermal Conductivity Coefficients of Dilute Argon Between 100 And 2000 K.  

National Technical Information Service (NTIS)

The variation of the force constants of the Lennard-Jones, Exp: 6, and Kihara potential functions was investigated by comparing the Chapman-Enskog kinetic theory expression for the viscosity coefficient with the experimental viscosity of dilute argon. It ...

H. J. M. Hanley



Simultaneous detection of multiple hydroxylated polychlorinated biphenyls from a complex tissue matrix using gas chromatography/isotope dilution mass spectrometry.  


In this study, we developed a comprehensive, highly sensitive, and robust method for determining 53 congeners of three to eight chlorinated OH-PCBs in liver and brain samples by using isotope dilution gas chromatography (GC) coupled with electron capture negative ionization mass spectrometry (ECNI-MS). These results were compared with those from GC coupled with electron ionization high-resolution mass spectrometry (EI-HRMS). Clean-up procedures for analysis of OH-PCBs homologs in liver and brain samples involve a pretreatment step consisting of acetonitrile partition and 5% hydrated silica-gel chromatography before derivatization. Recovery rates of tri- and tetra-chlorinated OH-PCBs in the acetonitrile partition method followed by the 5% hydrated silica-gel column (82% and 91%) were higher than conventional sulfuric acid treatment (2.0% and 3.5%). The method detection limits of OH-PCBs for each matrix obtained by GC/ECNI-MS and GC/EI-HRMS were 0.58-2.6 pg g(-1) and 0.36-1.6 pg g(-1) wet wt, respectively. Recovery rates of OH-PCB congeners in spike tests using sample matrices (10 and 50 pg) were 64.7-117% (CV: 4.7-14%) and 70.4-120% (CV: 2.3-12%), respectively. This analytical method may enable the simultaneous detection of various OH-PCBs from complex tissue matrices. Furthermore, this method allows more comprehensive assessment of the biological effects of OH-PCB exposure on critical organs. PMID:24274296

Eguchi, Akifumi; Nomiyama, Kei; Ochiai, Mari; Mizukawa, Hazuki; Nagano, Yasuko; Nakagawa, Katsuhiro; Tanaka, Kouki; Miyagawa, Haruhiko; Tanabe, Shinsuke



Studies of transport and collection characteristics of gaseous mercury in natural gases using amalgamation and isotope dilution analysis.  


Transport and collection characteristics were studied for gaseous elemental mercury (Hg(0)(g)) in natural gases using newly developed methodology based on amalgamation, isotope dilution with permeation tubes and inductively coupled plasma mass spectrometry. The study involved different Au-Pt collection tube designs, tubing materials and gaseous matrices, including air, natural and sales gas, as well as methane and sales gas to which hydrogen sulfide (H(2)S) had been added. The Hg(0)(g) capacity of the Au-Pt tubes was determined to 3.5 +/- 0.1 microg. Blanks and detection limits of gaseous mercury (Hg(g)) were 58 +/- 17 pg m(-3) and 50 pg m(-3), respectively, for a 60 L sample volume. For the gases tested, added Hg(0)(g) tracers could be collected with 90% or higher efficiency at flow rates and volumes of up to 10 L min(-1) and 100 L, respectively. The collection efficiency was found to be independent of the type of gas tested, even in the presence of H(2)S. However, for the gases containing H(2)S, the apparent transport efficiency of added Hg(0)(g) tracers through stainless steel tubing varied from 50 to 150% upon changing the temperature from 25 to 100 degrees C. The interaction of stainless steel with Hg(0)(g) leading to either a sink, or source of Hg, was not observed in the absence of H(2)S, nor was it observed for PTFE tubing in the presence of H(2)S. These observations raise questions about the applicability of currently used sampling procedures for determination of Hg(g) in H(2)S rich natural gases, including the 6978-2 ISO standard method, in which stainless steel is a prescribed material for tubing and valves of the sampling apparatus. PMID:17525816

Larsson, Tom; Frech, Wolfgang; Björn, Erik; Dybdahl, Björn



Measurement of mercury species in human blood using triple spike isotope dilution with SPME-GC-ICP-DRC-MS.  


The measurement of different mercury compounds in human blood can provide valuable information about the type of mercury exposure. To this end, our laboratory developed a biomonitoring method for the quantification of inorganic (iHg), methyl (MeHg), and ethyl (EtHg) mercury in whole blood using a triple-spike isotope dilution (TSID) quantification method employing capillary gas chromatography (GC) and inductively coupled dynamic reaction cell mass spectrometry (ICP-DRC-MS). We used a robotic CombiPAL® sample handling station featuring twin fiber-based solid-phase microextraction (SPME) injector heads. The use of two SPME fibers significantly reduces sample analysis cycle times making this method very suitable for high sample throughput, which is a requirement for large public health biomonitoring studies. Our sample preparation procedure involved solubilization of blood samples with tetramethylammonium hydroxide (TMAH) followed by the derivatization with sodium tetra(n-propyl)borate (NaBPr4) to promote volatility of mercury species. We thoroughly investigated mercury species stability in the blood matrix during the course of sample treatment and analysis. The method accuracy for quantifying iHg, MeHg, and EtHg was validated using NIST standard reference materials (SRM 955c level 3) and the Centre de Toxicologie du Québec (CTQ) proficiency testing (PT) samples. The limit of detection (LOD) for iHg, MeHg, and EtHg in human blood was determined to be 0.27, 0.12, and 0.16 ?g/L, respectively. PMID:24948088

Sommer, Yuliya L; Verdon, Carl P; Fresquez, Mark R; Ward, Cynthia D; Wood, Elliott B; Pan, Yi; Caldwell, Kathleen L; Jones, Robert L



An Isotope Dilution Method for High-frequency Measurements of Dissolved Inorganic Carbon concentration in the Surface Ocean  

NASA Astrophysics Data System (ADS)

Dissolved inorganic carbon (DIC) is one of the most important species in the ocean carbon system. An autonomous system using isotope dilution as its core method has been developed to obtain high-frequency measurements of dissolved inorganic carbon (DIC) concentrations in the surface ocean. This system accurately mixes a seawater sample and a 13C-labeled sodium bicarbonate solution (spike). The mixed solution is then acidified and sent through a gas permeable membrane contactor. CO2 derived from DIC in the mixture is extracted by a CO2-free gas stream, and is sent to a cavity ring-down spectrometer to analyze its 13C/12C ratio. [DIC] of the seawater can then be derived from the measured 13C/12C, the known mixing ratio and the [DI13C] of the spike. The method has been tested under a wide [DIC] range (1800-2800 ?mol/kg) in the laboratory. It has also been deployed on a cruise that surveyed ocean waters to the south of Florida. At a sampling resolution of 4 minutes (15 samples per hour), the relative standard deviation of DIC determined from the laboratory tests and the field deployment is ×0.07% and ×0.09%, respectively. The accuracy of the method is better than 0.1% except where [DIC] varies faster than 5 ?mol/kg per minute. Based on the laboratory and field evaluations, we conclude that this method can provide accurate underway [DIC] measurements at high resolution in most oceanic regions. Schematic illustration of the work flow.

Huang, K.; Bender, M. L.; Wanninkhof, R. H.; Cassar, N.



Simultaneous analysis of urinary phthalate metabolites of residents in Korea using isotope dilution gas chromatography-mass spectrometry.  


Phthalates are used in industry products, household items, and medical tools as plasticizers. Human exposure to phthalates has raised concern about its toxicity. In the present study, optimization was conducted for the simultaneous analysis of eight kinds of phthalate metabolites using gas chromatography-mass spectrometry (GC-MS): MEP, MiBP, MnBP, MBzP, MiNP, MEHP, MEOHP, and MEHHP. In order to minimize the matrix effect and to do quantitative analysis, isotope dilution and LLE-GC-MS methods were performed. Urine samples were enzymatically hydrolyzed, extracted with a mixture of n-hexane and ethyl ether (8:2; v:v), and subsequently derivatized with trimethylsilylation. All eight kinds of analytes showed clear resolution and high reproducibility in GC-MS results. The method detection limit ranged from 0.05 ng/mL to 0.2 ng/mL. Calibration curves were found to be linear from 0.2 to 100 ng/mL with -(2)>0.992. The relative standard deviation of the intraday precision using water and urine ranged from 2.1% to 16.3%. The analysis was performed with urine samples that were collected from adults residing in the Republic of Korea. The analyzed concentration results were compared according to gender and region. As a result, DEHP metabolites showed the highest detected concentration (75.92 ?g/g creatinine, 100%), and MiNP, a metabolite of DiNP, showed the lowest detected concentration (0.42 ?g/g creatinine, 22.5%). On average, female urine (200.76 ?g/g creatinine) had a higher detected concentration of ?8 phthalate metabolites than male urine. Samples from rural regions (211.96 ?g/g creatinine) had higher levels than samples from urban regions. PMID:23928369

Kim, Miok; Song, Na Rae; Choi, Jong-Ho; Lee, Jeongae; Pyo, Heesoo



Sulphur Speciation and Turnover in Soils: Evidence from Sulphur K-Edge XANES Spectroscopy and Isotope Dilution Studies  

SciTech Connect

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilization and gross mineralization were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralization during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralization in the short-term.

Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.



Sulphur Speciation and Turnover in Soils: Evidence from Sulfur K-Edge XANES Spectroscopy and Isotope Dilution Studies  

SciTech Connect

Sulphur K-edge X-ray absorption near edge structure (XANES) spectroscopy was used to quantify S species in humic substance extracts from ten soils from the UK, China and New Zealand, which differ in land use and agricultural management. XANES spectroscopy showed the presence of most reduced (sulphides, disulphides, thiols and thiophenes), intermediate (sulphoxides and sulphonates) and highly oxidised S (ester sulphates) forms, with the three groups representing 14-32%, 33-50% and 22-53% of the organic S in the humic substance extracts, respectively. Land use had a profound influence on the relative proportions of S species. Well-drained arable soils generally had a higher proportion of organic S present in the most oxidised form than the grassland soils collected nearby, whereas paddy soils showed a more reduced profile due to episodic flooding. In the Broadbalk Classical Experiment at Rothamsted, reversion of an arable system to grassland or woodland in the 1880s resulted in an increase of the most reduced and intermediate S species at the expense of the most oxidised S species. Long-term applications of farmyard manure to an arable plot also shifted S species from the most oxidised to the intermediate and the most reduced species. Sulphur immobilisation and gross mineralisation were determined in seven soils using the {sup 35}S isotope dilution method. Gross mineralisation during a 53-day incubation correlated more closely with the amounts of the most reduced and intermediate S species than with the most oxidised S species, suggesting that the former (C-bonded S) were the main source of organic S for mineralisation in the short-term.

Zhao,F.; Lehmann, J.; Solomon, D.; Fox, M.; McGrath, S.



Determination of Glyphosate, its Degradation Product Aminomethylphosphonic Acid, and Glufosinate, in Water by Isotope Dilution and Online Solid-Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry  

USGS Publications Warehouse

The U.S. Geological Survey method (0-2141-09) presented is approved for the determination of glyphosate, its degradation product aminomethylphosphonic acid (AMPA), and glufosinate in water. It was was validated to demonstrate the method detection levels (MDL), compare isotope dilution to standard addition, and evaluate method and compound stability. The original method USGS analytical method 0-2136-01 was developed using liquid chromatography/mass spectrometry and quantitation by standard addition. Lower method detection levels and increased specificity were achieved in the modified method, 0-2141-09, by using liquid chromatography/tandem mass spectrometry (LC/MS/MS). The use of isotope dilution for glyphosate and AMPA and pseudo isotope dilution of glufosinate in place of standard addition was evaluated. Stable-isotope labeled AMPA and glyphosate were used as the isotope dilution standards. In addition, the stability of glyphosate and AMPA was studied in raw filtered and derivatized water samples. The stable-isotope labeled glyphosate and AMPA standards were added to each water sample and the samples then derivatized with 9-fluorenylmethylchloroformate. After derivatization, samples were concentrated using automated online solid-phase extraction (SPE) followed by elution in-line with the LC mobile phase; the compounds separated and then were analyzed by LC/MS/MS using electrospray ionization in negative-ion mode with multiple-reaction monitoring. The deprotonated derivatized parent molecule and two daughter-ion transition pairs were identified and optimized for glyphosate, AMPA, glufosinate, and the glyphosate and AMPA stable-isotope labeled internal standards. Quantitative comparison between standard addition and isotope dilution was conducted using 473 samples analyzed between April 2004 and June 2006. The mean percent difference and relative standard deviation between the two quantitation methods was 7.6 plus or minus 6.30 (n = 179), AMPA 9.6 plus or minus 8.35 (n = 206), and glufosinate 9.3 plus or minus 9.16 (n = 16). The analytical variation of the method, comparison of quantitation by isotope dilution and multipoint linear regressed standard curves, and method detection levels were evaluated by analyzing six sets of distilled-water, groundwater, and surface-water samples spiked in duplicate at 0.0, 0.05, 0.10 and 0.50 microgram per liter and analyzed on 6 different days during 1 month. The grand means of the normalized concentration percentage recovery for glyphosate, AMPA, and glufosinate among all three matrices and spiked concentrations ranged from 99 to 114 plus or minus 2 to 7 percent of the expected spiked concentration. The grand mean of the percentage difference between concentrations calculated by standard addition and linear regressed multipoint standard curves ranged from 8 to 15 plus or minus 2 to 9 percent for the three compounds. The method reporting levels calculated from all the 0.05- microgram per liter spiked samples were 0.02 microgram per liter for all three compounds. Compound stability experiments were conducted on 10 samples derivatized four times for periods between 136 to 269 days. The glyphosate and AMPA concentrations remained relatively constant in samples held up to 136 days before derivatization. The half life of glyphosate varied from 169 to 223 days in the underivatized samples. Derivatized samples were analyzed the day after derivitization, and again 54 and 64 days after derivatization. The derivatized samples analyzed at days 52 and 64 were within 20 percent of the concentrations of the derivatized samples analyzed the day after derivatization.

Meyer, Michael T.; Loftin, Keith A.; Lee, Edward A.; Hinshaw, Gary H.; Dietze, Julie E.; Scribner, Elisabeth A.



Determination of radium isotope ratios and abundances in geologic samples by thermal ionization mass spectrometry.  


We describe chemical separation and mass spectrometric procedures for the measurement of radium isotopes in geologic samples. These methods provide 226Ra/228Ra ratio measurements for 1 g or less of rock sample containing subpicogram amounts of radium with precision better than 1.5% (95% confidence level). Radium-226 concentrations were measured by isotope dilution for smaller sample sizes (100-500 mg) containing as little as 1-10 fg of total 226Ra with similar high precision. PMID:1858983

Volpe, A M; Olivares, J A; Murrell, M T



Isotopic test of a thermally driven intraplate orogenic model, Australia  

NASA Astrophysics Data System (ADS)

A recently proposed model for intraplate orogenesis couples long-term self-heating of basement rocks by radioactive decay with thermal blanketing by overlying sedimentary deposits. This model has been tested in one of the type areas in central Australia, the Proterozoic Musgrave Complex, which was reworked in an Early Cambrian orogeny. We have determined the source of the pre orogenic and postorogenic sediments in the Amadeus basin immediately to the north of the reworked basement, including the fan deposits associated with uplift, comprising Uluru (Ayers Rock) and Kata Tjuta (Olgas). Detrital-zircon age populations indicate that all basin sediments were derived from the Musgrave Complex, which was therefore emergent rather than covered by sediments as required by the model. In the basement, the preservation of Mesoproterozoic mica ages during transpressive burial to depths of ˜40 km ca. 550 Ma indicates that the associated thermal pulse was short-lived, not long-lived as envisaged in the model. We conclude therefore that the thermal-blanketing model is inconsistent with the isotopic data and that the localization of deformation in intracratonic settings is associated with regions of contrasting strengths; in central Australia, these are along the margins of the Amadeus basin with the Musgrave Complex and Arunta inlier.

Camacho, A.; Hensen, B. J.; Armstrong, R.



Measurement of Mercury Species in Whole Blood Using Speciated Isotope Dilution Methodology Integrated with Microwave-Enhanced Solubilization and Spike Equilibration, Headspace-Solid-Phase Microextraction, and GC-ICP-MS Analysis.  


A biomonitoring method was developed for the determination of inorganic-, methyl-, and ethylmercury (Hg(2+), CH3Hg(+), and C2H5Hg(+), respectively) in whole blood by triple-spiking speciated isotope dilution mass spectrometry (SIDMS) using headspace (HS) solid-phase microextraction (SPME) in combination with gas chromatographic (GC) separation and inductively coupled plasma mass spectrometric (ICP-MS) detection. After spiking the blood sample with isotopically enriched analogues of the analytes ((199)Hg(2+), CH3(200)Hg(+) and C2H5(201)Hg(+)), the endogenous Hg species were solubilized in 2.0 mol L(-1) HNO3 and equilibrated with the spikes using a microwave-enhanced protocol. The microwaved sample was treated with a 1% (w/v) aqueous solution of sodium tetrapropylborate (buffered to pH 5.2), and the propylated Hg species were sampled in the HS using a Carboxen/polydimethylsiloxane-coated SPME fiber. The extracted species were thermally desorbed from the fiber in the GC injection port and determined by GC-ICP-MS. The analytes were quantified, with simultaneous correction for their method-induced transformation, on the basis of the mathematical relationship in triple-spiking SIDMS. The method was validated using a bovine blood standard reference material (SRM 966, Level 2). Analysis of human blood samples demonstrated the accuracy and reproducibility of the method, which can detect the Hg species down to 30 pg g(-1) in blood. The validity of the analytical results found for the blood samples was demonstrated using mass balance by comparing the sum of the concentrations of the individual Hg species with the total Hg in the corresponding samples; the latter was determined by isotope dilution mass spectrometry (IDMS) after decomposing the blood using EPA Method 3052 with single-spiking. PMID:24845130

Rahman, G M Mizanur; Wolle, Mesay Mulugeta; Fahrenholz, Timothy; Kingston, H M Skip; Pamuku, Matt



High-precision quadruple isotope dilution method for simultaneous determination of nitrite and nitrate in seawater by GCMS after derivatization with triethyloxonium tetrafluoroborate.  


Quadruple isotope dilution mass spectrometry (ID(4)MS) has been applied for simultaneous determination of nitrite and nitrate in seawater. ID(4)MS allows high-precision measurements and entails the use of isotopic internal standards ((18)O-nitrite and (15)N-nitrate). We include a tutorial on ID(4)MS outlining optimal experimental design which generates results with low uncertainties and obviates the need for direct (separate) evaluation of the procedural blank. Nitrite and nitrate detection was achieved using a headspace GCMS procedure based on single-step aqueous derivatization with triethyloxonium tetrafluoroborate at room temperature. In this paper the sample preparation was revised and fundamental aspects of this chemistry are presented. The proposed method has detection limits in the low parts-per-billion for both analytes, is reliable, precise, and has been validated using a seawater certified reference material (MOOS-2). Simplicity of the experimental design, low detection limits, and the use of quadruple isotope dilution makes the present method superior to the state-of-the-art for determination of nitrite and nitrate, and an ideal candidate for reference measurements of these analytes in seawater. PMID:24759746

Pagliano, Enea; Meija, Juris; Mester, Zoltán



Improved Isotopic Measurement of Plutonium by Thermal Ionization Mass Spectrometry  

SciTech Connect

Thermal ionization mass spectrometry (TIMS) is accepted widely as the benchmark method for precise and accurate isotopic determination of plutonium. TIMS is one of the few analytical methods capable of determining Pu in bioassay samples at the level required for detecting a 50 yr committed dose of 100 mRem resulting from an inhalation exposure to highly insoluble forms of Pu. Typically, Pu is measured in bioassay samples by radiochemical separation, electrodeposition onto a planchet, and radiometric determination by alpha spectrometry. If, based on the alpha spectrometry results, a sample is deemed to need a more sensitive analysis (i.e. suspected uptake, borderline alpha spectrometry positive for Pu uptake, etc.), then the sample is prepared for analysis by TIMS. Part of the development process for establishing a program to determine Pu in bioassay samples by TIMS at the Savannah River Site involved a careful evaluation of the Pu blank value in the reagents used for sample preparation and in urine blanks. This exercise allowed for the evaluation of the newly developed radiochemical separation procedure, the resin bead loading procedure, and the detection limits of the thermal ionization mass spectrometer.

Shick, C. Jr.



Geochemistry and isotope geochemistry of the Monfalcone thermal waters (northern Italy): inference on the deep geothermal reservoir  

NASA Astrophysics Data System (ADS)

Geochemical investigations were carried out to define the origin of the low- to moderate-temperature thermal waters feeding the Monfalcone springs in northern Italy. Chemical data indicate that waters approach the composition of seawater. Mixing processes with cold low-salinity waters are highlighted. The ?18O and ?D values are in the range -5.0 to -6.4 ‰, and -33 to -40 ‰, respectively, suggesting the dilution of the saline reservoir by karst-type freshwaters. A surplus of Ca2+ and Sr2+ ions with respect to a conservative mixing is ascribed to diagenetic reactions of the thermal waters with Cretaceous carbonates at depth. The measured Sr isotopic composition (87Sr/86Sr ratio) ranges between 0.70803 and 0.70814; after correction for the surplus Sr, a 87Sr/86Sr ratio indicating Miocene paleo-seawater is obtained. The dissolved gases indicate long-lasting gas-water interactions with a deep-originated gas phase of crustal origin, dominated by CO2 and marked by a water TDIC isotopic composition in the range -5.9 to-8.8 and helium signature with 0.08 < R/Ra < 0.27, which is a typical range for the crust. A possible scenario for the Monfalcone thermal reservoir consists of Miocene marine paleowaters which infiltrated through the karstic voids formed within the prevalently Cretaceous carbonates during the upper Eocene emersion of the platform, and which were entrapped by the progressive burial by terrigenous sediments.

Petrini, R.; Italiano, F.; Ponton, M.; Slejko, F. F.; Aviani, U.; Zini, L.



New commercial method for the enzymatic determination of creatinine in serum and urine evaluated: Comparison with a kinetic Jaffe method and isotope dilution-mass spectrometry  

SciTech Connect

We evaluated a new, simple, enzymatic kinetic method from Wako Chemicals GmbH in comparison with a kinetic Jaffe method by using isotope dilution-mass spectrometry (ID-MS) as a reference method. An ID-MS-calibrated serum standard was used. Both the enzymatic and the Jaffe method correlated well with ID-MS, except for sera with high concentrations of bilirubin. Ethyl acetoacetate, acetone, and glucose in serum interfered somewhat with the Jaffe method but not with the enzymatic method. We conclude that the present enzymatic method has merit as compared with a Jaffe method for routine work, but is more expensive.

Lindbaeck, B.B.; Bergman, A.



Investigation of the tungsten isotopes via thermal neutron capture  

NASA Astrophysics Data System (ADS)

Total radiative thermal neutron-capture ?-ray cross sections for the 182,183,184,186W isotopes were measured using guided neutron beams from the Budapest Research Reactor to induce prompt and delayed ? rays from natural and isotopically-enriched tungsten targets. These cross sections were determined from the sum of measured ?-ray cross sections feeding the ground state from low-lying levels below a cutoff energy, Ecrit, where the level scheme is completely known, and continuum ? rays from levels above Ecrit, calculated using the Monte Carlo statistical-decay code dicebox. The new cross sections determined in this work for the tungsten nuclides are ?0(182W)=20.5(14) b and ?11/2+(183Wm,5.2s )=0.177(18) b; ?0(183W)=9.37(38) b and ?5-(184Wm,8.33?s )=0.0247(55) b; ?0(184W)=1.43(10) b and ?11/2+(185Wm,1.67min)=0.0062(16) b; and, ?0(186W)=33.33(62) b and ?9/2+(187Wm,1.38?s)=0.400(16) b. These results are consistent with earlier measurements in the literature. The 186W cross section was also independently confirmed from an activation measurement, following the decay of 187W, yielding values for ?0(186W) that are consistent with our prompt ?-ray measurement. The cross-section measurements were found to be insensitive to choice of level density or photon strength model and only weakly dependent on Ecrit. Total radiative-capture widths calculated with dicebox showed much greater model dependence; however, the recommended values could be reproduced with selected model choices. The decay schemes for all tungsten isotopes were improved in these analyses. We were also able to determine new neutron-separation energies from our primary ?-ray measurements for the respective (n ,?) compounds: 183W [Sn=6190.88(6) keV]; 184W [Sn=7411.11(13) keV]; 185W [Sn=5753.74(5) keV]; and, 187W [Sn=5466.62(7) keV].

Hurst, A. M.; Firestone, R. B.; Sleaford, B. W.; Summers, N. C.; Révay, Zs.; Szentmiklósi, L.; Basunia, M. S.; Belgya, T.; Escher, J. E.; Krti?ka, M.



Chemical and Isotopic Data for Water from Thermal Springs and Wells of Oregon.  

National Technical Information Service (NTIS)

The thermal springs of Oregon range in composition from dilute NaHCO sub 3 waters to moderately saline CO sub 2 -charged NaCl-NaHCO sub 3 waters. Most of the thermal springs are located in southeastern or southcentral Oregon, with a few in northeastern Or...

R. H. Mariner J. R. Swanson G. J. Orris T. S. Presser W. C. Evans



Origin of isotopic heterogeneity in the solar nebula by thermal processing and mixing of nebular dust  

NASA Astrophysics Data System (ADS)

We have investigated Mo and W isotope compositions in acid leachates and an insoluble residue from the Murchison carbonaceous chondrite. The new data reveal variable enrichments of s- and r-process isotopes and demonstrate that several isotopically diverse presolar components are present in Murchison. The insoluble residue is enriched in s-process Mo and W, evidently due to the enrichment of presolar SiC grains. In contrast, Mo and W released by leaching with weak acids are depleted in s-process isotopes, most likely reflecting the isotope composition of the homogenized portion of the protosolar nebula. The Mo and W isotope compositions of the different leach steps are broadly correlated as expected from s-process nucleosynthesis theory, indicating that Mo and W are presumably hosted in the same carriers. However, at the bulk meteorite scale, no nucleosynthetic W isotope anomalies have been identified (except for IVB iron meteorites) in spite of large Mo isotope heterogeneities among the same samples. This decoupling of Mo and W isotopes in bulk meteorites may reflect physical mixing of varying proportions of isotopically diverse presolar components with a "normal" solar nebula component. Due to the high W/Mo ratio and near-terrestrial W isotope composition of the latter, such mixing has no measurable effect on W isotopes, but results in large Mo isotope variations. Alternatively, thermal processes within the solar nebula imparted Mo isotope heterogeneity on an initially homogeneous mixture of presolar dust, while W was not affected. Removal of volatile Mo oxides during the thermal destruction of fragile presolar components would have created isotopically heterogeneous reservoirs of nebular dust. Accretion of meteorite parent bodies from such variably processed dust would thus result in Mo isotope heterogeneities at the bulk meteorite scale. Other elements such as Os and W were not or only slightly affected because they were more refractory during thermal processing and, therefore, remained isotopically homogeneous. Thermal processing of presolar dust within the solar nebula can thus account for both isotope heterogeneities observed for some elements and the lack of such isotopic heterogeneity for other elements.

Burkhardt, Christoph; Kleine, Thorsten; Dauphas, Nicolas; Wieler, Rainer



Liquid-phase thermal diffusion isotope separation apparatus and method having tapered column  


A thermal diffusion counterflow method and apparatus for separating isotopes in solution in which the solution is confined in a long, narrow, vertical slit which tapers from bottom to top. The variation in the width of the slit permits maintenance of a stable concentration distribution with relatively long columns, thus permitting isotopic separation superior to that obtainable in the prior art.

Rutherford, William M. (Dayton, OH)



Determination of volatile elements in biological materials by isotopic dilution ETV-ICP-MS after dissolution with tetramethylammonium hydroxide or acid digestion.  


Isotopic dilution for the determination of Ag, Cd, Hg, Pb and Tl in biological materials by ETV-ICP-MS is proposed. The sample was simply dissolved with tetramethylammonium hydroxide (TMAH) or acid digested in a microwave furnace, with an on line matrix separation. When the dissolution was employed, Ir was used as a chemical modifier for Hg and Pb and Pd was used for Cd and Tl. No modifier was used for Ag. The pyrolysis temperatures were taken from pyrolysis temperature curves. The on line preconcentration was performed in a flow injection system with solenoid valves and was based on the analyte complexation with ammonium diethyldithiophosphate and sorption of the complexes on C(18) bonded to silica gel in a minicolumn. For the digested sample submitted to the analyte preconcentration procedure, a modifier, Ir, was only used for Hg. For the other analytes, since a low pyrolysis temperature, 300 degrees C, was employed, no modifier was added. The isotopic dilution calibration was applied to two certified materials, bovine liver and dog fish muscle, dissolved with TMAH or acid digested, and to another two certified materials, corn bran and rice flour, acid digested and submitted to analyte preconcentration. The obtained concentration values agree with the certified ones, showing that this calibration procedure leads to accurate results in the determination of low concentrations of volatile elements. Due to simplicity, the dissolution with TMAH is very attractive. PMID:18967922

Pozebon, D; Dressler, V L; Curtius, A J



Investigation of At-Vent Dynamics and Dilution of Gas Puffing Using Thermal Infrared Radiometers at Masaya Volcano, Nicaragua  

NASA Astrophysics Data System (ADS)

In order to develop a detailed understanding of the dynamics of gas puffing (gas release as a series of discrete clouds) and more sustained degassing (steady plumes of gas) during persistent volcanic degassing, measurements of gas mass flux are required in the vicinity of the volcanic vent. Masaya Volcano (Nicaragua), a persistently degassing system, is an ideal location for measuring the dynamics of releases of volcanic gas in the first few seconds of their propagation. We carried out two field experiments during February 2002 and March 2003, during which thermal infrared thermometers were targeted into the degassing vent at Masaya to record thermal variations related to variations in the at-vent gas emission over short (on the order of seconds) timescales. The thermometers recorded an oscillating signal as gas puffs passed through the field of view, detailing variations in the degassing process developing over time scales of seconds. These data were processed to extract puff frequencies, amplitudes, durations, emission velocities and volumes. These data showed that, over time periods of hours, the total gas flux was stable with little variation in the puffing frequency. However, between 2002 and 2003 we noted a systematic increase in mean plume temperature, puffing frequency, puff emission velocity and puff volume, as well as a decrease in mean puff duration. While the first 4 parameters respectively increased from 105 to 157°C, 6 to 7 puffs per minute, 2 to 3 m s^{- 1} and ~2300 to ~2900 m3, puff duration decreased from 10 to 8.5 seconds. These changes were consistent with a thermal-data-derived increase in emitted gas volume from 1.1 x 107 m3 d-1 to 1.6 x 107 m3 d-1 between 2002 and 2003. Turbulent gas puffs entrain surrounding air, and quantifying the magnitude of air entrainment, or dilution, represents a major challenge for the measurement of total volcanic gas emissions. Our observations of small gas puffs suggest that they behave as turbulent buoyant thermals, and we use equations for mass, momentum and buoyancy, coupled with the standard entrainment assumption for turbulent buoyant flows, to estimate the gas puff dilution. The theoretically calculated entrainment rate of 40% dilution between emission and detection yields total SO2 mass fluxes of 450 t d-1 and 640 t d-1 for 2002 and 2003, respectively. This compares well with UV-spectrometer SO2 fluxes of 470 and 680 t d-1 for February 2002 and March 2003, respectively.

Branan, Y. K.; Harris, A.; Watson, I.; Phillips, J.; Horton, K.; Williams-Jones, G.; Garbeil, H.



Isotope Production Facility Conceptual Thermal-Hydraulic Design Review and Scoping Calculations  

SciTech Connect

The thermal-hydraulic design of the target for the Isotope Production Facility (IPF) is reviewed. In support of the technical review, scoping calculations are performed. The results of the review and scoping calculations are presented in this report.

Pasamehmetoglu, K.O.; Shelton, J.D.



Determination of trace sulfur in biodiesel and diesel standard reference materials by isotope dilution sector field inductively coupled plasma mass spectrometry.  


A method is described for quantification of sulfur at low concentrations on the order of mgkg(-1) in biodiesel and diesel fuels using isotope dilution and sector field inductively coupled plasma mass spectrometry (ID-SF-ICP-MS). Closed vessel microwave-assisted digestion was employed using a diluted nitric acid and hydrogen peroxide decomposition medium to reduce sample dilution volumes. Medium resolution mode was employed to eliminate isobaric interferences at (32)S and (34)S related to polyatomic phosphorus and oxygen species, and sulfur hydride species. The method outlined yielded respective limits of detection (LOD) and limits of quantification (LOQ) of 0.7 mg kg(-1) S and 2.5 mg kg(-1) S (in the sample). The LOD was constrained by instrument background counts at (32)S but was sufficient to facilitate value assignment of total S mass fraction in NIST SRM 2723b Sulfur in Diesel Fuel Oil at 9.06±0.13 mg kg(-1). No statistically significant difference at a 95% confidence level was observed between the measured and certified values for certified reference materials NIST SRM 2773 B100 Biodiesel (Animal-Based), CENAM DRM 272b and NIST SRM 2723a Sulfur in Diesel Fuel Oil, validating method accuracy. PMID:24331043

Amais, Renata S; Long, Stephen E; Nóbrega, Joaquim A; Christopher, Steven J



A novel sample decomposition technique at atmospheric pressure for the determination of Os abundances in iron meteorites using isotope dilution inductively coupled plasma-mass spectrometry.  


A safe and reliable analytical technique for the determination of Os abundances in ten iron meteorites of various chemical groups was developed using isotope dilution inductively coupled plasma-mass spectrometry coupled with a sample decomposition technique. A major advantage of the sample decomposition technique developed here is that the pressure inside the reaction flask is not increased through the decomposition reaction because the flask is a fully opened system, obviating the risk of explosion of the glass apparatus. Another advantage is that there is no restriction in the sample size being decomposed. In this study, about 2 g of metallic sample were decomposed safely, and this sample size, > 10 times larger than that typically used for the Carius tube technique, allows one to obtain more reliable Os data for heterogeneous samples. The metallic samples were decomposed in a glass flask purged with Ar. Since the O2 was purged from the reaction flask, Os was not oxidised to volatile OsO4, thereby preventing significant evaporation loss of Os. The typical recovery of Os throughout the sample decomposition and separation processes was > 80%, and the total Os blank through the decomposition of a 1 g amount of sample was less than 20 pg. Os abundances were determined by means of stable isotope dilution mass spectrometry using a 190Os-enriched isotopic tracer. Except for Sikhote-Alin, the measured Os abundances in almost all the iron meteorites exhibited a good agreement with the previously published Os abundance data, within the analytical uncertainty achieved in this study (2-5%). For the Sikhote-Alin meteorite, on the basis of a better correlation between Os and Ir abundances, we believe that our Os abundance data should be more reliable. The Os abundance data obtained in this work clearly demonstrated the suitability of the newly developed sample decomposition procedure for low level Os determinations. PMID:11445949

Hattori, M; Hirata, T



Non-thermal plasma processing for environmental protection: decomposition of dilute VOCs in air  

Microsoft Academic Search

Non-thermal plasma processing is one of the most hopeful air-cleaning technologies to remove toxic gas contaminants in air. The historical background of the non-thermal plasma related with the electrostatics is described and the fundamental experimental system including the reactor designs and their power supplies is introduced. Some experimental results suggested the high potential of the plasma processing to decompose those

T. Oda



Stable isotope fractionation by thermal diffusion through partially molten wet and dry silicate rocks  

NASA Astrophysics Data System (ADS)

Water plays a fundamental role in affecting geochemical transport and physical properties of magmas. Here we show the previously undocumented behavior of water within partially molten silicate resting in a temperature gradient, producing O, Li and H isotope redistribution by thermal diffusion leading to enrichment of light isotopes at the hot end of the gradient. After weeks to months, fully molten as well as mostly crystalline portions of water-bearing experiments develop remarkably large isotope and chemical redistributions: up to 28‰ for ?18O, 144‰ for ?D, and 18‰ for ?7Li. In contrast, long-term dry experiments develop smaller (˜5‰ ?18O) isotopic fractionations only in the hotter end where it is molten or partially molten. Isotope fractionation of oxygen is linearly related to temperature, and the magnitude of isotopic separation per °C is ˜2× larger for wet experiments than dry ones. We explain this by water de-polymerizing the silicate structure leading to a smaller size of diffusing SiOx fragments. The magnitude of isotope separation between the hot and cold ends for Li, Mg, Fe, O, and H isotopes increases linearly with ?Mheavy-light/Mlight. These relationships provide predictive tests for natural rocks and highlight the role of water in isotope and compositional redistribution during temperature gradient mediated processes. We discuss the implications to natural environments in which the lightest stable isotopes (H, Li, O) with the greatest ?Mheavy-light/Mlight and fastest diffusion coefficients are capable of achieving mass-dependent redistribution in a transient temperature gradient. These experiments underscore the importance of solution-reprecipitation in wet subsolidus systems and demonstrate that isotopic redistribution can be established ˜6 orders of magnitude quicker than by diffusion through a traditional silicate melt at higher temperature. This has important implications for timescales of natural isotope and chemical redistribution by thermal diffusion.

Bindeman, I. N.; Lundstrom, C. C.; Bopp, C.; Huang, F.



Light stable isotope study of the Roosevelt Hot Springs thermal area, Southwestern Utah  

SciTech Connect

The isotopic composition of hydrogen, oxygen, and carbon has been determined for regional cold springs, thermal fluids, and rocks and minerals from the Roosevelt Hot Springs thermal area. The geothermal system has developed within plutonic granitic rocks and amphibolite facies gneiss, relying upon fracture-controlled permeability for the migration of the thermal fluids. Probably originating as meteoric waters in the upper elevations of the Mineral Mountains, the thermal waters sampled in the production wells display an oxygen isotopic shift of at least +1.2. Depletions of delta /sup 18/O in wole rock, K-feldspar, and biotite have a positive correlation with alteration intensity. W/R mass ratios, calculated from the isotopic shifts of rock and water, range up to 3.0 in a producing horizon of one well, although the K-feldspar has experienced only 30% exchange with the thermal waters. While veinlet quartz has equilibrated with the thermal waters, the /sup 18/O values of K-mica clay, an alteration product of plagioclase, mimic the isotopic composition of K-feldspar and whole rock. This suggests that locally small W/R ratios enable plagioclase to influence its alteration products by isotopic exchange.

Rohrs D.T.; Bowman, J.R.



Interfacing reversed-phase nanoHPLC with ICP-MS and on-line isotope dilution analysis for the accurate quantification of selenium-containing peptides in protein tryptic digests  

Microsoft Academic Search

An interface between nanoHPLC and ICP-MS was developed. It allowed the stable introduction into an ICP of mobile phases containing up to 90% of acetonitrile at flow rates of less than 500 nL min ? 1 . The on-line post-column addition of an isotopically enriched spike at flow rates of less than 4 mL min ? 1 enabled isotope dilution

Pierre Giusti; Dirk Schaumloffel; Jorge Ruiz Encinar; Joanna Szpunar



Combined method for the determination of ?-aminobutyric and ?-alanine in cerebrospinal fluid by stable isotope dilution mass spectrometry  

Microsoft Academic Search

A previously described method for the determination of GABA in CSF has been expanded to include both GABA and ?-ALA, using a single GC–MS analysis. A stable isotope labelled internal standard for ?-ALA was synthesised to achieve accurate quantification. This new combined method expands the diagnostic power compared to an isolated GABA measurement. Control values for free and total GABA

E. A Struys; W. S Guérand; H. J ten Brink; C Jakobs



Quantification by solid phase micro extraction and stable isotope dilution assay of norisoprenoid compounds in red wines obtained from Piedmont rare varieties.  


A method to identify and quantify megastigmane norisoprenoid compounds in wines was developed using headspace solid phase micro extraction (SPME) coupled with gas-chromatography/mass-spectrometry (GC-MS). Three different compounds were quantified by stable isotope dilution assay (SIDA): ?-damascenone, ?-ionone and ?-ionone. Particular attention was paid to maximising the method's sensitivity while reducing the extraction time. To optimise the extraction conditions, a statistically designed experiment was performed using extraction time, extraction temperature and ethanol content as operating variables. Five different SPME fibres suitable for the analysis of volatile compounds were compared. This study confirmed that the PDMS/DVB coating performs best for the quantification of ?-damascenone and ?-ionone, and the crucial influence of ethanol content of the sample on extraction effectiveness. Finally, the optimised method was applied to the study of various wines derived from rare and autochthonous grape varieties of north-western Italy. PMID:22980832

Petrozziello, Maurizio; Borsa, Daniela; Guaita, Massimo; Gerbi, Vincenzo; Bosso, Antonella



Improving gas chromatographic determination of residual solvents in pharmaceuticals by the combined use of headspace solid-phase microextraction and isotopic dilution.  


Cyclohexane and toluene were gas chromatographically determined via headspace solid-phase microextraction both in ketoprofen drug substance and ketoprofen capsules by a procedure relying on isotopic dilution (ID), an analytical tool derived from mass spectrometry (MS). This approach, using an internal standard method, gave mean precision and accuracy (RSD 2.56%, 2.97% and bias 0.21%, -0.99% for cyclohexane and toluene, respectively) not obtainable by the more commonly used external standard ones in the presence of real sample matrices. Optimisation of the operative conditions was also supported by experimental design. More generally, the proposed method, exploiting ID without resort to the costly MS instrumentation, could be recommended whenever opportune deuterated analogues of the target analytes and GC capillary columns able to separate all the peaks involved are ready available on the market. PMID:11358250

Coran, S A; Giannellini, V; Furlanetto, S; Bambagiotti-Alberti, M; Pinzauti, S



Sectional power-law correction for the accurate determination of lutetium by isotope dilution multiple collector-inductively coupled plasma-mass spectrometry  

NASA Astrophysics Data System (ADS)

In this study, we employ a sectional power-law (SPL) correction that provides accurate and precise measurements of 176Lu/ 175Lu ratios in geological samples using multiple collector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Three independent power laws were adopted based on the 176Lu/ 176Yb ratios of samples measured after chemical chromatography. Using isotope dilution (ID) techniques and the SPL correction method, the measured lutetium contents of United States Geological Survey rock standards (BHVO-1, BHVO-2, BCR-2, AGV-1, and G-2) agree well with the recommended values. Results obtained by conventional ICP-MS and INAA are generally higher than those obtained by ID-TIMS and ID-MC-ICP-MS; this discrepancy probably reflects oxide interference and inaccurate corrections.

Yuan, Hong-Lin; Gao, Shan; Zong, Chun-Lei; Dai, Meng-Ning



Application of amino acid analysis using hydrophilic interaction liquid chromatography coupled with isotope dilution mass spectrometry for peptide and protein quantification.  


Amino acid analysis that is based on the use of hydrophilic interaction liquid chromatography (HILIC) coupled with isotope dilution mass spectrometry (IDMS) has been developed for the accurate quantification of underivatized amino acids from hydrolyzed protein/peptide. Sufficient separation of amino acids on a zwitterion chromatography (ZIC)-HILIC column was achieved after removal of chloride ions in the hydrolyzate. The detection limits and quantification limits as concentration of the four amino acids ranged from 0.003 to 0.04pmol microL(-1) and from 0.01 to 0.1pmol microL(-1), respectively. The analytical results for the certified reference materials, angiotensin I and bovine serum albumin (BSA), were satisfactory. Furthermore, the quantitative results by this method were compared with those by the commercially available precolumn method, derivatizd with aminoquinolylhydroxysuccinimidyl carbamate (AQC method), and better recovery and more precise data were obtained with this method. PMID:19665950

Kato, Megumi; Kato, Hisashi; Eyama, Sakae; Takatsu, Akiko



Ultrasonication extraction and gel permeation chromatography clean-up for the determination of polycyclic aromatic hydrocarbons in edible oil by an isotope dilution gas chromatography–mass spectrometry.  


An analytical method for the determination of US EPA priority pollutant 16 polycyclic aromatic hydrocarbons (PAHs) in edible oil was developed by an isotope dilution gas chromatography-mass spectrometry (GC-MS). Extraction was performed with ultrasonication mode using acetonitrile as solvent, and subsequent clean-up was applied using narrow gel permeation chromatographic column. Three deuterated PAHs surrogate standards were used as internal standards for quantification and analytical quality control. The limits of quantification (LOQs) were globally below 0.5 ng/g, the recoveries were in the range of 81-96%, and the relative standard deviations (RSDs) were lower than 20%. Further trueness assessment of the method was also verified through participation in international cocoa butter proficiency test (T0638) organised by the FAPAS with excellent results in 2008. The results obtained with the described method were satisfying (z ? 2). The method has been applied to determine PAH in real edible oil samples. PMID:20627308

Wang, Jian-Hua; Guo, Cui



Accurate determination of sulfur in gasoline and related fuel samples using isotope dilution ICP-MS with direct sample injection and microwave-assisted digestion.  


Inductively coupled plasma isotope-dilution mass spectrometry (ICP-IDMS) with direct injection of isotope-diluted samples into the plasma, using a direct injection high-efficiency nebulizer (DIHEN), was applied for accurate sulfur determinations in sulfur-free premium gasoline, gas oil, diesel fuel, and heating oil. For direct injection a micro-emulsion consisting of the corresponding organic sample and an aqueous 34S-enriched spike solution with additions of tetrahydronaphthalene and Triton X-100, was prepared. The ICP-MS parameters were optimized with respect to high sulfur ion intensities, low mass-bias values, and high precision of 32S/34S ratio measurements. For validation of the DIHEN-ICP-IDMS method two certified gas oil reference materials (BCR 107 and BCR 672) were analyzed. For comparison a wet-chemical ICP-IDMS method was applied with microwave-assisted digestion using decomposition of samples in a closed quartz vessel inserted into a normal microwave system. The results from both ICP-IDMS methods agree well with the certified values of the reference materials and also with each other for analyses of other samples. However, the standard deviation of DIHEN-ICP-IDMS was about a factor of two higher (5-6% RSD at concentration levels above 100 mircog g(-1)) compared with those of wet-chemical ICP-IDMS, mainly due to inhomogeneities of the micro-emulsion, which causes additional plasma instabilities. Detection limits of 4 and 18 microg g(-1) were obtained for ICP-IDMS in connection with microwave-assisted digestion and DIHEN-ICP-IDMS, respectively, with a sulfur background of the used Milli-Q water as the main limiting factor for both methods. PMID:15232670

Heilmann, Jens; Boulyga, Sergei F; Heumann, Klaus G



Laser-induced migration and isotope separation of epi-thermal monomers and dimers in supercooled free jets  

NASA Astrophysics Data System (ADS)

Explicit relations are developed to estimate the outflux of migrating isotopomers iQF6 to the outskirts of a supersonic supercooled free jet whose core is irradiated by a co-axial laser beam and intercepted by a skimmer that separates core gas from peripheral gases. The QF6 target gas is diluted in carrier gas G (G = He, N2, Ar, Xe, SF6, etc.) which determines the jet's supersonic characteristics and forms QF6:G dimers at low temperatures. Under isotope-selective laser excitation, excited iQF6* convert their vibrational energy V into kinetic energy T after forming transient iQF6*:G dimers that dissociate in sub-microseconds. Three migrating groups with different transport parameters are created in the jet: thermal monomers, faster-moving epithermal monomers, and slower-moving dimers. Jet-core-fleeing QF6 is enriched in iQF6 due to enhanced outwards migration of iQF6! epithermals and reduced escape of jQF6:G dimers in the jet. Isotope enrichments in the rim gases are highest for heavier carrier gases such as G = Xe or G = SF6.

Eerkens, Jeff W.



Experimental investigation of sulphur isotope partitioning during outgassing of hydrogen sulphide from diluted aqueous solutions and seawater.  


The diffusion of hydrogen sulphide across the sediment-water interface and subsequent liberation to the atmosphere may occur in iron-deficient coastal marine environments with enhanced microbial activity in surface sediments and corresponding accumulation of dissolved H2S in near-surface pore waters. The involvement of analogue processes in periods of global mass extinctions during Earth's history (e.g. at the Permian-Triassic boundary) is currently in discussion [L.R. Kump, A. Pavlov, and M. Arthur,Massive Release of Hydrogen Sulfide to the Surface Ocean and Atmosphere During Intervals of Oceanic Anoxia, Geology 33, 397 (2005)]. The outgassing of H?S is associated with a fractionation of the stable sulphur isotopes, which has so far only been investigated experimentally at selected acidic and neutral pH values, and no experiments with seawater had been carried out. In this communication, we report on sulphur isotope fractionation that takes place during the experimental degassing of H?S from aqueous solution by an inert gas (N?) at 21 °C. Experiments were conducted in the pH range between 2.6 and 10.8, corresponding to the dominance fields of dissolved hydrogen sulphide (H?S(aq)), bisulphide (HS-(aq)), and mixtures of both sulphide species. Overall isotope enrichment factors between -1.6 and +3.0‰ were observed, with the residual dissolved sulphide being enriched or depleted in ³?S compared to the liberated H?S at low and high pH values, respectively. The difference in the low and high pH isotope fractionation effects can be explained by isotope exchange between H?S(aq) and HS-(aq) [B. Fry, H. Gest, and J.M. Hayes, Sulfur Isotope Effects Associated with Protonation of HS- and Volatilization of H?S, Chem. Geol. (Isot. Geosci. Sec.) 58, 253 (1986); R. Geßler and K. von Gehlen, Investigation of Sulfur Isotope Fractionation Between H2S Gas and Aqueous Solutions, Fresenius J. Anal. Chem. 324, 130 (1986)] followed by the subsequent transfer of H?S(aq) to the gaseous phase. The assumption of pure physical outgassing of H?S(aq) at low pH values leads to an isotope enrichment factor of -0.9 ± 0.4‰ (n = 14) which is caused by the combined differences in dehydration and diffusion coefficients of H?³²S(aq) and H?³?S(aq). In the pH range of natural surface and shallow pore waters, ³?S will be equal to or enriched in the gaseous phase compared to the aqueous solution, therefore creating no or a slight enrichment of ³²S in the aqueous solution. Experiments in seawater solution showed no significant influence of increased ionic strength and changed corresponding aqueous speciation on sulphur isotope effects. PMID:21154004

Baune, Claudia; Bottcher, Michael E



Gas chromatography-combustion-mass spectrometry with postcolumn isotope dilution for compound-independent quantification: its potential to assess HS-SPME procedures.  


A quadrupole GC-MS instrument with an electron ionization (EI) source has been modified to enable application of postcolumn isotope dilution analysis for the standardless quantification of organic compounds injected in the gas chromatograph. Instrumental modifications included the quantitative conversion of the separated compounds into CO(2), using a postcolumn combustion furnace, and the subsequent mixing of the gas with a constant flow of (13)CO(2) diluted in helium. The online measurement of the (12)CO(2)/(13)CO(2) (44/45) ratio in the EI-MS allowed us to obtain quantitative data without resorting to compound-specific standards. Validation of the procedure involved the analysis of standard solutions containing different families of organic compounds (C(9)-C(20) linear hydrocarbons, BTEX and esters) obtaining satisfactory results in all cases in terms of absolute errors (<6%) and precision (<4% RSD). The developed procedure showed excellent linearity over the range assayed (2 orders of magnitude) and adequate detection limits for carbon containing compounds (0.8 pg C s(-1)). The generic value of this compound-independent calibration approach was assessed by studying the quantitative performance of Head Space-Solid Phase Microextraction (HS-SPME). The proposed compound-independent quantification by EI-MS permits comparison of the performance of different fibers by assessing analyte recoveries with extreme robustness, simplicity, and precision. PMID:20704376

Cueto Díaz, Sergio; Ruiz Encinar, Jorge; Sanz-Medel, Alfredo; García Alonso, J Ignacio



Inoculation of Bacillus sphaericus UPMB-10 to Young Oil Palm and Measurement of Its Uptake of Fixed Nitrogen Using the 15N Isotope Dilution Technique  

PubMed Central

There are increasing applications of diazotrophic rhizobacteria in the sustainable agriculture system. A field experiment on young immature oil palm was conducted to quantify the uptake of N derived from N2 fixation by the diazotroph Bacillus sphaericus strain UPMB-10, using the 15N isotope dilution method. Eight months after 15N application, young immature oil palms that received 67% of standard N fertilizer application together with B. sphaericus inoculation had significantly lower 15N enrichment than uninoculated palms that received similar N fertilizers. The dilution of labeled N served as a marker for the occurrence of biological N2 fixation. The proportion of N uptake that was derived from the atmosphere was estimated as 63% on the whole plant basis. The inoculation process increased the N and dry matter yields of the palm leaflets and rachis significantly. Field planting of young, immature oil palm in soil inoculated with B. sphaericus UPMB-10 might mitigate inorganic fertilizer-N application through supplementation by biological nitrogen fixation. This could be a new and important source of nitrogen biofertilizer in the early phase of oil palm cultivation in the field.

Zakry, Fitri Abdul Aziz; Shamsuddin, Zulkifli H.; Rahim, Khairuddin Abdul; Zakaria, Zin Zawawi; Rahim, Anuar Abdul



On the origin of the two thermally driven relaxations in diluted spin ice Dy(1.6)Y(0.4)Ti2O7.  


We report quantitative analysis of the ac susceptibility of the diluted spin ice compound Dy(1.6)Y(0.4)Ti(2)O(7), by fitting the frequency spectra of the two observed relaxation modes with a double Cole-Cole formula. Our results suggest that both modes are thermally activated, with the same intrinsic frequency, but different activation barriers. We propose that these thermally activated relaxation modes can be attributed to correlated spin clusters. PMID:23256967

Xing, Hui; Guo, Hanjie; Feng, Chunmu; Xu, Zhu-An; Zeng, Hao



Radium isotope geochemistry of thermal waters, Yellowstone National Park, Wyoming, USA  

Microsoft Academic Search

Radium isotope activities ( 226 Ra, 228 Ra, and 224 Ra), chemical compositions, and sulfur isotope ratios in sulfate were determined for water samples from thermal areas in Yellowstone National Park, Wyoming. Activities of 226 Ra in these waters range from <0.2 to 37.9 dpm\\/kg. Activity ratios of 228 Ra \\/ 226 Ra range from 0.26 to 14.2, and those

N. C. Sturchio; J. K. Bohlke; F. J. Markun



Radium isotope geochemistry of thermal waters, Yellowstone National Park, Wyoming, USA  

Microsoft Academic Search

Radium isotope activities ([sup 226]Ra, [sup 228]Ra, and [sup 224]Ra), chemical compositions, and sulfur isotope ratios in sulfate were determined for water samples from thermal areas in Yellowstone National Park, Wyoming. Activities of [sup 226]Ra in these waters range from <0.2 to 37.9 dpm\\/kg. Activity ratios of [sup 228]Ra\\/[sup 226]Ra range from 0.26 to 14.2, and those of [sup 224]Ra\\/[sup

N. C. Sturchio; J. K. Bohlke; F. J. Markun



Development of a quantitative method for determination of acrylamide in infant powdered milk and baby foods in jars using isotope dilution liquid chromatography\\/electrospray ionization tandem mass spectrometry  

Microsoft Academic Search

An improved method has been developed for the determination of acrylamide in infant powdered milk and baby foods in jars, a particular class of foodstuffs which represent an important source of nutrition for young infants and babies. This method uses isotope dilution liquid chromatography coupled to a tandem mass spectrometer with electrospray ionization and is significantly more sensitive than previous

Jingjing Jiao; Yu Zhang; Yiping Ren; Xiaoqin Wu; Ying Zhang



Determination of Rhenium and Platinum in Natural Waters and Sediments, and Iridium in Sediments by Flow Injection Isotope Dilution Inductively Coupled Plasma Mass Spectrometry. (Reannouncement with New Availability Information).  

National Technical Information Service (NTIS)

Methods have been developed to measure Re, Ir, and Pt in natural waters and sediments by isotope dilution inductively coupled plasma mass spectrometry (ID-ICPMS). The techniques have been applied to determination of the three elements in sediments, Pt in ...

D. C. Colodner E. A. Boyle J. M. Edmond



Rapid and Precise Measurement of Serum Branched-Chain and Aromatic Amino Acids by Isotope Dilution Liquid Chromatography Tandem Mass Spectrometry  

PubMed Central

Background Serum branched-chain and aromatic amino acids (BCAAs and AAAs) have emerged as predictors for the future development of diabetes and may aid in diabetes risk assessment. However, the current methods for the analysis of such amino acids in biological samples are time consuming. Methods An isotope dilution liquid chromatography tandem mass spectrometry (ID-LC/MS/MS) method for serum BCAAs and AAAs was developed. The serum was mixed with isotope-labeled BCAA and AAA internal standards and the amino acids were extracted with acetonitrile, followed by analysis using LC/MS/MS. The LC separation was performed on a reversed-phase C18 column, and the MS/MS detection was performed via the positive electronic spray ionization in multiple reaction monitoring mode. Results Specific analysis of the amino acids was achieved within 2 min. Intra-run and total CVs for the amino acids were less than 2% and 4%, respectively, and the analytical recoveries ranged from 99.6 to 103.6%. Conclusion A rapid and precise method for the measurement of serum BCAAs and AAAs was developed and may serve as a quick tool for screening serum BCAAs and AAAs in studies assessing diabetes risk.

Yang, Ruiyue; Dong, Jun; Guo, Hanbang; Li, Hongxia; Wang, Shu; Zhao, Haijian; Zhou, Weiyan; Yu, Songlin; Wang, Mo; Chen, Wenxiang



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

PubMed Central

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

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



Simultaneous analysis of phthalates, adipate and polycyclic aromatic hydrocarbons in edible oils using isotope dilution-gas chromatography-mass spectrometry.  


A method for simultaneous determination of 12 priority phthalates, adipate and polycyclic aromatic hydrocarbons (PAHs) in edible oils by isotope dilution-gas chromatography-mass spectrometry (ID-GC-MS) was developed for fast, accurate and trace analysis. The extraction and clean-up procedures were optimised, and using stable isotope-labelled internal standards for each analyte, relative standard deviations (RSDs) of 0.92-10.6% and spiked sample recoveries of 80.6-97.8% were obtained. Limits of detection for PAHs were in the range of 0.15-0.77 µg/kg and those for phthalates were in the range of 4.6-10.0 µg/kg. The calibration curves exhibited good linearities with regression coefficients of R(2) ? 0.99. Twelve edible oils were examined to evaluate the efficiency of this method. Among the 12 analytes, dibutyl phthalates (DBP), diethylhexyl phthalates (DEHP), diethylhexyl adipate (DEHA), benzo[a]anthracene (B[a]A), chrysene (Chry) and benzo[b]fluoranthene (B[b]F) were detected in the range of 1.17-806 µg/kg. PMID:25029399

Oh, Min-Seok; Lee, Seon-Hwa; Moon, Myeong Hee; Lee, Dong Soo; Park, Hyun-Mee



Determination of steroid hormones in a human-serum reference material by isotope dilution--mass spectrometry: A candidate definitive method for cortisol  

SciTech Connect

We report a method, based on isotope dilution--mass spectrometry, for determining cortisol in a pooled specimen of human serum. Isotopically labeled cortisol is added to 5.0 mL of serum so that the molar concentrations of labeled cortisol and unlabeled cortisol are approximately equal. The specimen and two calibration standards are extracted with dichloromethane, and the extracted cortisol is converted to the methoxime-trimethylsilyl ether derivative. Samples and standards are analyzed by gas chromatography--mass spectrometry by monitoring the peak areas for m/z 605 and 608. The cortisol concentration is calculated by linear interpolation between the two bracketing standards. Variances of data collected during six weeks showed that the overall coefficient of variation (CV) was 0.69% (n . 32); the within-vial CV, 0.63%; the among-vial CV, 0.22%; and the among-day CV, 0.15% (means . 3.973 nmol/vial). Method specificity was demonstrated by liquid chromatographic as well as C/sub 8/ mini-column cleanup of samples before derivation, by alternative ion monitoring at m/z 636 and 639, and by negative-ion chemical ionization at m/z 459 and 462. Derivatives of all observed degradation products of cortisol under basic, neutral, and acidic conditions did not interfere.

Patterson, D.G.; Patterson, M.B.; Culbreth, P.H.; Fast, D.M.; Holler, J.S.; Sampson, E.J.; Bayse, D.D.



Improved Optoelectronic Properties of Rapid Thermally Annealed Dilute Nitride GaInNAs Photodetectors  

NASA Astrophysics Data System (ADS)

We investigate the optical and electrical characteristics of GaInNAs/GaAs long-wavelength photodiodes grown under varying conditions by molecular beam epitaxy and subjected to postgrowth rapid thermal annealing (RTA) at a series of temperatures. It is found that the device performance of the nonoptimally grown GaInNAs p +- i- n + structures, with nominal compositions of 10% In and 3.8% N, can be improved significantly by the RTA treatment to match that of optimally grown structures. The optimally annealed devices exhibit overall improvement in optical and electrical characteristics, including increased photoluminescence brightness, reduced density of deep-level traps, reduced series resistance resulting from the GaAs/GaInNAs heterointerface, lower dark current, and significantly lower background doping density, all of which can be attributed to the reduced structural disorder in the GaInNAs alloy.

Tan, S. L.; Hunter, C. J.; Zhang, S.; Tan, L. J. J.; Goh, Y. L.; Ng, J. S.; Marko, I. P.; Sweeney, S. J.; Adams, A. R.; Allam, J.; David, J. P. R.



Determination of serum uric acid using high-performance liquid chromatography (HPLC)/isotope dilution mass spectrometry (ID-MS) as a candidate reference method.  


Uric acid is an important diagnostic marker of catabolism of the purine nucleosides, and accurate measurements of serum uric acid are necessary for proper diagnosis of gout or renal disease appearance. A candidate reference method involving isotope dilution coupled with liquid chromatography/mass spectrometry (LC/MS) has been described. An isotopically labeled internal standard, [1,3-(15)N(2)] uric acid, was added to serum, followed by equilibration and protein removal clean up to prepare samples for liquid chromatography/mass spectrometry electrospray ionization (LC/MS-ESI) analyses. (M-H)(-) ions at m/z 167 and 169 for uric acid and its labeled internal standard were monitored for LC/MS. The accuracy of the measurement was evaluated by a comparison of results of this candidate reference method on lyophilized human serum reference materials for uric acid (Standard Reference Materials SRM909b) with the certified values determined by gas chromatography/mass spectrometry reference methods and by a recovery study for the added uric acid. The method performed well against the established reference method of ion-exchange followed by derivatization isotope dilution (ID) gas chromatography mass spectrometry (ID-GC/MS). The results of this method for uric acid agreed well with the certified values and were within 0.10%. The amounts of uric acid recovered and added were in good agreement for the three concentrations. This method was applied to determine uric acid in samples of frozen serum pools. Excellent precision was obtained with within-set CVs of 0.08-0.18% and between-set CVs of 0.02-0.07% for LC/MS analyses. Liquid chromatography/tandem mass spectrometry electrospray ionization (LC/MS/MS-ESI) analysis was also performed. The LC/MS and LC/MS/MS results were in very good agreement (within 0.14%). This LC/MS method, which demonstrates good accuracy and precision, and is in the speed of analysis without the need for a derivatization stage, qualifies as a candidate reference method. This method can be used as an alternative reference method to provide an accuracy base to which the routine methods can be compared. PMID:17704012

Dai, Xinhua; Fang, Xiang; Zhang, Chunmei; Xu, Ruifeng; Xu, Bei



Cadmium determination in natural waters at the limit imposed by European legislation by isotope dilution and TiO2 solid-phase extraction.  


The cadmium content in surface water is regulated by the last European Water Framework Directive to a maximum between 0.08 and 0.25 ?g L(-1) depending on the water type and hardness. Direct measurement of cadmium at this low level is not straightforward in real samples, and we hereby propose a validated method capable of addressing cadmium content below ?g L(-1) level in natural water. It is based on solid-phase extraction using TiO(2) nanoparticles as solid sorbent (0.05 g packed in mini-columns) to allow the separation and preconcentration of cadmium from the sample, combined to direct isotope dilution and detection by inductively coupled plasma mass spectrometry (ID-ICP-MS). The extraction setup is miniaturised and semi-automated to reduce risks of sample contamination and improve reproducibility. Procedural blanks for the whole measurement process were 5.3 ± 2.8 ng kg(-1) (1 s) for 50 g of ultrapure water preconcentrated ten times. Experimental conditions influencing the separation (including loading pH, sample flow rates, and acid concentration in the eluent) were evaluated. With isotope dilution the Cd recovery rate does not have to be evaluated carefully. Moreover, the mathematical model associated to IDMS is known, and provides transparency for the uncertainty propagation. Our validation protocol was in agreement with guidelines of the ISO/IEC 17025 standard (chapter 5.4.5). Firstly, we assessed the experimental factors influencing the final result. Secondly, we compared the isotope ratios measured after our separation procedure to the reference values obtained with a different protocol for the digested test material IMEP-111 (mineral feed). Thirdly, we analysed the certified reference material BCR-609 (groundwater). Finally, combined uncertainties associated to our results were estimated according to ISO-GUM guidelines (typically, 3-4% k = 2 for a cadmium content of around 100 ng kg(-1)). We applied the developed method to the groundwater and wastewater samples ERM-CA615 and BCR-713, respectively, and results agreed with certificate values within uncertainty statements. PMID:21858497

García-Ruiz, Silvia; Petrov, Ivan; Vassileva, Emilia; Quétel, Christophe R



Chemical and isotopic data for water from thermal springs and wells of Oregon  

SciTech Connect

The thermal springs of Oregon range in composition from dilute NaHCO/sub 3/ waters to moderately saline CO/sub 2/-charged NaCl-NaHCO/sub 3/ waters. Most of the thermal springs are located in southeastern or southcentral Oregon, with a few in northeastern Oregon and near the contact of the Western Cascades with the High Cascades. Thermal springs in the central and northern parts of the Cascades generally issue moderately saline NaCl waters. Farther south in the Cascades, the thermal waters are high in CO/sub 2/ as well as chloride. Most thermal springs in northeastern Oregon issue dilute NaHCO/sub 3/ waters of high pH (>8.5). These waters are similar to the thermal waters which issue from the Idaho batholith, farther east. Most of the remaining thermal waters are Na mixed-anion waters. Based on the chemical geothermometers, Mickey Srpings, Hot Borax Lake, Alvord Hot Springs, Neal Hot Springs, Vale Hot Springs, Crump Well, Hunters (Lakeview) Hot Springs, and perhaps some of the springs in the Cascades are associated with the highest temperature systems (>150/sup 0/C).

Mariner, R.H.; Swanson, J.R.; Orris, G.J.; Presser, T.S.; Evans, W.C.



Thermal property characterization of single crystal diamond with varying isotopic composition  

SciTech Connect

The mirage-effect/thermal wave technique as a modern technique for thermal property characterization is described. The thermal diffusivity of a material is determined by measuring the time and space varying temperature distribution (thermal wave) in the material generated by an intensity modulated heating laser beam. These thermal waves are detected through the deflection of a probe laser beam due to modulation of gradient of the index of refraction (mirage effect) either in the air above the specimens (the in-air technique) or in the specimen itself (the in-solid technique). Three-dimensional theories, for both in-air and in-solid mirage techniques, are represented. In order to extract the material parameters by comparing the theory with experimental data, an extensive data analysis procedure based on multiparameter-least-squares has been developed. The experimental and data analysis details are discussed. Topics concerns with the quality and reliability of the measurements are addressed. This technique has been successfully applied to the thermal property characterization of single crystal diamond with varying isotope contents. The results showed a 50% enhancement in the thermal conductivity by removal of C[sup 13] content from 1.1% to 0.1% in diamond at room temperature. The technique has also been adapted to function in cryogenic temperatures. The temperature dependence of thermal conductivity in the temperature range 80-378K for natural IIA specimen and 187-375K for isotopically enriched specimen are obtained, the former results agree with previous works and the latter results demonstrate the isotope effect on the thermal conductivity of single crystal diamond consistently in a large temperature range. The physical source of this enhancement in diffusivity due to the isotope effect in diamond is discussed. The discussion is based on the full Callaway's theory with emphasizing the role of N-processes in the phonon scattering mechanism.

Wei, L.



Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry  

NASA Technical Reports Server (NTRS)

A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

Bandy, Alan R.; Thornton, Donald C.; Driedger, Arthur R., III



Identification of ground water contaminations by landfills using precise boron isotope ratio measurements with negative thermal ionization mass spectrometry  

Microsoft Academic Search

Precise boron isotope ratio measurements with negative thermal ionization mass spectrometry were used for the identification\\u000a of ground water contaminations by leakages of landfills. BO-\\u000a 2thermal ions were produced to determine the 11B\\/10B isotope ratio, which was expressed as ?11B value in ‰ normalized to the standard reference material NIST SRM 951. For example, household waste influences the boron\\u000a isotope

S. Eisenhut; K. G. Heumann



Helium-carbon isotopic composition of thermal waters from Tunisia  

NASA Astrophysics Data System (ADS)

Tunisia has numerous thermo-mineral springs. Previous studies have shown that their chemical composition and occurrence are strongly influenced by the regional geology, however little work has been conducted to date to investigate the isotopic composition of volatiles associated with these geothermal manifestations. Here, we report the results of an extensive survey of both natural hot springs and production wells across Tunisia aimed at investigating the spatial distribution of the 3He/4He ratio and associated carbon isotopic compositions. With respect to helium isotopes, not unexpectedly, the lowest 3He/4He values (0.01-0.02 Ra) are associated with the old groundwaters of the “Continental Intercalaire” aquifer of the stable Saharan Platform. The 3He/4He values are equal to the crustal production ratio, with no detectable amount of mantle-derived 3He, in agreement with previous studies of helium isotopes in sedimentary basin, which conclude that tectonically-stable regions are essentially impermeable to mantle volatiles. The low 3He/4He domain extends to the entire Atlasic domain of central Tunisia. This Atlasic domain also displays the highest helium concentrations : along the Gafsa Fault, helium concentrations of 1777 and 4723 x 10-8 cm3STP/g (the highest value of our data set) are observed in the production wells of Sidi Ahmed Zarrouk. This emphasizes the role of deep tectonic features in channelling and transporting deep crustal volatiles to shallow levels. The eastern margin of Tunisia displays higher 3He/4He values indicative of a substantial mantle volatile input. The highest value is recorded in the carbo-gaseous mineral water of Ain Garci (2.4 Ra). This northeastern part of the African plate commonly referred to as the Pelagian block extends from Tunisia to Sicily and is characterized by strong extensional tectonics (Pantelleria rift zone) and present-day magmatic activity. This lithospheric stretching and decompressional mantle melts production in the central portion of the Pelagian Block may facilitate the transport of mantle helium through the thinned crust away from the rift zone across the existing network of fractures and deep faults. Samples were also collected for water chemistry, ?D, ?18O, and carbon isotopic composition. ?13C(TDC) data are highly heterogeneous (ranging from -11.2 to +2.9 ‰ vs. V-PDB), in particular, revealing a complex origin for total dissolved carbon (TDC) in groundwaters. We interpret these variable isotopic compositions as reflecting mixture of biogenically derived carbon with abiogenic (mantle-derived or metamorphic) CO2. A detailed discussion of the whole chemistry and isotopic data set will be presented and the results will be examined in relation to the geological and structural framework of Tunisia.

Fourré, E.; Aiuppa, A.; di Napoli, R.; Parello, F.; Gaubi, E.; Jean-Baptiste, P.; Allard, P.; Calabrese, S.; Ben Mammou, A.



Quantification of Activated NF-?B/RelA Complexes Using ssDNA Aptamer Affinity - Stable Isotope Dilution--Selected Reaction Monitoring--Mass Spectrometry*  

PubMed Central

Nuclear Factor-?B (NF-?B) is a family of inducible transcription factors regulated by stimulus-induced protein interactions. In the cytoplasm, the NF-?B member RelA transactivator is inactivated by binding inhibitory I?Bs, whereas in its activated state, the serine-phosphorylated protein binds the p300 histone acetyltransferase. Here we describe the isolation of a ssDNA aptamer (termed P028F4) that binds to the activated (I?B?-dissociated) form of RelA with a KD of 6.4 × 10?10, and its application in an enrichment-mass spectrometric quantification assay. ssDNA P028F4 competes with cognate duplex high affinity NF-?B binding sites for RelA binding in vitro, binds activated RelA in eukaryotic nuclei and reduces TNF?-stimulated endogenous NF-?B dependent gene expression. Incorporation of P028F4 as an affinity isolation step enriches for serine 536 phosphorylated and p300 coactivator complexed RelA, simultaneously depleting I?B?·RelA complexes. A stable isotope dilution (SID)-selected reaction monitoring (SRM)- mass spectrometry (MS) assay for RelA was developed that produced a linear response over 1,000 fold dilution range of input protein and had a 200 amol lower limit of quantification. This multiplex SID-SRM-MS RelA assay was used to quantify activated endogenous RelA in cytokine-stimulated eukaryotic cells isolated by single-step P028F4 enrichment. The aptamer-SID-SRM-MS assay quantified the fraction of activated RelA in subcellular extracts, detecting the presence of a cytoplasmic RelA reservoir unresponsive to TNF? stimulation. We conclude that aptamer-SID-SRM-MS is a versatile tool for quantification of activated NF-?B/RelA and its associated complexes in response to pathway activation.

Zhao, Yingxin; Widen, Steven G.; Jamaluddin, Mohammad; Tian, Bing; Wood, Thomas G.; Edeh, Chukwudi B.; Brasier, Allan R.



Reduced thermal conductivity of isotope substituted carbon nanomaterials: Nanotube versus graphene nanoribbon  

NASA Astrophysics Data System (ADS)

Non-equilibrium molecular dynamics (MD) simulations of isotopically impure carbon nanotubes (CNTs) and graphene nanoribbons (GNRs) of varying lengths reveal that the relative decrease in thermal conductivity (k) in both the nanostructures are similar for constant isotope substitution. We find that the delocalized transverse modes in CNTs and the out-of-plane flexural modes in GNRs exert a substantial contribution to the thermal transport whereas the influence of isotope substitution on the phonon density of states (DOS) is similar in all directions. The vibrational spectra for different length scales consistently show that the energy modes shift to lower wave numbers reflecting the strong influence of mass disorder that reduces the energy transport through these nanomaterials, consequently lowering k.

Ray, Upamanyu; Balasubramanian, Ganesh



Chlorine stable isotopes: a comparison of dual inlet and thermal ionization mass spectrometric measurements  


Chlorine stable isotope ratios, 37Cl/35Cl, currently are measured using dual-inlet and thermal-ionization mass spectrometry. These two different analytical techniques, however, have never been cross calibrated. A set of samples with chlorine stable isotope delta values ranging from -4.4 to +0.3 % relative to standard mean ocean water chloride has been analyzed using both of these techniques. Our data show that both techniques can yield similar results within analytical uncertainty. CsCl thermal ionization data are extremely sensitive to the amount of chlorine being measured and cannot be used to determine absolute ratios without an independent means of correcting for machine-induced mass fractionation. As long as standards and samples are of equivalent size, however, the differences between samples measured by thermal ionization remain constant Dual inlet stable isotope mass spectrometry is suited best for samples of > 10 micromol Cl, yielding chlorine stable isotope data with < or =0.1% reproducibilities (2sigma). Thermal ionization mass spectrometry easily accommodates samples of approximately0.1-0.3 micromol Cl, with achievable uncertainties of < or =0.2% (2sigma). PMID:10845372

Rosenbaum; Cliff; Coleman



A site-specific, multiplexed kinase activity assay using stable-isotope dilution and high-resolution mass spectrometry  

PubMed Central

Most kinases are capable of recognizing and phosphorylating peptides containing short, linear sequence motifs. To measure the activation state of many kinases from the same cell lysate, we created a multiplexed, mass-spectrometry-based in vitro kinase assay. Ninety chemically synthesized peptides derived from well-characterized peptide substrates and in vivo phosphorylation sites with either known or previously unidentified upstream kinases were reacted individually in a plate format with crude cell lysates and ATP. Phosphorylation rates were directly measured based on the addition of 90 same-sequence, site-specific phosphopeptides enriched in stable isotopes to act as ideal quantitative internal standards for analysis by liquid chromatography coupled to tandem mass spectrometry. This approach concurrently measured up to 90 site-specific peptide phosphorylation rates, reporting a diagnostic fingerprint for activated kinase pathways. We applied this unique kinome-activity profiling strategy in a variety of cellular settings, including mitogen stimulation, cell cycle, pharmacological inhibition of pathways, and to a panel of breast cancer cell lines. Finally, we identified the source of activity for a peptide (derived from a PI3K regulatory subunit) from our library. This peptide substrate demonstrated mitotic and tyrosine-specific phosphorylation, which was confirmed to be a novel Src family kinase site in vivo.

Yu, Yonghao; Anjum, Rana; Kubota, Kazuishi; Rush, John; Villen, Judit; Gygi, Steven P.



Seasonal changes of total body water and water intake in Shetland ponies measured by an isotope dilution technique.  


Water is an essential nutrient necessary to support life, and adequate water supply is crucial for animal survival and productivity. The present study was designed to determine seasonal changes in the water metabolism of horses under outdoor conditions. Total body water (TBW) and total water intake (TWI) of 10 adult Shetland pony mares were estimated at monthly intervals for 14 mo by using the deuterium dilution technique. During the last 4 mo, 5 ponies were fed restrictively to simulate natural feed shortage in winter, and 5 ponies served as controls. The TBW (kg) was closely related to body mass [TBW (kg) = -2.86 + 0.67 × body mass (kg); P < 0.001; n = 105] explaining 86% of the variation. In contrast to TBW (kg), TBW (%) remained relatively stable across all measurements (57.8 to 71.2%). The TWI showed an increase in summer and a decrease in winter [TWI (mL·kg(-1)·d(-1)) = 15.07 + 23.69 × month - 1.45 × month(2) (R(2) = 0.64, P < 0.01)]. However, TWI measured at ambient temperatures (Ta) < 0°C did not follow the same trend as TWI at Ta > 0°C. Therefore, removing TWI values measured at Ta < 0°C from the analysis resulted in high correlations with locomotor activity (r = 0.87), Ta (r = 0.86), and resting heart rate (r = 0.88). The multiple regression among TWI, Ta, and heart rate explained 84% of the variation in TWI [TWI (mL·kg(-1)·d(-1)) = -13.38 + 1.77 × heart rate (beats/min) + 2.11 × Ta (°C); P < 0.001]. Feed restriction had no effect on TWI and TBW. The TBW content was unaffected by season and physical activity. The established regression equation for TBW and body mass can be used to predict TBW from body mass in ponies under field conditions. The comparison of TWI with published data on drinking water intake revealed that ponies had 1.7 to 5.1 times greater total water intakes when other sources of water such as feed and metabolic water were included. The TWI was highly influenced by environmental conditions and metabolic rate. Contrary to expectation, water supply during the cold seasons might be more critical than under summer conditions when water content of grass is high to allow for the compensation of limited availability of drinking water. PMID:23736044

Brinkmann, L; Gerken, M; Riek, A



[A novel method for absolute protein quantification using 18O isotope labeled concatamers of Q peptides combined with isotope dilution-multiple reaction monitoring mass spectrometry].  


A method of concatamers of Q peptides (QconCATs) protein labeled with 18O-multiple reaction monitoring mass spectrometry for absolute quantification of proteins is established. The purity of the QconCAT recombinant protein was characterized by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE), and its purity was above 99%. The relative molecular mass was approximately 63.4 kDa. The peptides digested from the QconCAT recombinant protein and the extract of Thermoanaerobacter tengcongensis (TTE) were analyzed by mass spectrometry. The raw data were processed by pFind and pLabel softwares. The results showed that the efficiencies of protein digestion and the 18O labeling efficiency were able to meet the need of the protein quantification. The performance of the method was evaluated. The absolute contents of the selected proteins in TTE were determined with the relative standard deviations of less than 20% and the accuracy is high. The method not only avoid using the expensive reagent of stable isotope labeling with amino acids in cell culture (SILAC), but also provides an alternative way for the accurately absolute quantification of proteins in biological samples for quantitative proteomic research. PMID:24063190

Li, Nannan; Zhou, Lianqi; Mao, Xinli; Zhang, Jiao; Wei, Junying; Lin, Hongjun; Li, Jiabin; Tian, Fang; Zhang, Yangjun; Qian, Xiaohong



Regional water-quality analysis of 2,4-D and dicamba in river water using gas chromatography-isotope dilution mass spectrometry  

USGS Publications Warehouse

Gas chromatography with isotope dilution mass spectrometry (GC-MS) and enzyme-linked immunosorbent assay (ELISA) were used in regional National Water Quality Assessment studies of the herbicides, 2,4-D and dicamba, in river water across the United States. The GC-MS method involved solid-phase extraction, derivatized with deutemted 2,4-D, and analysis by selected ion monitoring. The ELISA method was applied after preconcentration with solid-phase extraction. The ELISA method was unreliable because of interference from humic substances that were also isolated by solid-phase extraction. Therefore, GC-MS was used to analyzed 80 samples from river water from 14 basins. The frequency of detection of dicamba (28%) was higher than that for 2,4-D (16%). Concentrations were higher for dicamba than for 2,4-D, ranging from less than the detection limit (<0.05 ??g/L) to 3.77 ??g/L, in spite of 5 times more annual use of 2,4-D as compared to dicamba. These results suggest that 2,4-D degrades more rapidly in the environment than dicamba.

Thurman, E. M.; Zimmerman, L. R.; Aga, D. S.; Gilliom, R. J.



Analysis of matrix-bound nitrofuran residues in worldwide-originated honeys by isotope dilution high-performance liquid chromatography-tandem mass spectrometry.  


A sensitive and selective isotope dilution liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESIMS/MS) method is presented for the simultaneous analysis of the metabolites of four nitrofuran veterinary drugs, that is, furazolidone, furaltadone, nitrofurantoin, and nitrofurazone, in honey samples. The method entails a combined hydrolysis of protein-bound drug metabolites and derivatization of the resulting metabolites with 2-nitrobenzaldehyde (NBA) during an overnight incubation, followed by a liquid-liquid extraction and a cleanup on a polymeric solid-phase extraction cartridge. Mass spectral acquisition is carried out in the positive ion mode by applying multiple reaction monitoring (MRM) of three diagnostic transition reactions for each analyte under survey. A reliable quantification is obtained by the use of one deuterated analogue per analyte (NBA-d(4) derivative). The method has been validated in honey according to the European Union criteria for the analysis of veterinary drug residues in food. Expressed in underivatized nitrofuran metabolite concentrations, the decision limits (CCalpha) ranged within 0.07-0.46 microg/kg, and the detection capabilities (CCbeta) were within 0.12-0.56 microg/kg. The method has been successfully applied in a survey of honeys of various geographical origins, showing that furazolidone is the main nitrofuran antibiotic administered to treat bacterial diseases of bees. PMID:15315362

Khong, Seu-Ping; Gremaud, Eric; Richoz, Janique; Delatour, Thierry; Guy, Philippe A; Stadler, Richard H; Mottier, Pascal



Double spike isotope dilution GC-ICP-MS for evaluation of mercury species transformation in real fish samples using ultrasound-assisted extraction.  


Sample preparation continues being a key factor to obtain fast and reliable quantification of Hg species. Assisted procedures enhance the efficiency and reduce the extraction time; however, collateral species transformations have been observed. Moreover, differential interconversions have been observed even between similar matrixes, which introduce an important uncertainty for real sample analysis. Trying to minimize Hg species transformations, we have tested a soft ultrasound-assisted extraction procedure. Species quantification and transformations have been evaluated using double spike isotope dilution analysis (IDA) together with gas chromatography inductively coupled plasma mass spectrometry (GC-ICP-MS) for a CRM material (Tort-2) and shark and swordfish muscle samples. Optimum extraction solution and sonication time led to quantitative extraction and accurate determination of MeHg and IHg in a short time, although different behaviors regarding species preservation were observed depending on the sample. Negligible species transformations were observed in the analysis of the CRM, while a small but significant demethylation factor was observed in the case of real samples. In comparison with other extraction procedures, species transformations became smaller, and fewer differences between fish species were found. Similar results were obtained for fresh and lyophilized samples of both fish samples, which permit one to analyze the fresh sample directly and save time in the sample preparation step. The high grade of species preservation and the affordability of the extraction procedure allow one to obtain accurate determinations even for routine laboratories using quantification techniques, which do not estimate species transformations. PMID:22827829

Esteban-Fernández, Diego; Mirat, Manuela; de la Hinojosa, M Ignacia Martín; Alonso, J Ignacio García



Precision of glucose measurements in control sera by isotope dilution/mass spectrometry: proposed definitive method compared with a reference method  

SciTech Connect

This improved isotope-dilution gas chromatographic/mass spectrometric (GC/MS) method, in which (/sup 13/C)glucose is the internal standard, meets the requirements of a Definitive Method. In a first study with five reconstituted lyophilized sera, a nested analysis of variance of GC/MS values indicated considerable among-vial variation. The CV for 32 measurements per serum ranged from 0.5 to 0.9%. However, concentration and uncertainty values (mmol/L per gram of serum) assigned to one serum by the NBS Definitive Method (7.56 +/- 0.28) were practically identical to those obtained with the proposed method (7.57 +/- 0.20). In the second study, we used twice more (/sup 13/C)glucose diluent to assay four serum pools and two lyophilized sera. The CV ranged from 0.26 to 0.5% for the serum pools and from 0.28 to 0.59% for the lyophilized sera. In comparison, results by the hexokinase/glucose-6-phosphate dehydrogenase reference method agreed within acceptable limits with those by the Definitive Method but tended to be slightly higher (up to 3%) for lyophilized serum samples or slightly lower (up to 2.5%) for serum pools.

Pelletier, O.; Arratoon, C.



Solid sampling electrothermal vaporization inductively coupled plasma mass spectrometry for the direct determination of Hg in different materials using isotope dilution with a gaseous phase for calibration  

NASA Astrophysics Data System (ADS)

This paper evaluates the potential of electrothermal vaporization-inductively coupled plasma mass spectrometry (ETV-ICPMS) for the direct determination of Hg in solid samples, using a 200Hg-enriched gaseous phase for calibration based on isotope dilution. Three different samples were studied, BCR CRM 320 River sediment, IAEA-086 Hair and a real (wet) freshwater fish sample (M1). The samples selected show important differences in their matrix composition, and especially the fish sample constitutes a challenge as a result of its high water content (?80%). The main conclusion of the work is that the calibration approach investigated succesfully corrects for all the matrix effects (suppression) observed during Hg vaporization, allowing accurate values to be obtained in all cases. Moreover, practically the same operating conditions could be used for all sample types. The method finally proposed presents interesting features for the direct determination of this challenging element in solid samples, such as: a low sample consumption (a few milligrams), a high sample throughput (10 min/sample), a low limit of detection (6 ng g -1) and a reduced risk of analyte losses or contamination. Precision values depend on the homogeneity of the sample studied, and are typically in the vicinity of 10% RSD, except for the more inhomogenous river sediment (18% RSD).

Resano, M.; Gelaude, I.; Dams, R.; Vanhaecke, F.



Determination of nerve agent metabolites in human urine by isotope-dilution gas chromatography-tandem mass spectrometry after solid phase supported derivatization.  


A simple and sensitive method has been developed and validated for determining ethyl methylphosphonic acid (EMPA), isopropyl methylphosphonic acid (IMPA), isobutyl methylphosphonic acid (iBuMPA), and pinacolyl methylphosphonic acid (PMPA) in human urine using gas chromatography-tandem mass spectrometry (GC-MS/MS) coupled with solid phase derivatization (SPD). These four alkyl methylphosphonic acids (AMPAs) are specific hydrolysis products and biomarkers of exposure to classic organophosphorus (OP) nerve agents VX, sarin, RVX, and soman. The AMPAs in urine samples were directly derivatized with pentafluorobenzyl bromide on a solid support and then extracted by liquid-liquid extraction. The analytes were quantified with isotope-dilution by negative chemical ionization (NCI) GC-MS/MS in a selected reaction monitoring (SRM) mode. This method is highly sensitive, with the limits of detection of 0.02 ng/mL for each compound in a 0.2 mL sample of human urine, and an excellent linearity from 0.1 to 50 ng/mL. It is proven to be very suitable for the qualitative and quantitative analyses of degradation markers of OP nerve agents in biomedical samples. PMID:24633564

Lin, Ying; Chen, Jia; Yan, Long; Guo, Lei; Wu, Bidong; Li, Chunzheng; Feng, Jianlin; Liu, Qin; Xie, Jianwei



Determination of ochratoxin A in food: comparison of a stable isotope dilution assay, liquid chromatography-fluorescence detection and an enzyme-linked immunosorbent assay.  


Quantitative results for the mycotoxin ochratoxin A (OTA), obtained by a stable isotope dilution assay (SIDA) were compared with two commonly used analytical methods for OTA quantitation. For this, different types of food, such as wheat, coffee, sultanas, and blood sausages, were analyzed. Because results obtained by the SIDA method were closest to the certified contents of an OTA reference material, data obtained by this method were considered as reference data. For liquid chromatography-fluorescence detection, a clean-up by solid phase extraction on silica was found to be necessary, and a correction for recovery had to be performed to match the data from the SIDA experiments. The enzyme-linked immunosorbent assay (ELISA) strongly overestimated the OTA content in coffee and nutmeg therefore an extract clean-up by immunoaffinity chromatography had to be used to match the SIDA results. Following this sample preparation, ELISA gave correct qualitative and semiquantitative results, and proved to be a suitable screening method. SIDA was also established as a valuable tool to quantify OTA in meat products, when using a clean-up procedure developed recently for blood samples. PMID:23605702

Lindenmeier, Michael; Schieberle, Peter; Rychlik, Michael



Medium-chain acyl-CoA dehydrogenase deficiency. Diagnosis by stable-isotope dilution measurement of urinary n-hexanoylglycine and 3-phenylpropionylglycine  

SciTech Connect

Medium-chain acyl-CoA dehydrogenase (MCAD) deficiency, one of the most common inherited metabolic disorders, is often mistaken for the sudden infant death syndrome or Reye's syndrome. Diagnosing it has been difficult because of a lack of fast and reliable diagnostic methods. We developed a stable-isotope dilution method to measure urinary n-hexanoylglycine, 3-phenylpropionylglycine, and suberylglycine, and we retrospectively tested its accuracy in diagnosing MCAD deficiency. We measured the concentrations of these three acylglycines in 54 urine samples from 21 patients with confirmed MCAD deficiency during the acute and asymptomatic phases of the illness and compared the results with the concentrations in 98 samples from healthy controls and patient controls with various diseases. The levels of urinary hexanoylglycine and phenylpropionylglycine were significantly increased in all samples from the patients with MCAD deficiency, clearly distinguishing them from both groups of controls. Although urinary suberylglycine was increased in the patients, the range of values in the normal controls who were receiving formula containing medium-chain triglycerides was very wide, overlapping somewhat with the values in the patients with asymptomatic MCAD deficiency. These results indicate that the measurement of urinary hexanoylglycine and phenylpropionylglycine by our method is highly specific for the diagnosis of MCAD deficiency. The method is fast and can be applied to random urine specimens, without any pretreatment of patients.

Rinaldo, P.; O'Shea, J.J.; Coates, P.M.; Hale, D.E.; Stanley, C.A.; Tanaka, K.



Measurement of 2-carboxyarabinitol 1-phosphate in plant leaves by isotope dilution. [Spinacea oleracea; Triticum aestivum; Arabidopsis thaliana; Maize; Phaseolus vulgaris; Petunia hybrida  

SciTech Connect

The level of 2-carboxyarabinitol 1-phosphate (CA1P) in leaves of 12 species was determined by an isotope dilution assay. {sup 14}C-labeled standard was synthesized from (2-{sup 14}C)carboxyarabinitol 1,5-bisphosphate using acid phosphatase, and was added at the initial point of leaf extraction. Leaf CA1P was purified and its specific activity determined. CA1P was found in dark-treated leaves of all species examined, including spinach (Spinacea oleracea), wheat (Triticum aestivum), Arabidopsis thaliana, and maize (Zea mays). The highest amounts were found in bean (Phaseolus vulgaris) and petunia (Petunia hybrida), which had 1.5 to 1.8 moles CA1P per mole ribulose 1,5-bisphosphate carboxylase catalytic sites. Most species had intermediate amounts of CA1P (0.2 to 0.8 mole CA1P per mole catalytic sites). Such intermediate to high levels of CA1P support the hypothesis that CA1P functions in many species as a light-dependent regulator of ribulose 1,5-bisphosphate carboxylase activity and whole leaf photosynthetic CO{sub 2} assimilation. However, CA1P levels in spinach, wheat, and A. thaliana were particularly low (less than 0.09 mole CA1P per mole catalytic sites). In such species, CA1P does not likely have a significant role in regulating ribulose 1,5-bisphosphate carboxylase activity, but could have a different physiological role.

Moore, B.D.; Kobza, J.; Seemann, J.R. (Univ. of Nevada, Reno (United States))



Quantification of 2-acetyl-1-pyrroline in rice by stable isotope dilution assay through headspace solid-phase microextraction coupled to gas chromatography-tandem mass spectrometry.  


A new and convenient synthesis of 2-acetyl-1-pyrroline (2AP), a potent flavor compound in rice, and its ring-deuterated analog, 2-acetyl-1-d(2)-pyrroline (2AP-d(2)), was reported. A stable isotope dilution assay (SIDA), involving headspace solid-phase microextraction (HS-SPME) combined with gas chromatography-positive chemical ionization-ion trap-tandem mass spectrometry (GC-PCI-IT-MS-MS), was developed for 2AP quantification. A divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was used for HS-SPME procedure and parameters affecting analytes recovery, such as extraction time and temperature, pH and salt, were studied. The repeatability of the method (n=10) expressed as relative standard deviation (RSD) was 11.6%. A good linearity was observed from 5.9 to 779 ng of 2AP (r(2)=0.9989). Limits of detection (LOD) and quantification (LOQ) for 2AP were 0.1 and 0.4 ng g(-1) of rice, respectively. The recovery of spiked 2AP from rice matrix was almost complete. The developed method was applied to the quantification of 2AP in aerial parts and grains of scented and non-scented rice cultivars. PMID:20800726

Maraval, Isabelle; Sen, Kemal; Agrebi, Abdelhamid; Menut, Chantal; Morere, Alain; Boulanger, Renaud; Gay, Frédéric; Mestres, Christian; Gunata, Ziya



Comparison of digestion procedures and methods for quantification of trace lead in breast milk by isotope dilution inductively coupled plasma mass spectrometry  

PubMed Central

Measurement of lead in breast milk is an important public health consideration and can be technically quite challenging. The reliable and accurate determination of trace lead in human breast milk is difficult for several reasons including: potential for contamination during sample collection, storage, and analysis; complexities related to the high fat content of human milk; and poor analytic sensitivity at low concentrations. Breast milk lead levels from previous published studies should therefore be reviewed with caution. Due to the difficulty in identifying a method that would successfully digest samples with 100% efficiency, we evaluated three different digestion procedures including: (1) dry ashing in a muffle furnace, (2) microwave oven digestion, and (3) digestion in high pressure asher. High temperature, high pressure asher digestion was selected as the procedure of choice for the breast milk samples. Trace lead analysis was performed using isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS). Measured lead concentrations in breast milk samples (n = 200) from Mexico ranged from 0.2 to 6.7 ng ml?1. The precision for these measurements ranged from 0.27–7.8% RSD. Use of strict contamination control techniques and of a very powerful digestion procedure, along with an ID-ICP-MS method for lead determination, enables us to measure trace lead levels as low as 0.2 ng ml?1 in milk (instrument detection limit = 0.01 ng ml?1).

Amarasiriwardena, Chitra J.; Jayawardene, Innocent; Lupoli, Nicola; Barnes, Ramon M.; Hernandez-Avila, Mauricio; Hu, Howard



Studies on the analysis of 25-hydroxyvitamin D(3) by isotope-dilution liquid chromatography-tandem mass spectrometry using enzyme-assisted derivatisation.  


The total serum concentration of 25-hydroxyvitamins D (25-hydroxyvitamin D3 and 25-hydroxyvitamin D2) is currently used as an indicator of vitamins D status. Vitamins D insufficiency is claimed to be associated with multiple diseases, thus accurate and precise reference methods for the quantification of 25-hydroxyvitamins D are needed. Here we present a novel enzyme-assisted derivatisation method for the analysis of vitamins D metabolites in adult serum utilising 25-[26,26,26,27,27,27-(2)H6]hydroxyvitamin D3 as the internal standard. Extraction of 25-hydroxyvitamins D from serum is performed with acetonitrile, which is shown to be more efficient than ethanol. Cholesterol oxidase is used to oxidize the 3?-hydroxy group in the vitamins D metabolites followed by derivatisation of the newly formed 3-oxo group with Girard P reagent. 17?-Hydroxysteroid dehydrogenase type 10 is shown to oxidize selectively the 3?-hydroxy group in the 3?-hydroxy epimer of 25-hydroxyvitamin D3. Quantification is achieved by isotope-dilution liquid chromatography-tandem mass spectrometry. Recovery experiments for 25-hydroxyvitamin D3 performed on adult human serum give recovery of 102-106%. Furthermore in addition to 25-hydroxyvitamin D3, 24,25-dihydroxyvitamin D3 and other uncharacterised dihydroxy metabolites, were detected in adult human serum. PMID:24486315

Abdel-Khalik, Jonas; Crick, Peter J; Carter, Graham D; Makin, Hugh L; Wang, Yuqin; Griffiths, William J



Determination of bisphenol A, triclosan and their metabolites in human urine using isotope-dilution liquid chromatography-tandem mass spectrometry.  


Bisphenol A (BPA) and triclosan (TCS) are ubiquitous environmental phenols exhibiting endocrine disrupting activities that may be involved in various health disorders in humans. There is a need to measure separately free forms and conjugated metabolites because only the former are biologically active. We have developed sensitive methods using isotope-dilution liquid chromatography-tandem mass spectrometry for individual measurements of free BPA and TCS as well as their metabolites, BPA glucuronide (BPAG), BPA monosulfate (BPAS), BPA disulfate (BPADS), TCS glucuronide (TCSG) and TCS sulfate (TCSS) in urine. Comparative analyses of urine samples from 46 volunteers living in the Quebec City area using the new methods and a GC-MS/MS method previously used in our laboratory revealed very strong correlations for total BPA (Spearman's rs=0.862, p<0.0001) and total TCS concentrations (rs=0.942, p<0.0001). Glucuronide metabolites were the most abundant BPA and TCS species in urine samples (>94% of total urinary concentrations). Unconjugated TCS concentrations represented a small proportion of total TCS species (median=1.6%) but its concentration was likely underestimated due to losses by adsorption to the surface of polypropylene tubes used for sample storage. To our knowledge, we are the first to report levels of free, sulfated and glucuronidated TCS levels in human urine. PMID:24835763

Provencher, Gilles; Bérubé, René; Dumas, Pierre; Bienvenu, Jean-François; Gaudreau, Eric; Bélanger, Patrick; Ayotte, Pierre



An Update on the Non-Mass-Dependent Isotope Fractionation under Thermal Gradient  

NASA Technical Reports Server (NTRS)

Mass flow and compositional gradient (elemental and isotope separation) occurs when flu-id(s) or gas(es) in an enclosure is subjected to a thermal gradient, and the phenomenon is named thermal diffusion. Gas phase thermal diffusion has been theoretically and experimentally studied for more than a century, although there has not been a satisfactory theory to date. Nevertheless, for isotopic system, the Chapman-Enskog theory predicts that the mass difference is the only term in the thermal diffusion separation factors that differs one isotope pair to another,with the assumptions that the molecules are spherical and systematic (monoatomic-like structure) and the particle collision is elastic. Our previous report indicates factors may be playing a role because the Non-Mass Dependent (NMD) effect is found for both symmetric and asymmetric, linear and spherical polyatomic molecules over a wide range of temperature (-196C to +237C). The observed NMD phenomenon in the simple thermal-diffusion experiments demands quantitative validation and theoretical explanation. Besides the pressure and temperature dependency illustrated in our previous reports, efforts are made in this study to address issues such as the role of convection or molecular structure and whether it is a transient, non-equilibrium effect only.

Sun, Tao; Niles, Paul; Bao, Huiming; Socki, Richard; Liu, Yun



Mass-independent fractionation of oxygen isotopes during thermal decomposition of carbonates  

PubMed Central

Nearly all chemical processes fractionate 17O and 18O in a mass-dependent way relative to 16O, a major exception being the formation of ozone from diatomic oxygen in the presence of UV radiation or electrical discharge. Investigation of oxygen three-isotope behavior during thermal decomposition of naturally occurring carbonates of calcium and magnesium in vacuo has revealed that, surprisingly, anomalous isotopic compositions are also generated during this process. High-precision measurements of the attendant three-isotope fractionation line, and consequently the magnitude of the isotopic anomaly (?17O), demonstrate that the slope of the line is independent of the nature of the carbonate but is controlled by empirical factors relating to the decomposition procedure. For a slope identical to that describing terrestrial silicates and waters (0.5247 ± 0.0007 at the 95% confidence level), solid oxides formed during carbonate pyrolysis fit a parallel line offset by ?0.241 ± 0.042‰. The corresponding CO2 is characterized by a positive offset of half this magnitude, confirming the mass-independent nature of the fractionation. Slow, protracted thermolysis produces a fractionation line of shallower slope (0.5198 ± 0.0007). These findings of a 17O anomaly being generated from a solid, and solely by thermal means, provide a further challenge to current understanding of the nature of mass-independent isotopic fractionation.

Miller, Martin F.; Franchi, Ian A.; Thiemens, Mark H.; Jackson, Teresa L.; Brack, Andre; Kurat, Gero; Pillinger, Colin T.



Helium and Carbon isotopes of thermal springs hosted by deep faults in South China  

NASA Astrophysics Data System (ADS)

Helium and carbon isotopes were important indicators to identify the origin of volatile dissolved in groundwater. Four thermal springs were sampled and discussed by helium and carbon isotopes for they were hosted by local deep faults and had significant connection to deep geothermal activity in Guangdong, China. 4He content of four thermal springs varied greatly from 3.72×10-8 to 199.54×10-8 cm3STP/mL, and 20Ne content varied greatly from 0.21×10-8 to 2.96×10-8 cm3STP/mL. While 3He/4He varied slightly from 0.36 to 0.57Ra (atmosphere 3He/4He ratio Ra=1.4×10-6). It indicated that the mixing of a lot of noble gases from other sources besides atmosphere not only changed the content of noble gases in groundwater, but also changed the isotopic compositions of noble gases, during the runoff process of groundwater. Because 22Ne was almost derived from atmosphere, an improved method of 4He/22Ne - 3He/4He was used to identify the origin of helium. 4% to 6% mantle He in thermal springs revealed that significant mantle He migrating in deep faults can bring a certain amount of energy along with thermal volatile and contribute to thermal spring formation. The ?13C value of four thermal springs was -3.79‰ to -2.17‰. Then dissolved inorganic carbon in thermal springs was speculated from rock metamorphism, it indicated geothermal activity. The four thermal springs were illustrated in the zone of crustal CO2 of rock inorganic chemistry, near to that of crust-mantle mixing CO2. It seemed that negligible or a small amount of volcanic mantle CO2 mixed with crustal CO2, and dissolved in thermal groundwater. So, ?13C revealed that dissolved inorganic carbon in thermal springs was from rock metamorphism occurred in certain deep crust as geothermal activity, which maybe the main energy source of thermal springs. Fig. 1. AIR (ASW)-MORB-CRUST mixing model of He and Ne isotopes. Fig. 2. CO2 origin identified by the relationship of ?13C and 3He/ 4He.

Mao, X.; Wang, Y.; Yuan, J.



Effect of isotope substitution in binary liquids with Thermal-Lens spectroscopy  

NASA Astrophysics Data System (ADS)

Effect of isotope substitution from the modulation of Thermal-Lens (TL) signals in binary liquid mixtures is explored using femtosecond pump-probe mode-mismatched Z-scan TL spectroscopy. Binary solutions of water and heavy water with pure methanol at various concentrations are used for the study, where pure methanol acts as the TL marker across the different samples. The TL signal is found to be effectively modulated by isotope substitution under the experimental conditions, indicating that TL signal depends on hydrogen bonding.

Bhattacharyya, Indrajit; Kumar, Pardeep; Goswami, Debabrata



Reverse isotope dilution alpha spectrometry using plutionium-239 spike for determining plutonium concentration in high burn-up fuel samples without purification from americium-241 and a bulk of other impurities  

Microsoft Academic Search

A reverse isotope dilution alpha spectrometric \\/R-IDAS\\/ method using239Pu as a spike is described for the determination of plutonium concentration in high burn-up fuel samples wth238Pu\\/(239Pu+240Pu) alpha activity ratio >0.5, without resorting to any purification from241Am and a bulk of other impurities. It involves the addition of a pre-clibrated spike solution to a known aliquot of the plutonium sample solution

S. K. Aggarwal; G. Chourasiya; R. K. Duggal; R. Rao; P. A. Ramasubramanian; H. C. Jain



Determination of ultra-trace amounts of Fe in AgNO 3 solutions by means of isotope dilution analysis applying an inductively coupled plasma mass spectrometer equipped with a dynamic reaction cell  

Microsoft Academic Search

.  The development of an ICP-MS method for the determination of ultra-trace amounts of Fe in AgNO3 solutions using isotope dilution for calibration is described. AgNO3 solutions are used as raw materials in the production of traditional photographic materials, and it is known that contamination with metal traces can influence the quality of the films thus produced. After adding an appropriate

Lieve Balcaen; Ingrid Geuens; Luc Moens; Frank Vanhaecke



Determination of methionine and selenomethionine in selenium-enriched yeast by species-specific isotope dilution with liquid chromatography-mass spectrometry and inductively coupled plasma mass spectrometry detection  

Microsoft Academic Search

Selenomethionine (SeMet) and methionine (Met), liberated by acid hydrolysis of selenium-enriched yeast, were quantified by liquid chromatography-mass spectrometry (LC\\/MS) using standard additions calibrations as well as isotope dilution (ID) based on species-specific 13C-enriched spikes. LC inductively coupled plasma mass spectrometry (ICPMS) was also employed for the quantification of SeMet, and 74Se-enriched SeMet was used for ID calibration. The results were

Shona McSheehy; Lu Yang; Ralph Sturgeon; Zoltan Mester



Producing SI-traceable reference values for Cd, Cr and Pb amount contents in polyethylene samples from the Polymer Elemental Reference Material (PERM) project using isotope dilution mass spectrometry  

Microsoft Academic Search

The present paper describes the certification of the amount content of Cd, Cr and Pb in two different polyethylene materials\\u000a within the third phase of the Polyethylene Elemental Reference Material (PERM) project. The analytical procedure to establish\\u000a the reference values for Cd, Cr and Pb amount contents in these materials is based on isotope dilution mass spectrometry used\\u000a as a

J. Vogl; D. Liesegang; M. Ostermann; J. Diemer; M. Berglund; C. R. Quétel; P. D. P. Taylor; K. G. Heumann



Automated high-speed analysis of selected organic compounds in urban air by on-line isotopic dilution cryofocusing gas chromatography/mass spectrometry.  


An automated environmental air monitor has been developed to measure selected organic compounds in urban air. The instrument is based on a cryofocusing-thermal desorption gas chromatographic mass spectrometry technique where the mass spectrometer is a slightly modified residual gas analyzer (RGA). The RGA was chosen as a detector because the whole system must be robust for long periods, with 24-h continuous air monitoring. RCA are extremely simple and seemed the most reliable mass spectrometers for this purpose. Moreover, because they have no physically limited ion source, contamination is considerably reduced, so maintenance intervals are longer.The gas chromatograph is equipped with a computer-controlled six-way sampling valve, with a 100-mL sampling loop and thermal desorption cold trap injector. Environmental air is enriched with an isotopically labeled internal standard in the sampling line. This internal standard is added with a validated, custom-made, permeation tube device. The "on-line" internal standard provides for high quality quantitative data because all variations in instrument sensitivity in cryofocusing or in thermal desorption efficiency are taken into account. High repetition rates (down to 5 min for a full analytical cycle) are obtained with the use of an isothermal gas chromatography program, microbore capillary column, and environmental air sampling during the gas chromatography run. PMID:24226389

Davoli, E; Cappellini, L; Maggi, M; Fanelli, R



A Sr-isotopic comparison between thermal waters, rocks, and hydrothermal calcites, Long Valley caldera, California  

USGS Publications Warehouse

The 87Sr/86Sr values of thermal waters and hydrothermal calcites of the Long Valley caldera geothermal system are more radiogenic than those of young intracaldera volcanic rocks. Five thermal waters display 87Sr/86Sr of 0.7081-0.7078 but show systematically lighter values from west to east in the direction of lateral flow. We believe the decrease in ratio from west to east signifies increased interaction of deeply circulating thermal water with relatively fresh volcanic rocks filling the caldera depression. All types of pre-, syn-, and post-caldera volcanic rocks in the west and central caldera have (87Sr/86Sr)m between about 0.7060 and 0.7072 and values for Sierra Nevada granodiorites adjacent to the caldera are similar. Sierran pre-intrusive metavolcanic and metasedimentary rocks can have considerably higher Sr-isotope ratios (0.7061-0.7246 and 0.7090-0.7250, respectively). Hydrothermally altered volcanic rocks inside the caldera have (87Sr/86Sr)m slightly heavier than their fresh volcanic equivalents and hydrothermal calcites (0.7068-0.7105) occupy a midrange of values between the volcanic/plutonic rocks and the Sierran metamorphic rocks. These data indicate that the Long Valley geothermal reservoir is first equilibrated in a basement complex that contains at least some metasedimentary rocks. Reequilibration of Sr-isotope ratios to lower values occurs in thermal waters as convecting geothermal fluids flow through the isotopically lighter volcanic rocks of the caldera fill. ?? 1991.

Goff, F.; Wollenberg, H. A.; Brookins, D. C.; Kistler, R. W.



Determination of mycotoxins in milk-based products and infant formula using stable isotope dilution assay and liquid chromatography tandem mass spectrometry.  


A stable isotope dilution assay and liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed and validated for the determination of 12 mycotoxins, aflatoxins B?, B?, G?, G?, and M?, deoxynivalenol, fumonisins B?, B?, and B?, ochratoxin A, T-2 toxin, and zearalenone, in milk-based infant formula and foods. Samples were fortified with 12 ¹³C uniformly labeled mycotoxins ([¹³C]-mycotoxins) that correspond to the 12 target mycotoxins and prepared by dilution and filtration, followed by LC-MS/MS analysis. Quantitation was achieved using the relative response factors of [¹³C]-mycotoxins and target mycotoxins. The average recoveries in fortified milk, milk-based infant formula, milk powder, and baby yogurt of aflatoxins B?, B?, G?, and G? (2, 10, and 50 ?g/kg), aflatoxin M? (0.5, 2.5, and 12.5 ?g/kg), deoxynivalenol, fumonisins B?, B?, and B? (40, 200, and 1000 ?g/kg), ochratoxin A, T-2 toxin, and zearalenone (20, 100, and 500 ?g/kg), range from 89 to 126% with RSDs of <20%. The individual recoveries in the four fortified matrices range from 72% (fumonisin B?, 20 ?g/kg, milk-based infant formula) to 136% (T-2 toxin, 20 ?g/kg, milk powder), with RSDs ranging from 2 to 25%. The limits of quantitation (LOQs) were from 0.01 ?g/kg (aflatoxin M?) to 2 (fumonisin B?) ?g/kg. Aflatoxin M? was detected in two European Reference materials at 0.127 ± 0.013 ?g/kg (certified value = 0.111 ± 0.018 ?g/kg) and 0.46 ± 0.04 ?g/kg (certified value = 0.44 ± 0.06 ?g/kg), respectively. In 60 local market samples, aflatoxins B? (1.14 ± 0.10 ?g/kg) and B? (0.20 ± 0.03 ?g/kg) were detected in one milk powder sample. Aflatoxin M? was detected in three imported samples (condensed milk, milk-based infant formula, and table cream), ranging from 0.10 to 0.40 ?g/kg. The validated method provides sufficient selectivity, sensitivity, accuracy, and reproducibility to screen for aflatoxin M? at nanograms per kilogram concentrations and other mycotoxins, without using standard addition or matrix-matched calibration to compensate for matrix effects. PMID:23746324

Zhang, Kai; Wong, Jon W; Hayward, Douglas G; Vaclavikova, Marta; Liao, Chia-Ding; Trucksess, Mary W



Direct determination of methylmercury and inorganic mercury in biological materials by solid sampling-electrothermal vaporization-inductively coupled plasma-isotope dilution-mass spectrometry.  


This paper reports on the use of solid sampling-electrothermal vaporization-inductively coupled plasma mass spectrometry (SS-EIV-ICPMS) for the direct and simultaneous determination of methylmercury and inorganic mercury in biological materials. The main advantage of this fast and sensitive method is that no sample preparation is required. In this way, the sample throughput can be considerably increased, problems of contamination and analyte losses are kept to a minimum and, even more important, the original chemical form of the different analyte species in the solid samples is preserved. To achieve this goal, a solid sample is inserted into a graphite furnace of the boat-in-tube type and is subsequently submitted to an appropriate temperature program, leading to the separate vaporization of methylmercury and inorganic mercury, which are transported into the ICP by means of an argon carrier gas. The separation was accomplished within 75 s. For the quantification of the two peaks, species-unspecific isotope dilution was used. For this purpose, a stable flow of argon loaded with gaseous Hg isotopically enriched in 200Hg was generated using a permeation tube that was constructed in-house. Its emission rate was determined by collecting the mercury released during a given time interval on a gold-coated silica absorber, after which the amount collected was released by heating of the absorber and determined by cold vapor atomic absorption spectrometry (CVAAS) and cold vapor atomic fluorescence spectrometry (CVAFS). A reference material from the Canadian National Research Council (NRC) (TORT-2) was used to assess the accuracy of the method. For the application of the method to samples with diverse mercury contents, the spike/sample ratio can be optimized by varying the emission rate of the permeation tube simply by adapting its temperature. To prove the feasibility of this approach, two reference materials (BCR 463 and DORM-2) with a methylmercury content more than 10 times higher than that of TORT-2 were also analyzed. The detection limits obtained for 1 mg of sample (2 ng g(-1) and 6 ng g(-1) for methylmercury and inorganic mercury, respectively) were found to be sufficiently low for this kind of application and are competitive when compared to other techniques. PMID:12175173

Gelaude, I; Dams, R; Resano, M; Vanhaecke, F; Moens, L



Determination of 11-deoxycortisol (Reichstein's compound S) in human plasma by clinical isotope dilution mass spectrometry using benchtop gas chromatography-mass selective detection.  


A first assay based on stable isotope dilution/gas chromatography-mass spectrometry (ID/GC-MS) has been developed for plasma 11-deoxycortisol (Reichstein's compound S), the leading hormonal marker of 11beta-hydroxylase deficiency. A suitable internal standard being unavailable, we synthesized dideuterated 11-deoxycortisol according to a newly devised synthetic procedure. 17,21-Dihydroxy-pregna-1,4-diene-3,20-dione underwent selective deuteration using Wilkinson's catalyst. Our product [1alpha,2alpha-2H2]11-deoxycortisol was obtained in good yield (35.6%) and high isotopic purity (0.1% 2H0, 99.9% 2H2). Structural confirmation was done by MS and NMR. Our plasma work up consisted of equilibration of plasma with internal standard ([1alpha,2alpha-2H2]11-deoxycortisol), solid phase extraction with Extrelut NT columns, a clean up step using Sephadex LH-20 mini columns and preparation of heptafluorobutyrates as derivatives. Quantification was achieved by selected ion monitoring of m/z 465.40 (analyte) and m/z 467.40 (internal standard). One hundred twenty picograms of 11-deoxycortisol gave a signal to noise ratio of 10. Calibration plot was linear. Spiking experiments showed good accuracy with relative errors <3.0%. Intraassay precision CV was 4.78% and interassay precision CV was 4.56%. We succeeded in integrating our new analyte into our already existing multisteroid ID/GC-MS plasma assay, which now, in its expanded version, is capable of determining all major diagnostic steroids of androgen related disorders in a single profile: 11-deoxycortisol, 17alpha-hydroxyprogesterone, testosterone, 4-androstenedione, 17alpha-hydroxypregnenolone, dehydroepiandrosterone, androstanediol and 5alpha-dihydrotestosterone. The diagnostic potential of our multisteroid ID/GC-MS assay, the small amounts of plasma (0.5 ml) required, the rapid and convenient sample work up, the application of benchtop GC-MS instrumentation, and highest specificity offered by mass spectrometric detection prove our assay suitable for routine clinical use, especially in pediatric endocrinology. PMID:12231120

Wudy, Stefan A; Hartmann, Michaela; Homoki, Janos



Strontium isotopes as an indicator of water-rock reaction for the Coupled Thermal-Hydrological-Mechanical-Chemical-Biological (THMCB) Experimental Facility at DUSEL  

NASA Astrophysics Data System (ADS)

The Thermal-Hydrological-Mechanical-Chemical-Biological (THMCB) Experimental Facility is a proposed facility at the DUSEL-Homestake that will be used to investigate reactive transport, heat transfer and the resulting biological responses within a natural fractured rock. As part of THMCB facility design we are characterizing the current geochemical conditions and developing geochemical and isotopic indicators for fluid flow paths and reaction rates. The proposed experimental site is located at a depth of 4850 feet, primarily in the Homestake and Poorman Formations. At the experimental site, these formations are a quartz-chlorite-siderite iron formation and alumina-poor metapelite, respectively. Water samples from fractures and boreholes indicate that the pore fluid is a dilute Na-HCO3 water. The strontium isotope 87Sr/86Sr composition of surface waters is approximately 0.7106 based on stream water collected near the DUSEL site. The 87Sr/86Sr of subsurface waters sampled from fractures and boreholes throughout the mine varies from 0.7144 to 0.8145. 87Sr/86Sr and strontium concentrations suggest that calcite precipitation removes strontium and calcium from solution at shallow depths in the mine (< 3000 ft), consistent with pervasive calcite accumulation observed in the tunnels at these levels. 87Sr/86Sr values generally increase with depth and are highest in slow flowing fractures where they approach the isotopic value of the Poorman Formation (ca. 0.83±0.06). Collectively the data suggest that the Sr isotopic composition of the mine water is controlled by the flow rate of water and the extent of exchange with the surrounding rock matrix. Additionally, 87Sr/86Sr and temperature are positively correlated in the Poorman and Homestake Formations suggesting that temperature may be an additional tracer for fluid flow. Other isotopic tracers including 234U/238U, ?18O, ?D, ?13C and ?30Si are also being evaluated for use in the THMCB experimental facility.

Maher, K.; Olsen, N. J.; Harris, C.; Jones, T. L.; Conrad, M. E.; Sonnenthal, E. L.; Elsworth, D.; Uzunlar, N.; Mailloux, B. J.; Lowell, R. P.



Zn speciation in the organic horizon of a contaminated soil by micro-X-ray fluorescence, micro- and powder-EXAFS spectroscopy, and isotopic dilution.  


Soils that have been acutely contaminated by heavy metals show distinct characteristics, such as colonization by metal-tolerant plant species and topsoil enrichment in weakly degraded plant debris, because biodegradation processes are strongly inhibited by contamination. Such an organic topsoil, located downwind of an active zinc smelter and extremely rich in Zn (approximately 2%, dry weight), was investigated by X-ray diffraction, synchrotron-based X-ray microfluorescence, and powder- and micro-extended X-ray absorption fine structure (EXAFS) spectroscopy for Zn speciation and by isotopic dilution for Zn lability. EXAFS spectra recorded on size fractions and on selected spots of thin sections were analyzed by principal component analysis and linear combination fits. Although Zn primary minerals (franklinite, sphalerite, and willemite) are still present (approximately 15% of total Zn) in the bulk soil, Zn was found to be predominantly speciated as Zn-organic matter complexes (approximately 45%), outer-sphere complexes (approximately 20%), Zn-sorbed phosphate (approximately 10%), and Zn-sorbed iron oxyhydroxides (approximately 10%). The bioaccumulated Zn fraction is likely complexed to soil organic matter after the plants' death. The proportion of labile Zn ranges from 54 to 92%, depending on the soil fraction, in agreement with the high proportion of organically bound Zn. Despite its marked lability, Zn seems to be retained in the topsoil thanks to the huge content of organic matter, which confers to this horizon a high sorption capacity. The speciation of Zn in this organic soil horizon is compared with that found in other types of soils. PMID:15212252

Sarret, Géraldine; Balesdent, Jérome; Bouziri, Lamia; Garnier, Jean-Marie; Marcus, Matthew A; Geoffroy, Nicolas; Panfili, Frédéric; Manceau, Alain



Simultaneous analysis of oxybutynin and its active metabolite N-desethyl oxybutynin in human plasma by stable isotope dilution LC-MS/MS to support a bioequivalence study.  


An isotope dilution high performance liquid chromatography-tandem mass spectrometry (LC-MS/MS) method has been developed for the simultaneous determination of oxybutynin and its pharmacologically active metabolite N-desethyl oxybutynin in human plasma. Extraction of oxybutynin, its metabolite and their deuterated analogs as internal standards (ISs) from 300 ?L human plasma was carried out by liquid-liquid extraction with methyl tert-butyl ether-ethyl acetate solvent mixture. Chromatographic separation of analytes was performed on Cosmosil C18 (150 mm × 4.6 mm, 5 ?m) column under isocratic conditions with acetonitrile-1.0mM ammonium acetate (90:10, v/v) as the mobile phase. Six endogenous plasma phospholipids (496.3/184.0, 524.3/184.0, 758.5/184.0, 786.5/184.0, 806.5/184.0 and 810.5/184.0) were monitored to determine the extraction efficiency under different extraction conditions. The precursor?product ion transition for both the analytes and ISs were monitored on a triple quadrupole mass spectrometer, operating in the multiple reaction monitoring and positive ionization mode. The method was validated over a concentration range of 0.050-10.0 ng/mL for oxybutynin and 0.500-100 ng/mL for N-desethyl oxybutynin. The mean extraction recovery for analytes (80.4%) and ISs (76.9%) was consistent across five QC levels. Bench top, wet and dry extract, freeze-thaw and long term stability was evaluated for both the analytes. The method was applied to support a bioequivalence study of 5mg tablet formulation in 74 healthy Indian subjects. Assay reproducibility was demonstrated by reanalysis of 344 incurred samples. PMID:23867086

Sharma, Primal; Patel, Daxesh P; Sanyal, Mallika; Berawala, Hiren; Guttikar, Swati; Shrivastav, Pranav S



Simultaneous quantification of S-adenosyl methionine and S-adenosyl homocysteine in human plasma by stable-isotope dilution ultra performance liquid chromatography tandem mass spectrometry.  


S-adenosyl methionine (SAM) is an important methyl group donor that is formed from methionine. S-adenosyl homocysteine (SAH) is formed after demethylation of SAM and represents a potent inhibitor of many methyltransferases. We developed an improved stable-isotope dilution ultra performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS) method for the simultaneous quantification of SAM and SAH in biological samples. The method comprises a phenylboronic acid-containing solid-phase extraction procedure, serving for binding and clean-up of SAM and SAH. After extraction, samples were separated and detected using either a HPLC SymmetryShield RP(18) or an Acquity UPLC BEH C(18) column with a HPLC-MS/MS or an UPLC-MS/MS system. The best results were obtained by Acquity UPLC BEH C(18) column. In plasma samples, the estimated intraassay coefficients of variation (CVs) for SAM and SAH were 3.3% and 3.9%, respectively, the interassay CVs were 10.1% for SAM and 8.3% for SAH. Mean recovery of SAM and SAH at two different concentrations was 100.0% for SAM and 101.7% for SAH. The quantification limits were 0.5 and 0.7nmol/L for SAM and SAH, respectively. In 31 plasma samples, the mean concentrations (SD) were 85.5 (11.1)nmol/L for SAM and 13.3 (5.0)nmol/L for SAH with a SAM/SAH ratio of 7.0 (1.8). The new UPLC-MS/MS method showed very high sensitivity and selectivity for SAM and SAH, low CVs and fast sample preparation (40 samples in 60min) and analysis time (3min). This new assay can be used for large-scale clinical studies. PMID:19828381

Kirsch, Susanne H; Knapp, Jean-Pierre; Geisel, Jürgen; Herrmann, Wolfgang; Obeid, Rima



Detection of triclocarban and two co-contaminating chlorocarbanilides in US aquatic environments using isotope dilution liquid chromatography tandem mass spectrometry  

SciTech Connect

The antimicrobial compound triclocarban (TCC; 3,4,4'-trichlorocarbanilide; CAS-bar 101-20-2) is a high-production-volume chemical, recently suggested to cause widespread contamination of US water resources. To test this hypothesis, we developed an isotope dilution liquid chromatography electrospray ionization tandem mass spectrometry method for ultratrace analysis of TCC (0.9ng/L detection limit) and analyzed low-volume water samples (200mL) along with primary sludge samples from across the United States. All river water samples (100%) collected downstream of wastewater treatment plants had detectable levels of TCC, as compared to 56% of those taken upstream. Concentrations of TCC (mean+/-standard deviation) downstream of sewage treatment plants (84+/-110ng/L) were significantly higher (P<0.05; Wilcoxon rank sum test) than those of samples taken upstream (12+/-15ng/L). Compared to surface water, mean TCC concentrations found in dried, primary sludge obtained from municipal sewage treatment plants in five states were six orders of magnitude greater (19,300+/-7100{mu}g/kg). Several river samples contained a co-contaminant, identified based on its chromatographic retention time, molecular base ion, and MS/MS fragmentation behavior as 4,4'-dichlorocarbanilide (DCC; CAS-bar 1219-99-4). In addition to TCC and DCC, municipal sludge contained a second co-contaminant, 3,3',4,4'-tetrachlorocarbanilide (TetraCC; CAS-bar 4300-43-0). Both newly detected compounds were present as impurities (0.2%{sub w/w} each) in technical grade TCC (99%). Application of the new method for chlorocarbanilide analysis yielded TCC occurrence data for 13 US states, confirmed the role of sewage treatment plants as environmental inputs of TCC, and identified DCC and TetraCC as previously unrecognized pollutants released into the environment alongside TCC.

Sapkota, Amir [Department of Environmental Health Sciences, Johns Hopkins University, Bloomberg School of Public Health, Johns Hopkins University Center for Water and Health, Baltimore, MD 21205-2103 (United States); Heidler, Jochen [Department of Environmental Health Sciences, Johns Hopkins University, Bloomberg School of Public Health, Johns Hopkins University Center for Water and Health, Baltimore, MD 21205-2103 (United States); Halden, Rolf U. [Department of Environmental Health Sciences, Johns Hopkins University, Bloomberg School of Public Health, Johns Hopkins University Center for Water and Health, Baltimore, MD 21205-2103 (United States)]. E-mail:



Simultaneous determination of four sulfur mustard-DNA adducts in rabbit urine after dermal exposure by isotope-dilution liquid chromatography-tandem mass spectrometry.  


Sulfur mustard (SM) is a classic vesicant agent, which has been greatly employed in several wars or military conflicts. The most lesion mechanism is its strong alkylation of DNAs in vivo. Until now there are four specific DNA adducts of SM identified for further retrospective detection, i.e., N(7)-(2-hydroxyethylthioethyl)-2'-guanine (N(7)-HETEG), bis(2-ethyl-N(7)-guanine)thioether (Bis-G), N(3)-(2-hydroxyethylthioethyl)-2'-adenine (N(3)-HETEA) and O(6)-(2-hydroxyethylthioethyl)-2'-guanine (O(6)-HETEG), respectively. Here, a novel and sensitive method of isotope-dilution ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) combining with solid phase extraction was reported for the simultaneous determination of four SM-DNA adducts. A lower limit of detection of 2-5ngL(-1), and a lower limit of quantitation of 5-10ngL(-1) were achieved, respectively, and the recoveries ranged from 87% to 116%. We applied this method in the determination of four SM-DNA adducts in rabbit urine after dermal exposure by SM in three dose levels (2, 5, 15mgkg(-1)), so as to investigate the related metabolic behavior in vivo. For the first time, in SM exposed rabbit urine, our results revealed the relative accumulation abundance of four SM-DNA adducts, i.e., 67.4% for N(7)-HETEG, 22.7% for Bis-G, 9.8% for N(3)-HETEA, 0.1% for O(6)-HETEG, and significant dose and time dependent responses of these SM-DNA adducts. The four adducts were detectable after 8h, afterwards, their contents continuously increased, achieved maximum in the first two or three days and then gradually decreased till the end of one month. Meanwhile, the amounts of SM-DNA adducts were positively correlated with the exposure doses. PMID:24858262

Zhang, Yajiao; Yue, Lijun; Nie, Zhiyong; Chen, Jia; Guo, Lei; Wu, Bidong; Feng, Jianlin; Liu, Qin; Xie, Jianwei



Identification and Quantification of DNA Repair Protein Apurinic/Apyrimidinic Endonuclease 1 (APE1) in Human Cells by Liquid Chromatography/Isotope-Dilution Tandem Mass Spectrometry  

PubMed Central

Unless repaired, DNA damage can drive mutagenesis or cell death. DNA repair proteins may therefore be used as biomarkers in disease etiology or therapeutic response prediction. Thus, the accurate determination of DNA repair protein expression and genotype is of fundamental importance. Among DNA repair proteins involved in base excision repair, apurinic/apyrimidinic endonuclease 1 (APE1) is the major endonuclease in mammals and plays important roles in transcriptional regulation and modulating stress responses. Here, we present a novel approach involving LC-MS/MS with isotope-dilution to positively identify and accurately quantify APE1 in human cells and mouse tissue. A completely 15N-labeled full-length human APE1 was produced and used as an internal standard. Fourteen tryptic peptides of both human APE1 (hAPE1) and 15N-labeled hAPE1 were identified following trypsin digestion. These peptides matched the theoretical peptides expected from trypsin digestion and provided a statistically significant protein score that would unequivocally identify hAPE1. Using the developed methodology, APE1 was positively identified and quantified in nuclear and cytoplasmic extracts of multiple human cell lines and mouse liver using selected-reaction monitoring of typical mass transitions of the tryptic peptides. We also show that the methodology can be applied to the identification of hAPE1 variants found in the human population. The results describe a novel approach for the accurate measurement of wild-type and variant forms of hAPE1 in vivo, and ultimately for defining the role of this protein in disease development and treatment responses.

Kirkali, Guldal; Jaruga, Pawel; Reddy, Prasad T.; Tona, Alessandro; Nelson, Bryant C.; Li, Mengxia; Wilson, David M.; Dizdaroglu, Miral



Quantification of serum C-peptide by isotope-dilution liquid chromatography-tandem mass spectrometry: enhanced detection using chemical modification and immunoaffinity purification.  


A method was developed to quantify human serum C-peptide by isotope-dilution mass spectrometry (ID MS). This new approach used immunoaffinity purification and chemical modification to improve the sensitivity which covered the wide range of reference interval of serum C-peptide. The immunoaffinity purification was performed using monoclonal antibody against human C-peptide that was immobilized on magnetic beads, and the purified C-peptide was chemically modified using 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC) prior to liquid chromatography-tandem mass spectrometry (LC-MS/MS). With this method, the LC-MS/MS peak area increased 23-fold compared with the conventional purification by solid-phase extraction and without chemical modification. The limit of quantification was estimated to be 0.003ng on column, which was lower than previously reported. The validation study showed that (1) the response in the 0.003-2.9ng range on column was linear (regression coefficient, r(2)=0.9994), (2) the relative standard deviation (RSD) within and between days was inferior to 4.0%, and (3) the spike and recovery test showed the mean recoveries ranging between 99% and 108%. Comparison with an established commercial immunoassay showed high correlation (r(2)=0.9994) at serum concentration of 0.19-8.49ng/mL. These assessments suggest that this ID MS-based approach can quantify human serum C-peptide with high sensitivity and precision in the reference interval and find a potential use in the reference measurement procedure of serum C-peptide, allowing traceable measurement. This method may also generally be applied to peptide quantification in biological fluids with high sensitivity. PMID:24607695

Kinumi, Tomoya; Mizuno, Ryoko; Takatsu, Akiko



Quantitative determination of free and hydrolytically liberated beta-damascenone in red grapes and wines using a stable isotope dilution assay.  


Quantitative analysis of free and hydrolytically liberated beta-damascenone in grapes and wines was developed, using a stable isotope dilution assay. Free beta-damascenone was isolated from grapes and wines by diethyl ether-hexane (1:1, v/v) extraction and the precursor(s) (glycosidic, polyols) of beta-damascenone using Sep-Pak Plus C18 RP cartridges. Hydrolytically liberated beta-damascenone was generated by acid hydrolysis from the precursor(s) extract. Red wines from Bordeaux (Merlot, Cabernet Sauvignon and Cabernet Franc, 1995 and 1996 vintage), Burgundy (Pinot Noir, 1995 and 1996 vintage) regions and Grenache wines from Chateauneuf du Pape and Côtes du Rhône (1995 vintage) were analysed to quantify free beta-damascenone. The wines made from Grenache and Cabernet Sauvignon (1996 vintage) grapes presented the highest mean amounts of free beta-damascenone, 5.4 and 5.5 micrograms l-1, respectively. Merlot, Cabernet Sauvignon and Cabernet Franc grapes of Bordeaux (1996 vintage) and their corresponding wines were analysed for quantification of free and hydrolytically liberated beta-damascenone. The levels of hydrolytically liberated beta-damascenone in grapes could predict closely the levels of free beta-damascenone in the corresponding wines after one year of ageing, i.e., almost half the levels found for the grape samples. The influence of enzyme and heat treatment of Merlot wine samples on their beta-damascenone levels was studied. Heat treatment doubled the levels of this compound, but enzyme treatment generated, in the corresponding wines, half the levels of beta-damascenone found in the non-enzyme treated wines. PMID:10444847

Kotseridis, Y; Baumes, R L; Skouroumounis, G K



Determination of tellurium in urine by isotope dilution gas chromatography/mass spectrometry using (4-fluorophenyl)magnesium bromide as a derivatizing agent and a comparison with electrothermal atomic absorption spectrometry.  


The antitumor drug AS-101 [ammoniumtrichloro (dioxoethylene-O,O')tellurate(IV)] is the first tellurium-containing compound that has been identified as possessing immunomodulating properties and minimal toxicity. We have developed a stable isotope dilution gas chromatography/mass spectrometry method using 120Te as an internal standard and (4-fluorophenyl)magnesium bromide as a derivatizing agent for Te determination in urine. The urine samples were digested using HNO3 + H2O2 prior to derivatization with lithium bis(trifluoroethyl)dithiocarbamate at a pH of 3. The trifluorodiethyldithiocarbamate of tellurium was reacted with the Grignard reagent in anhydrous diethyl ether to obtain Te-(FC6H4)2 for GC/MS analysis. All isotope ratio measurements were made by selected ion monitoring with a Finnigan MAT 8230 organic mass spectrometer using a 10-m fused silica capillary column. Overall percision values for the five major Te isotopes relative to 130Te were 0.6-3.1% when 10-ng samples of chelated Te were analyzed. No appreciable memory or carry-over effect was observed when two synthetic mixtures differing in 120Te:130Te ratios by a factor of 50 were sequentially analyzed. The isotope dilution GC/MS method was validated by determining Te in urine samples and comparing the values with electrothermal atomic absorption spectrometry. Te concentrations were determined in the 100-500 micrograms/L range with CVs of 1-4%. PMID:8210046

Aggarwal, S K; Kinter, M; Nicholson, J; Herold, D A



Essentials of iron, chromium, and calcium isotope analysis of natural materials by thermal ionization mass spectrometry  

USGS Publications Warehouse

The use of isotopes to understand the behavior of metals in geological, hydrological, and biological systems has rapidly expanded in recent years. One of the mass spectrometric techniques used to analyze metal isotopes is thermal ionization mass spectrometry, or TIMS. While TIMS has been a useful analytical technique for the measurement of isotopic composition for decades and TIMS instruments are widely distributed, there are significant difficulties associated with using TIMS to analyze isotopes of the lighter alkaline earth elements and transition metals. Overcoming these difficulties to produce relatively long-lived and stable ion beams from microgram-sized samples is a non-trivial task. We focus here on TIMS analysis of three geologically and environmentally important elements (Fe, Cr, and Ca) and present an in-depth look at several key aspects that we feel have the greatest potential to trouble new users. Our discussion includes accessible descriptions of different analytical approaches and issues, including filament loading procedures, collector cup configurations, peak shapes and interferences, and the use of isotopic double spikes and related error estimation. Building on previous work, we present quantitative simulations, applied specifically in this study to Fe and Ca, that explore the effects of (1) time-variable evaporation of isotopically homogeneous spots from a filament and (2) interferences on the isotope ratios derived from a double spike subtraction routine. We discuss how and to what extent interferences at spike masses, as well as at other measured masses, affect the double spike-subtracted isotope ratio of interest (44Ca/40Ca in the case presented, though a similar analysis can be used to evaluate 56Fe/54Fe and 53Cr/52Cr). The conclusions of these simulations are neither intuitive nor immediately obvious, making this examination useful for those who are developing new methodologies. While all simulations are carried out in the context of a specific isotope system, it should be noted that the same methods can be used to evaluate any isotope system of interest. ?? 2008 Elsevier B.V.

Fantle, M. S.; Bullen, T. D.



The effects of liquid immiscibility and thermal diffusion on oxygen isotopes in silicate liquids  

NASA Astrophysics Data System (ADS)

Differences between the ?18O values of Si- and Fe-rich immiscible liquids in the system Fe2SiO4-KAlSi2O6-SiO2 (Fa-Lc-Q) in isothermal experiments at 0.1MPa have been determined experimentally to be 0.6 permil. The observed partition of 18O into the Si-rich liquid is consistent with previous experience with the preferential partition of 18O into Si-rich minerals in isothermal equilibrium with minerals of less polymerized structure. Crystallochemical principles affect the distribution of oxygen isotopes in coexisting isothermal liquids in the same way as they apply to isothermally coexisting crystals. The effects of Soret (thermal) diffusion on the distribution of oxygen isotopes in silicate liquids above the solvus in the system Fa-Lc-Q under conditions of an imposed temperature gradient of ca. 250°C over 4mm and at 2GPa have also been investigated experimentally. Both the magnitude and the direction of separation of oxygen isotopes as a result of Soret diffusion are unexpected. For each of the silicate liquids, the cold end of the charge is enriched in 18O by up to 4.7 permil, and the highest ?18O values are associated with the most silica-poor compositions. The distribution of oxygen isotopes appears to be similar in each liquid, regardless of their chemical compositions, which is in contrast to the behaviour of cations whose distributions are compositionally dependent and characterized by strong crystallochemical effects wherein network-forming species such as Si and Al separate to the hot end and Mg, Fe and Ca are segregated preferentially to the cold end. Structural units in the melts are evidently less selective between oxygen isotopes than between cations, because oxygen redistribution over all possible sites in these units proceeds according to mass. Self-diffusion coefficients of oxygen in basaltic liquids estimated from the Soret experiments are in accord with those from other isotope tracer experiments, and comparable to those of Si. The possible effects of Soret diffusion on the oxygen isotopic composition of metasomatic veins in the mantle are examined in light of these data, and indicate that decay of the thermal gradients in the veins exceeds that of the diffusion of oxygen needed to produce variations in the ?18O values of mantle minerals. Variations in oxygen isotope ratios in most natural systems as a result of Soret effects are unlikely.

Kyser, T. K.; Lesher, C. E.; Walker, D.



SciTech Connect

Based on the mineralogy and petrography, coarse-grained, igneous, anorthite-rich (Type C) calcium-aluminum-rich inclusions (CAIs) in the CV3 carbonaceous chondrite Allende have been recently divided into three groups: (i) CAIs with melilite and Al,Ti-diopside of massive and lacy textures (coarse grains with numerous rounded inclusions of anorthite) in a fine-grained anorthite groundmass (6-1-72, 100, 160), (ii) CAI CG5 with massive melilite, Al,Ti-diopside and anorthite, and (iii) CAIs associated with chondrule material: either containing chondrule fragments in their peripheries (ABC, TS26) or surrounded by chondrule-like, igneous rims (93) (Krot et al., 2007a,b). Here, we report in situ oxygen isotopic measurements of primary (melilite, spinel, Al,Ti-diopside, anorthite) and secondary (grossular, monticellite, forsterite) minerals in these CAIs. Spinel ({Delta}{sup 17}O = -25{per_thousand} to -20{per_thousand}), massive and lacy Al,Ti-diopside ({Delta}{sup 17}O = -20{per_thousand} to -5{per_thousand}) and fine-grained anorthite ({Delta}{sup 17}O = -15{per_thousand} to -2{per_thousand}) in 100, 160 and 6-1-72 are {sup 16}O-enriched relative spinel and coarse-grained Al,Ti-diopside and anorthite in ABC, 93 and TS26 ({Delta}{sup 17}O ranges from -20{per_thousand} to -15{per_thousand}, from -15{per_thousand} to -5{per_thousand}, and from -5{per_thousand} to 0{per_thousand}, respectively). In 6-1-72, massive and lacy Al,Ti-diopside grains are {sup 16}O-depleted ({Delta}{sup 17}O {approx} -13{per_thousand}) relative to spinel ({Delta}{sup 17}O = -23{per_thousand}). Melilite is the most {sup 16}O-depleted mineral in all Allende Type C CAIs. In CAI 100, melilite and secondary grossular, monticellite and forsterite (minerals replacing melilite) are similarly {sup 16}O-depleted, whereas grossular in CAI 160 is {sup 16}O-enriched ({Delta}{sup 17}O = -10{per_thousand} to -6{per_thousand}) relative to melilite ({Delta}{sup 17}O = -5{per_thousand} to -3{per_thousand}). We infer that CAIs 100, 160 and CG5 experienced melting in an {sup 16}O-rich ({Delta}{sup 17}O < -20{per_thousand}) nebular gas in the CAI-forming region. The Type C and Type-B-like portions of CAI 6-1-72 experienced melting in an {sup 16}O-depleted ({Delta}{sup 17}O {ge} -13{per_thousand}) nebular gas. CAIs ABC, TS26 and 93 experienced isotopic exchange during re-melting in the presence of an {sup 16}O-poor ({Delta}{sup 17}O {ge} -10{per_thousand}) nebular gas in the chondrule-forming region(s). Subsequently, Allende Type C CAIs experienced post-crystallization isotopic exchange with an {sup 16}O-poor reservoir that affected largely melilite and anorthite. Because pseudomorphic replacement of lacy melilite by grossular, monticellite and forsterite occurred during thermal metamorphism, some oxygen isotopic exchange of melilite and anorthite must have continued after formation of these secondary minerals. We suggest that some or all oxygen isotopic exchange in melilite and anorthite occurred during fluid-assisted thermal metamorphism on the CV parent asteroid. Similar processes may have also affected melilite and anorthite of CAIs in metamorphosed CO chondrites.

Krot, A N; Chaussidon, M; Yurimoto, H; Sakamoto, N; Nagashima, K; Hutcheon, I D; MacPherson, G J



Thermal conduction mechanisms in isotope-disordered boron nitride and carbon nanotubes  

NASA Astrophysics Data System (ADS)

We present first principles studies which determine dominant effects limiting the heat conduction in isotope-disordered boron nitride and carbon nanotubes [1]. Using an ab initio atomistic Green's function approach, we demonstrate that localization cannot be observed in the thermal conductivity measurements [1], and that diffusive scattering is the dominant mechanism which reduces the thermal conductivity [2]. We also give concrete predictions of the magnitude of the isotope effect on the thermal conductivities of carbon and boron nitride single-walled nanotubes [2]. We furthermore show that intershell scattering is not the main limiting mechanism for the heat flow through multi-walled boron nitride nanotubes [1], and that heat conduction restricted to a few shells leads to the low thermal conductivities experimentally measured [1]. We consequently successfully compare the results of our calculations [3] with the experimental measurements [1]. [1] C. W. Chang, A. M. Fennimore, A. Afanasiev, D. Okawa, T. Ikuno, H. Garcia, D. Li, A. Majumdar, A. Zettl, Phys. Rev. Lett. 2006, 97, 085901. [2] I. Savic, N. Mingo, D. A. Stewart, Phys. Rev. Lett. 2008, 101, 165502. [3] I. Savic, D. A. Stewart, N. Mingo, to be published.

Savic, Ivana; Mingo, Natalio; Stewart, Derek



Measuring technique for thermal ionisation mass spectrometry of human tracer kinetic study with stable cerium isotopes.  


Thermal ionisation mass spectrometry (TIMS) method has been developed for the simultaneous detection of different cerium isotopes in biological samples (i.e., blood and urine) at very low concentrations. The work has been done in the frame of a biokinetic study, where different stable cerium isotopes have been administered orally and intravenously as tracers to the human body. In order to develop an appropriate detection method for the tracers in the biological samples, an optimum sample preparation technique has been set and adapted to the specific requirements of the analysis technique used, i.e., TIMS. For sample evaporation and ionisation, the double tantalum filament technique showed the best results. The ions produced were simultaneously collected on a secondary electron multiplier so that the isotopic ratios of the cerium isotopes in the biological samples could be measured. The technique has been optimised for the determination of cerium down to 1 ng loaded on the evaporation filament corresponding to cerium concentrations of down to 1 ng ml(-1) in the blood or urine samples. It has been shown that the technique is reliable in application and enables studies on cerium metabolism and biokinetics in humans without employing radioactive tracers. PMID:21644136

Keiser, Teresa; Höllriegl, Vera; Giussani, Augusto; Oeh, Uwe



Disturbance of isotope systematics in meteorites during shock and thermal metamorphism and implications for shergottite chronology  

SciTech Connect

Shock and thermal metamorphism of meteorites from differentiated bodies such as the Moon and Mars have the potential to disturb chronometric information contained in these meteorites. In order to understand the impact-related mechanisms and extent of disturbance to isochrons, we undertook experiments to shock and heat samples of 10017, a 3.6 billion year old lunar basalt. One sub-sample was shocked to 55 GPa, a second subsample was heated to 1000 C for one week, and a third sub-sample was maintained as a control sample. Of the isotope systems analyzed, the Sm-Nd system was the least disturbed by shock or heat, followed by the Rb-Sr system. Ages represented by the {sup 238}U-{sup 206}Pb isotope system were degraded by shock and destroyed with heating. In no case did either shock or heating alone result in rotated or reset isochrons that represent a spurious age. In some cases the true crystallization age of the sample was preserved, and in other cases age information was degraded or destroyed. Although our results show that neither shock nor thermal metamorphism alone can account for the discordant ages represented by different isotope systems in martian meteorites, we postulate that shock metamorphism may render a meteorite more susceptible than unshocked material to subsequent disturbance during impact-related heating or aqueous alteration on Mars or Earth. The combination of these processes may result in the disparate chronometric information preserved in some meteorites.

Gaffney, A M; Borg, L E; Asmerom, Y



Quantitation of benzo[a]pyrene metabolic profiles in human bronchoalveolar (H358) cells by stable isotope dilution liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.  


Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants and are carcinogenic in multiple organs and species. Benzo[a]pyrene (B[a]P) is a representative PAH and has been studied extensively for its carcinogenicity and toxicity. B[a]P itself is chemically inert and requires metabolic activation to exhibit its toxicity and carcinogenicity. Three major metabolic pathways have been well documented. The signature metabolites generated from the radical cation (peroxidase or monooxygenase mediated) pathway are B[a]P-1,6-dione and B[a]P-3,6-dione, the signature metabolite generated from the diol-epoxide (P450 mediated) pathway is B[a]P-r-7,t-8,t-9,c-10-tetrahydrotetrol (B[a]P-tetrol-1), and the signature metabolite generated from the o-quinone (aldo-keto reductase mediated) pathway is B[a]P-7,8-dione. The contributions of these different metabolic pathways to cancer initiation and the exploitation of this information for cancer prevention are still under debate. With the availability of a library of [(13)C(4)]-labeled B[a]P metabolite internal standards, we developed a sensitive stable isotope dilution atmospheric pressure chemical ionization tandem mass spectrometry method to address this issue by quantitating B[a]P metabolites from each metabolic pathway in human lung cells. This analytical method represents a 500-fold increased sensitivity compared with that of a method using HPLC-radiometric detection. The limit of quantitation (LOQ) was determined to be 6 fmol on column for 3-hydroxybenzo[a]pyrene (3-OH-B[a]P), the generally accepted biomarker for B[a]P exposure. This high level of sensitivity and robustness of the method was demonstrated in a study of B[a]P metabolic profiles in human bronchoalveolar H358 cells induced or uninduced with the AhR ligand, 2,3,7,8-tetrachlorodibenzodioxin (TCDD). All the signature metabolites were detected and successfully quantitated. Our results suggest that all three metabolic pathways contribute equally in the overall metabolism of B[a]P in H358 cells with or without TCDD induction. The sensitivity of the method should permit the identification of cell-type differences in B[a]P activation and detoxication and could also be used for biomonitoring human exposure to PAH. PMID:21962213

Lu, Ding; Harvey, Ronald G; Blair, Ian A; Penning, Trevor M



Monitoring urinary metabolites resulting from sulfur mustard exposure in rabbits, using highly sensitive isotope-dilution gas chromatography-mass spectrometry.  


A highly sensitive method for the determination of sulfur mustard (SM) metabolites thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in urine was established and validated using isotope-dilution negative-ion chemical ionization (NICI) gas chromatography-mass spectrometry (GC-MS). TDGO in the samples was reduced with TiCl3, and then determined together with TDG as a single analyte. The sample preparation procedures, including two solid-phase-extraction (SPE) clean-up steps, were optimized to improve the sensitivity of the method. The limits of detection (LOD) for both TDG and TDG plus TDGO (TDG + TDGO) were 0.1 ng mL(-1), and the limits of quantitation (LOQ) for both were 0.3 ng mL(-1). The method was used in a rabbit cutaneous SM exposure model. Domestic rabbits were exposed to neat liquid SM at three dosage levels (0.02, 0.05, and 0.15 LD50), and the urinary excretion of four species of hydrolysis metabolites, namely free TDG, free plus conjugated TDG (total TDG), free TDG + TDGO, and free plus conjugated TDG + TDGO (total TDG + TDGO), was evaluated to investigate the metabolic processes. The total urinary excretion profiles of the metabolites, including the peak time, time window, and dose-response and time-response relationships, were clarified. The results revealed that the concentrations of TDG and TDG + TDGO in the urine increased quickly and then decreased rapidly in the first two days after SM exposure. The cumulative amount of total TDG + TDGO excreted in urine during the first five days accounted for 0.5-1 % of the applied dose of SM. It is also concluded that TDG and TDGO in urine existed mainly in free form, the levels of glucuronide and of sulfate conjugates of TDG or TDGO were very low, and most hydrolysis metabolites were present in the oxidized form (TDGO). The study indicates that the abnormal increase of TDG and TDGO excretion levels can be used as a diagnostic indicator and establishes a reference time-window for retrospective analysis and sampling after SM exposure. PMID:24924210

Nie, Zhiyong; Zhang, Yajiao; Chen, Jia; Lin, Ying; Wu, Bidong; Dong, Yuan; Feng, Jianlin; Liu, Qin; Xie, Jianwei



Isotope dilution liquid chromatography-tandem mass spectrometry for simultaneous identification and quantification of beta-casomorphin 5 and beta-casomorphin 7 in yoghurt.  


A highly selective and sensitive liquid chromatography-tandem mass spectrometry method was developed and validated for the simultaneous identification and quantification of beta-casomorphin 5 (BCM5) and beta-casomorphin 7 (BCM7) in yoghurt. The method used deuterium labelled BCM5-d10 and BCM7-d10 as surrogate standards for confident identification and accurate and quantification of these analytes in yoghurt. Linear responses for BCM5 and BCM7 (R(2)=0.9985 and 0.9986, respectively) was observed in the range 0.01-10ng/?L. The method limits of detection (MLDs) in yoghurt extracts were found to be 0.5 and 0.25ng/g for BCM5 and BCM7, respectively. Analyses of spiked samples were used to provide confirmation of accuracy and precision of the analytical method. Recoveries relative to the surrogate standards of these spikes were in the range of 95-106% for BCM5 and 103-109% for BCM7. Precision from analysis of spiked samples was expressed as relative standard deviation (%RSD) and values were in the range 1-16% for BCM5 and 1-6% for BCM7. Inter-day reproducibility was between 2.0-6.4% for BCM5 and between 3.2-6.1% for BCM7. The validated isotope dilution LC-MS/MS method was used to measure BCM5 and BCM7 in ten commercial and laboratory prepared samples of yoghurt and milk. Neither BCM5 nor BCM7 was detected in commercial yoghurts. However, they were observed in milk and laboratory prepared yoghurts and interestingly their levels decreased during processing. BCM5 decreased from 1.3ng/g in milk to 1.1ng/g in yoghurt made from that milk at 0day storage and

Nguyen, D D; Solah, V A; Johnson, S K; Charrois, J W A; Busetti, F



Selenium and Tellurium concentrations of ultradepleted peridotites determined by isotope dilution ICPMS: implications for Se-Te systematics of the Earth's mantle  

NASA Astrophysics Data System (ADS)

As for highly siderophile elements, selenium and tellurium may constitute key tracers for planetary processes such as formation of the Earth's core and the Late Veneer composition, provided that their geochemical behaviour and abundances in the primitive upper mantle (PUM) are constrained. Within this scope, we have developed a high precision analytical method for the simultaneous determination of selenium and tellurium concentrations from a single sample aliquot and various rock matrices, including ultradepleted peridotites. The technique employs isotope dilution, thiol cotton fiber (TCF) separation and hydride generation MC-ICP-MS. A selection of international mafic and ultramafic rock reference materials BIR-1, BE-N, TDB-1, UB-N, FON B 93, BIR-1 and BHVO-2 with a range of 30 to 350 ppb Se and 0.7 to 12 ppb Te show external reproducibilities of 3 to 8% for Se and 0.4 to 11% for Te (2 relative standard deviations (r.s.d.)). We have applied this method to a suite of refractory mantle peridotites (Al2O3 <1.5 wt. %) from Lherz, previously shown to be strongly and uniformly depleted in Se, Te and incompatible elements by high degree of partial melting (20 ± 5%). In contrast to fertile lherzolites which remain at broadly chondritic values (Se/Te = 9), the ultradepleted harzburgites show highly fractionated and up to suprachondritic Se/Te (< 35) that correlate with decreasing Te concentrations. The fractionation is displayed by the depleted peridotites as well as multiple analysis of a single Lherz harzburgite sample (64-3). This shows 1) a strong sample heterogeneity effect for Te and 2) a more incompatible behaviour of Te compared to Se on the whole rock scale, once base metal sulfides are highly depleted and in some cases entirely consumed by partial melting. The marked differences in Se-Te systematics observed between fertile lherzolites and depleted harzburgites can be explained by the combined effect of i) different abundances and proportions of residual and metasomatic base metal sulfides ii) discrete micrometric platinum-group minerals. In addition to re-fertilized lherzolites, harzburgites therefore offer new insights into the behaviour of Se and Te during mantle depletion which is a prerequisite to further constrain the Se and Te abundances of the primitive upper mantle.

König, S.; Luguet, A.; Lorand, J.-P.; Wombacher, F.; Lissner, M.



Quantitation of Benzo[a]pyrene Metabolic Profiles in Human Bronchoalveolar H358) Cells by Stable Isotope Dilution Liquid Chromatography-Atmospheric Chemical Ionization Mass Spectrometry  

PubMed Central

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants and are carcinogenic in multiple organs and species. Benzo[a]pyrene (B[a]P) is a representative PAH and has been studied extensively for its carcinogenicity and toxicity. B[a]P itself is chemically inert and requires metabolic activation to exhibit its toxicity and carcinogenicity. Three major metabolic pathways have been well documented. The signature metabolites generated from the radical cation (peroxidase or monooxygenase mediated) pathway are B[a]P-1,6-dione and B[a]P-3,6-dione, the signature metabolite generated from the diol-epoxide (P450 mediated) pathway is B[a]P-r-7,t-8,t-9,c-10-tetrahydrotetrol (B[a]P-tetrol-1) and the signature metabolite generated from the o-quinone (aldo-keto reductase mediated) pathway is B[a]P-7,8-dione. The contributions of these different metabolic pathways to cancer initiation and the exploitation of this information for cancer prevention are still under debate. With the availability of a library of [13C4]-labeled B[a]P metabolite internal standards, we developed a sensitive stable isotope dilution atmospheric pressure chemical ionization tandem mass spectrometry method to address this issue by quantitating B[a]P metabolites from each metabolic pathway in human lung cells. This analytical method represents a 500 fold increased sensitivity compared with a method using HPLC-radiometric detection. The limit of quantitation (LOQ) was determined to be 6 fmol on column for 3-hydroxybenzo[a]pyrene (3-OH-B[a]P), the generally accepted biomarker for B[a]P exposure. This high level of sensitivity and robustness of the method was demonstrated in a study of B[a]P metabolic profiles in human bronchoalveolar H358 cells induced or uninduced with the AhR ligand, 2,3,7,8-tetrachlorodibenzodioxin (TCDD). All the signature metabolites were detected and successfully quantitated. Our results suggest that all three metabolic pathways contribute equally in the overall metabolism of B[a]P in H358 cells with or without TCDD induction. The sensitivity of the method should permit the identification of cell-type differences in B[a]P activation and detoxication and could also be used for biomonitoring human exposure to PAH.

Lu, Ding; Harvey, Ronald G.; Blair, Ian A.; Penning, Trevor M.



A Transient Model of Induced Natural Circulation Thermal Cycling for Hydrogen Isotope Separation  

SciTech Connect

The property of selective temperature dependence of adsorption and desorption of hydrogen isotopes by palladium is used for isotope separation. A proposal to use natural circulation of nitrogen to alternately heat and cool a packed bed of palladium coated beads is under active investigation, and a device consisting of two interlocking natural convection loops is being designed. A transient numerical model of the device has been developed to aid the design process. It is a one-dimensional finite-difference model, using the Boussinesq approximation. The thermal inertia of the pipe walls and other heat structures as well as the heater control logic is included in the model. Two system configurations were modeled and results are compared.




Multiple Export Production and Sulfur Isotope Records over the Paleocene Eocene Thermal Maximum  

NASA Astrophysics Data System (ADS)

The Paleocene Eocene Thermal Maximum (PETM) was a global climatic event that occurred 55 million years ago. ?18O values from benthic foraminifera indicate that temperatures rose 4-5°C coeval with a precipitous drop in ?13C values that indicate a new source of carbon rapidly entered the global carbon cycle. Marine barite (BaSO4) was used to evaluate the 1) barite accumulation rate that serves a proxy for export production and 2) the sulfur isotopic composition of seawater that reflects the mass balance of oceanic sulfate (SO42-). Increased barite accumulation rates at the PETM suggest that increased export production and CO2 sequestration was in direct response to the carbon isotope excursion, although not all of the increases are accounted for. High resolution ?34S values are lower but within reasonable range of previously observed values and indicate a decrease in sulfate removal by pyrite deposition.

Gray, E.; Paytan, A.



Global warming leads the carbon isotope excursion at the Paleocene-Eocene thermal maximum  

NASA Astrophysics Data System (ADS)

The prominent negative carbon isotope excursion (CIE) at the Paleocene-Eocene thermal maximum (55.5 Ma) is generally accepted to reflect a transient, massive input of isotopically light carbon into the ocean- atmosphere system. Many authors have assumed that this carbon led to pronounced global greenhouse warming. Here we show, from an expanded record in New Jersey, that both the onset of the global abundance of the subtropical dinoflagellate Apectodinium and surface-ocean warming as recorded by TEX86 preceded the CIE by several thousands of years. The offset between Apectodinium and the CIE was confirmed in other sites from New Jersey, the North Sea and New Zealand. The approximately 3 kyrs time lag between the onset of warming and the CIE is consistent with the expected lag between bottom water warming and submarine methane hydrate dissociation, suggesting that the latter mechanism indeed caused the CIE.

Sluijs, A.; Brinkhuis, H.; Schouten, S.; Zachos, J. C.; Bohaty, S.; John, C.; Deltrap, R.; Reichart, G.; Sinninghe Damsté, J.; Crouch, E.



Certification of the Cu and Cd amount contents in artificial food digest using isotope dilution inductively coupled plasma mass spectrometry for Pilot Study 13 of the Comité Consultatif pour la Quantité de Matière  

NASA Astrophysics Data System (ADS)

The Comité Consultatif pour la Quantité de Matière (CCQM) launched the Pilot Study 13, an interlaboratory comparison between the metrological organizations worldwide on the determination of Ca, Cu and Cd in artificial food digests. These samples (available in 7% HNO 3 and with a salinity evaluated around 370 mg kg -1, including approx. 30 mg Na kg -1) were prepared by gravimetrical mixing, and thus reference values traceable to the Kg for the three elements were available eventually. This paper describes the contribution of IRMM for the certification of the Cu and the Cd amount contents. The analytical protocol developed was based on isotope dilution associated to inductively coupled plasma mass spectrometry (ID-ICP-MS). The Cu measurements required 125-fold dilution of the initial sample solution. An interference of 23Na 40Ar + on 63Cu + was identified but, since the ratio between both species was over 1000, it was successfully overcome by the calculation of a correction factor for its effect on the Cu amount content directly. Dilution of the sample was not possible for Cd only present at the low ng g -1 level. Up to 1% difference was observed on Cd isotope ratio results between measurements performed directly or after matrix separation. This is rarely shown. As similar results could be obtained either way after the necessary corrections, the direct measurements approach associated to a correction for mass discrimination effects using the CCQM-P13 sample itself (and the IUPAC table values as reference for the natural Cd isotopic composition) was preferred as it was the easiest. SI traceable values were obtained for Cu and Cd with less than 1 and 1.5% combined uncertainty, respectively (6 995±55 ( k=2) nmol kg -1 and 45.53±0.64 ( k=2) nmol kg -1). The excellent agreement between these results and the reference values (less than 0.6 and 0.08% difference) further validated the analytical protocols developed.

Vassileva, E.; Quétel, C. R.; Petrov, I.



Ammonium in thermal waters of Yellowstone National Park: processes affecting speciation and isotope fractionation  

USGS Publications Warehouse

Dissolved inorganic nitrogen, largely in reduced form (NH4(T)?NH4(aq)++NH3(aq)o), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH4(T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH4(T) concentration and ?18O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH4(T) and other solutes in some areas. The isotopic composition of dissolved NH4(T) is highly variable (?15N = ?6‰ to +30‰) and is positively correlated with pH values. In comparison to likely ?15N values of nitrogen source materials (+1‰ to +7‰), high ?15N values in hot springs with pH >5 are attributed to isotope fractionation associated with NH3(aq)o loss by volatilization. NH4(T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative ?15N values that are attributed to NH3(g)o condensation. NH4(T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH4(T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.

Holloway, J. M.; Nordstrom, D. K.; Bohlke, J. K.; McCleskey, R. B.; Ball, J. W.



Ammonium in thermal waters of Yellowstone National Park: Processes affecting speciation and isotope fractionation  

NASA Astrophysics Data System (ADS)

Dissolved inorganic nitrogen, largely in reduced form ( NH(T)?NH4(aq)++NH3(aq)o), has been documented in thermal waters throughout Yellowstone National Park, with concentrations ranging from a few micromolar along the Firehole River to millimolar concentrations at Washburn Hot Springs. Indirect evidence from rock nitrogen analyses and previous work on organic compounds associated with Washburn Hot Springs and the Mirror Plateau indicate multiple sources for thermal water NH 4(T), including Mesozoic marine sedimentary rocks, Eocene lacustrine deposits, and glacial deposits. A positive correlation between NH 4(T) concentration and ? 18O of thermal water indicates that boiling is an important mechanism for increasing concentrations of NH 4(T) and other solutes in some areas. The isotopic composition of dissolved NH 4(T) is highly variable (? 15N = -6‰ to +30‰) and is positively correlated with pH values. In comparison to likely ? 15N values of nitrogen source materials (+1‰ to +7‰), high ? 15N values in hot springs with pH >5 are attributed to isotope fractionation associated with NH3(aq)o loss by volatilization. NH 4(T) in springs with low pH typically is relatively unfractionated, except for some acid springs with negative ? 15N values that are attributed to NH3(g)o condensation. NH 4(T) concentration and isotopic variations were evident spatially (between springs) and temporally (in individual springs). These variations are likely to be reflected in biomass and sediments associated with the hot springs and outflows. Elevated NH 4(T) concentrations can persist for 10s to 1000s of meters in surface waters draining hot spring areas before being completely assimilated or oxidized.

Holloway, JoAnn M.; Nordstrom, D. Kirk; Böhlke, J. K.; McCleskey, R. Blaine; Ball, James W.



Light-stable-isotope studies of spring and thermal waters from the Roosevelt Hot Springs and Cove Fort/Sulphurdale Thermal areas and of clay minerals from the Roosevelt Hot Springs thermal area  

SciTech Connect

The isotopic compositions of hydrogen and oxygen have been determined for spring waters and thermal fluids from the Roosevelt Hot Springs and Cove Fort-Sulphurdale thermal areas, for clay mineral separates from shallow alteration of the acid-sulfate type in the Roosevelt Hot Springs area, and for spring and well waters from the Goshen Valley area of central Utah. The water analyses in the Roosevelt Hot Springs thermal area confirm the origin of the thermal fluids from meteoric water in the Mineral Range. The water analyses in the Cove Fort-Sulphurdale thermal area restrict recharge areas for this system to the upper elevations of the Pavant and/or Tushar Ranges. The low /sup 18/O shift observed in these thermal fluids (+0.7 permil) implies either high water/rock ratios or incomplete isotope exchange or both, and further suggests minimal interaction between the thermal fluid and marble country rock in the system. Hydrogen and oxygen-isotope data for clay mineral separates from shallow alteration zones in the Roosevelt Hot Springs thermal system suggest that the fluids responsible for the shallow acid-sulfate alteration were in part derived from condensed steam produced by boiling of the deep reservoir fluid. The isotope evidence supports the chemical model proposed by Parry et al. (1980) for origin of the acid-sulfate alteration at Roosevelt Hot Springs. The isotope analyses of spring and well waters from the Goshen Valley area indicate only a general correlation of isotope composition, salinity and chemical temperatures.

Bowman, J.R.; Rohrs, D.T.



Stable-isotope dilution gas chromatography–mass spectrometric measurement of 3-hydroxyglutaric acid, glutaric acid and related metabolites in body fluids of patients with glutaric aciduria type 1 found in newborn screening  

Microsoft Academic Search

We developed a simple and sensitive stable-isotope dilution method for the quantification of 3-hydroxyglutaric acid (3HGA) and glutaric acid (GA) in body fluids. In our method, tert-butyldimethylsilyl (tBDMS) derivatives of 3HGA and GA were measured with a conventional electron-impact ionization (EI) mode in gas chromatography–mass spectrometry (GC–MS). The control values for 3HGA in nmol\\/ml were 0.15±0.08 (serum; n=10) and 0.07±0.03

Yosuke Shigematsu; Ikue Hata; Yukie Tanaka; Go Tajima; Nobuo Sakura; Etsuo Naito; Toru Yorifuji



An experimental and numerical investigation on the influence of external gas recirculation on the HCCI autoignition process in an engine: Thermal, diluting, and chemical effects  

SciTech Connect

In order to contribute to the solution of controlling the autoignition in a homogeneous charge compression ignition (HCCI) engine, parameters linked to external gas recirculation (EGR) seem to be of particular interest. Experiments performed with EGR present some difficulties in interpreting results using only the diluting and thermal aspect of EGR. Lately, the chemical aspect of EGR is taken more into consideration, because this aspect causes a complex interaction with the dilution and thermal aspects of EGR. This paper studies the influence of EGR on the autoignition process and particularly the chemical aspect of EGR. The diluents present in EGR are simulated by N{sub 2} and CO{sub 2}, with dilution factors going from 0 to 46 vol%. For the chemically active species that could be present in EGR, the species CO, NO, and CH{sub 2}O are used. The initial concentration in the inlet mixture of CO and NO is varied between 0 and 170 ppm, while that of CH{sub 2}O alters between 0 and 1400 ppm. For the investigation of the effect of the chemical species on the autoignition, a fixed dilution factor of 23 vol% and a fixed EGR temperature of 70 C are maintained. The inlet temperature is held at 70 C, the equivalence ratios between 0.29 and 0.41, and the compression ratio at 10.2. The fuels used for the autoignition are n-heptane and PRF40. It appeared that CO, in the investigated domain, did not influence the ignition delays, while NO had two different effects. At concentrations up until 45 ppm, NO advanced the ignition delays for the PRF40 and at higher concentrations, the ignition delayed. The influence of NO on the autoignition of n-heptane seemed to be insignificant, probably due to the higher burn rate of n-heptane. CH{sub 2}O seemed to delay the ignition. The results suggested that especially the formation of OH radicals or their consumption by the chemical additives determines how the reactivity of the autoignition changed. (author)

Machrafi, Hatim; Cavadias, Simeon [UPMC Universite Paris 06, LGPPTS, Ecole Nationale Superieure de Chimie de Paris, 11, rue de Pierre et Marie Curie, 75005 Paris (France); UPMC Universite Paris 06, FRT, Institut Jean Le Rond D'Alembert, 2, place de la Gare de Ceinture, 78210 St Cyr l'Ecole (France); Guibert, Philippe [UPMC Universite Paris 06, FRT, Institut Jean Le Rond D'Alembert, 2, place de la Gare de Ceinture, 78210 St Cyr l'Ecole (France)



Determination of the four natural Ra isotopes in thermal waters by gamma-ray spectrometry.  


Our method for the simultaneous determination of the four natural Ra isotopes ((226)Ra, (228)Ra, (224)Ra and (223)Ra) in thermal waters involves a separation of Ra on a selective filter (3M EMPORE Radium Rad disk), and a single counting using a broad-energy HPGe detector (BE Ge manufactured by CANBERRA). The calculation of (223)Ra and (228)Ra activities requires interference and cascade summing corrections. The (226)Ra activities in CO(2)-rich thermal waters of the Lodève Basin (South of France) range from 530 to 2240mBq/l. The low ((228)Ra/(226)Ra) activity ratios (0.19-0.29) suggest that Ra is mostly derived from the aquifer carbonates. The short-lived (224)Ra and (223)Ra are probably added to the water through recoil or desorption processes from Th-enriched coatings on the fracture walls. PMID:19954987

Condomines, M; Rihs, S; Lloret, E; Seidel, J L



Hydrogen and oxygen isotope geochemistry of cold and warm springs from the Tuscarora, Nevada thermal area  

SciTech Connect

Eighteen cold and warm spring water samples from the Tuscarora, Nevada KGRA have been analyzed for hydrogen and oxygen isotope composition and fluid chemistry. Warm springs have deltaD values (-128 to -137 permil) significantly lower than those of cold springs to the north and east of the area, but similar to the deltaD values of cold springs to the west and south (-131 to -135 permil). The recharge area for the warm springs is unlikely to be to the immediate north, which is the local topographic highland in the area. The hydrogen isotope data would permit recharge from areas to the southwest or from high elevations to the southeast (Independence Mountains), a sector consistent with electrical resistivity evidence of fluid flow. Warm springs are HCO/sub 3//sup -/-rich waters, enriched by a factor of 3 to 10 in Na, HCO{sub 3}/{sup -} and SiO{sub 2} relative to local cold springs. Average quartz (no steam loss) and Na/K/Ca geothermometer estimates suggest subsurface temperatures of 145{sup 0} and 196{sup 0}C, respectively. The warm springs exhibit poor correlations between either hydrogen or oxygen isotope composition and water temperature or chemistry. The absence of such correlations suggests that there is no single coherent pattern of cold water mixing or evaporation in the thermal spring system.

Bowman, J.R.; Cole, D.



Liquid chromatography/electrospray ionization/isotopic dilution mass spectrometry analysis of n-(phosphonomethyl) glycine and mass spectrometry analysis of aminomethyl phosphonic acid in environmental water and vegetation matrixes.  


A liquid chromatography/electrospray/mass spectrometry (LC/ES/MS) method was developed for the analysis of glyphosate (n-phosphonomethyl glycine) and its metabolite, aminomethyl phosphonic acid (AMPA) using isotope-labelled glyphosate as a method surrogate. Optimized parameters were achieved to derivatize glyphosate and AMPA using 9-fluorenylmethyl chloroformate (FMOC-Cl) in borate buffer prior to a reversed-phase LC analysis. Method spike recovery data obtained using laboratory and real world sample matrixes indicated an excellent correlation between the recovery of the native and isotope-labelled glyphosate. Hence, the first performance-based, isotope dilution MS method with superior precision, accuracy, and data quality was developed for the analysis of glyphosate. There was, however, no observable correlation between the isotope-labelled glyphosate and AMPA. Thus, the use of this procedure for the accurate analysis of AMPA was not supported. Method detection limits established using standard U.S. Environmental Protection Agency protocol were 0.06 and 0.30 microg/L, respectively, for glyphosate and AMPA in water matrixes and 0.11 and 0.53 microg/g, respectively, in vegetation matrixes. Problems, solutions, and the method performance data related to the analysis of chlorine-treated drinking water samples are discussed. Applying this method to other environmental matrixes, e.g., soil, with minimum modifications is possible, assuring accurate, multimedia studies of glyphosate concentration in the environment and the delivery of useful multimedia information for regulatory applications. PMID:11767144

Grey, L; Nguyen, B; Yang, P



Noble gas isotopic signatures in thermal waters of the Dead Sea Transform  

NASA Astrophysics Data System (ADS)

Noble gas isotope composition in thermal groundwater provides information about crust-mantle interactions, in form of geotectonic activity, volcanism and advective heat transfer. The knowledge of the geothermal state of the crust is useful for the indication of thermal energy resources, which are of significant environmental and economic importance. In this study, groundwater samples were collected in Israel and Jordan in 2012, along the east and west sides of the central Dead Sea Transform. The helium isotope ratio, 3He/4He, is a well-established marker to discriminate three different geochemical reservoirs: Atmosphere, crust and mantle. The distinct isotope ratios in each reservoir make it possible to separate the total helium concentration in groundwater into mantle, crustal (radiogenic) and atmospheric components. The 3He/4He ratios of all sampled waters exceed the typical crustal ratio, indicating contributions of mantle-derived helium to the total helium concentration. Most of the samples contain less than 3% atmospheric helium, whereas the mantle-derived helium component ranges from 1% to 61%. In Israel, a clear trend is observed. Samples from the northern parts of the sampling area show higher 3He/4He ratios than samples from southern parts. These findings confirm Torfstein et al. [1], who analyzed thermal groundwaters from Israel. In our data from Jordan, however, no north-south trend is seen, but a local anomaly is observed in the area between the Dead Sea and the Sea of Galilee, with a 3He/4He ratio that is 5 times higher than the atmospheric 3He/4He ratio. Moreover, some samples from North Jordan exhibit only minor mantle contributions, compared to the samples from the north of Israel. Our results emphasize the importance of local faulting patterns, which enable a better transfer of mantle derived helium into the shallow crust. In addition to helium, the origin of CO2 in the water was examined. Measurements of ?13C suggest that CO2 originates from metamorphic processes rather than from the mantle. Furthermore, ?18O and ?2H data indicate a water reservoir temperature above 100°C only at one location. References: [1] Torfstein, A. et al. 2013: Helium isotopes in Dead Sea Transform waters. Chemical Geology, 352, 188-201

Tsur, Neta; Kaudse, Tillmann; Aeschbach-Hertig, Werner



System and method for measuring cardiac output via thermal dilution using an implantable medical device with an external ultrasound power delivery system  

US Patent & Trademark Office Database

The implantable device is capable of performing thermal dilution analysis of the cardiac output of a patient using power delivered from an external source. By using power from an external source, the implantable device conserves its power resources for other purposes, such as for pacing or defibrillation therapy. In one example, an external programmer or bedside monitor provides power through a hand-held power delivery wand via electromagnetic induction, with the power routed from a subcutaneous coil to a heating element implanted in the right atrium, which heats blood as it passes through the right atrium. In another example, the heating element is formed of a material that generates heat in response to a beam of ultrasound provided by the wand. In either case, a downstream blood temperature profile is detected using a thermistor implanted in the pulmonary artery and cardiac output is then estimated by analyzing the temperature profile.



Dilution Confusion: Conventions for Defining a Dilution  

ERIC Educational Resources Information Center

Two conventions for preparing dilutions are used in clinical laboratories. The first convention defines an "a:b" dilution as "a" volumes of solution A plus "b" volumes of solution B. The second convention defines an "a:b" dilution as "a" volumes of solution A diluted into a final volume of "b". Use of the incorrect dilution convention could affect…

Fishel, Laurence A.



Mineralogical and isotopic constraints on chondrule formation from shock wave thermal histories  

NASA Astrophysics Data System (ADS)

When a shock wave passes through a nebular gas, increasing water enrichment leads to higher temperatures and post-shock P, but lower cooling rates. A kinetic evaporation model is developed for tracking the chemical and isotopic changes that would occur in a clump of chondrule precursor dust surrounded by nebular gas in a closed system traversed by a nebular shock wave, taking into account effects of non-equilibrium melting and fractional crystallization on the liquid composition and the temperature difference between the gas and the droplet. A range of shock wave temperature-pressure histories computed for systems enriched relative to solar composition by factors of 550 in water, to achieve the redox state of chondrules, and 600 in dust, to retard evaporation, are employed, and redox changes are assumed to occur on the time-scale of heating and cooling in each. Two different system compositions are assumed, with the mean Fe/Si ratios of Types I and II chondrules. Two different textural outcomes are modeled, PO, in which nuclei are preserved and olivine crystallization begins immediately upon reaching saturation, and BO, in which no nuclei are preserved and olivine crystallization begins only after 300-400 K of supersaturation. In all cases, all iron evaporates, regardless of its oxidation state, as well as alkalis and smaller fractions of Mg and Si. In most cases, recondensation occurs on the time-scale of cooling, resulting in droplets whose bulk compositions have small isotopic anomalies in Mg, Si and Fe, comparable to those seen in bulk chondrules. Because fractional crystallization of olivine occurs before recondensation is complete, however, large isotopic variations, especially for iron, would have been recorded both within olivine crystals and between olivine and glass within these objects. Even after diffusive relaxation during crystal growth and cooling, variations in ?25Mg of several tenths of a ‰ to several ‰, in ?29Si of 0.1‰ to several ‰ and in ?56Fe of several ‰ would be measurable within large grains that grew throughout the olivine crystallization interval in many cases, and olivine-glass differences of ?several tenths of a ‰ in ?29Si, and of several ‰ in ?56Fe would be preserved. Such internal isotopic heterogeneities have not yet been observed in chondrules, suggesting that the latter did not form in these shock wave thermal histories. Suppression of production of internal isotopic variations requires heating times that are shorter by a factor of 100, combined with dust enrichments ? 6 × 104 and/or P?10-2 bar. Together with relatively high f, these constraints suggest that chondrules formed in clouds of liquid and vapor generated by impact on ice-rich planetesimals.

Fedkin, Alexei V.; Grossman, Lawrence; Ciesla, Fred J.; Simon, Steven B.



Thermally-induced protein unfolding probed by isotope-edited IR spectroscopy  

PubMed Central

Infrared (IR) spectroscopy has been widely utilized for the study of protein folding, unfolding and misfolding processes. We have previously developed a theoretical method for calculating IR spectra of proteins in the amide I region. In this work, we apply this method, in combination with replica-exchange molecular dynamics simulations, to study the equilibrium thermal unfolding transition of the villin headpiece subdomain (HP36). Temperature-dependent IR spectra and spectral densities are calculated. The spectral densities correctly reflect the unfolding conformational changes in the simulation. With the help of isotope labeling, we are able to capture the feature that helix 2 of HP36 loses its secondary structure before global unfolding occurs, in agreement with experiment.

Wang, Lu; Skinner, James L.



Use of stable sulphur isotopes to monitor directly the behaviour of sulphur in coal during thermal desulphurization  

USGS Publications Warehouse

A method has been developed using stable sulphur isotope analyses to monitor the behaviour of sulphur forms in a coal during thermal desulphurization. In this method, the natural stable isotopic composition of the pyritic and organic sulphur in coal is used as a tracer to follow their mobility during the desulphurization process. This tracer method is based on the fact that the isotopic compositions of pyritic and organic sulphur are significantly different in some coals. Isotopic results of pyrolysis experiments at temperatures ranging from 350 to 750 ??C indicate that the sulphur released with the volatiles is predominantly organic sulphur. The pyritic sulphur is evolved in significant quantities only when pyrolysis temperatures exceed 500 ??C. The presence of pyrite seems to have no effect on the amount of organic sulphur evolved during pyrolysis. The chemical and isotopic mass balances achieved from three different samples of the Herrin (No. 6) coal of the Illinois Basin demonstrate that this stable isotope tracer method is quantitative. The main disadvantage of this tracing technique is that not all coals contain isotopically distinct organic and pyritic sulphur. ?? 1987.

Liu, C. L.; Hackley, K. C.; Coleman, D. D.



Solar Carbon Monoxide, Thermal Profiling, and the Abundances of C, O, and Their Isotopes  

NASA Astrophysics Data System (ADS)

A solar photospheric ``thermal profiling'' analysis is presented, exploiting the infrared (2.3-4.6 ?m) rovibrational bands of carbon monoxide (CO) as observed with the McMath-Pierce Fourier transform spectrometer (FTS) at Kitt Peak, and from above the Earth's atmosphere by the Shuttle-borne ATMOS experiment. Visible continuum intensities and center-limb behavior constrained the temperature profile of the deep photosphere, while CO center-limb behavior defined the thermal structure at higher altitudes. The oxygen abundance was self-consistently determined from weak CO absorptions (for C/O?0.5). Our analysis was meant to complement recent studies based on three-dimensional (3D) convection models, which, among other things, have revised the historical solar oxygen (and carbon) abundance downward by a factor of nearly 2, although in fact our conclusions do not support such a revision. Based on various considerations, an ?O=700+/-100 ppm (parts per million relative to hydrogen) is recommended; the large uncertainty reflects the model sensitivity of CO. New solar isotopic ratios also are reported: 12C/13C=80+/-1, 16O/17O=1700+/-220, and 16O/18O=440+/-6-all significantly lower than terrestrial. CO synthesis experiments utilizing a stripped down version of the 3D model-which has large temperature fluctuations in the middle photosphere, possibly inconsistent with CO ``movies'' from the Infrared Imaging Spectrometer (IRIS), and a steeper mean temperature gradient than matches visible continuum center-limb measurements-point to a lower oxygen abundance (~500 ppm) and isotopic ratios closer to terrestrial. A low oxygen abundance from CO-and other molecules like OH-thus hinges on the reality of the theoretically predicted midphotospheric convective properties.

Ayres, Thomas R.; Plymate, Claude; Keller, Christoph U.



Halogen Chemistry and Stable Cl Isotope Composition of Thermal Springs in the Cascade Arc  

NASA Astrophysics Data System (ADS)

The Cascade volcanic arc is located above a young (~6Ma) and slowly subducting (~4 cm/y) Juan de Fuca plate. Because of the high temperatures in the subduction slab, dehydration reactions are thought to occur at shallow depth to the west of the Cascade volcanic front. Spatial devolatization trends may be observed at the surface by examining geochemical trends from along and across the volcanic front. We have measured the concentration of halogens (F, Cl, Br, I) and the stable Cl isotope compositions of thermal spring waters and primitive basalts along and across the Cascade arc in order to further quantify the extent of halogen cycling through the Cascadia subduction system. Thermal springs from 13 localities, between north-central Washington to Lassen, Northern California with Cl concentrations ranging from 250 to 180,000 ppm (Bergfeld et al., 2008, Hurwitz et al., 2005) were analyzed for their Cl isotope composition. The ?37Cl values range from -2.1 to +1.3 ‰ (n=17), and show no correlation with Cl concentrations and sample location along the arc. The majority of samples are characterized by slightly positive values, whereas only three have negative values (-0.9‰, -1.6‰, -2.1‰). Given the upper mantle has a ?37Cl value near 0‰, the variation in the Cl isotope data suggests either that the chloride isotope compositions of these spring waters were modified upon ascent to the surface by the interaction of underlying sediment and/or contain a subducted slab derived component. Nine well characterized basalt samples from across the southern Washington Cascades, (Leeman et al., 2005) were analyzed for their bulk halogen concentrations. Cl concentrations are highest at the volcanic front (140-157 ppm Mt. St. Helens and Mt. Adams) compared to the forearc (17-82 ppm) and in the backarc (19-65 ppm). Br shows a similar trend to Cl with the highest concentrations at the volcanic front (0.22-0.31 ppm) compared to the forearc (0.08-0.13 ppm) and in the backarc (<0.06 ppm). In contrast, F and I show decreasing concentrations from the forearc to the backarc. F concentrations are highest in the forearc (144-600 ppm) decreasing to 120-197 ppm at the volcanic front and 75-164 ppm in the backarc. Iodine concentrations are highest in the forearc (0.09 to 0.10 ppm) to <0.03 ppm in the volcanic front and backarc. Like F and I, B concentrations decrease steadily toward the backarc (Leeman et al., 2004). Bergfeld et al., 2008, USGS Prof. Paper 1750, chap. 25, 523-542. Hurwitz et al., 2005,EPSL., 235, 700-71. Leeman et al., 2004, ChemGeol. 212, 101-124. Leeman et al., 2005, JVGR. 140, 67-105.

Cullen, J.; Barnes, J.; Hurwitz, S.; Leeman, W. P.



Inorganic origin of carbon dioxide during low temperature thermal recovery of bitumen: Chemical and isotopic evidence  

NASA Astrophysics Data System (ADS)

Carbon dioxide, produced at low temperatures, is the dominant gaseous species evolved during steam-assisted thermal recovery of bitumen at the Tucker Lake pilot, Cold Lake, Alberta. Two possible sources for the produced CO 2 are considered: pyrolysis of bitumen and dissolution of carbonate minerals. Data from natural systems and experiments by other authors suggest that clay-carbonate reactions are the dominant source of CO 2. Carbon isotope and chemical analyses of produced gas and water reveal that CO 2 and HCO 3- become more enriched in 13C, and concentrations of Ca 2+ and HCO 3- rise during production. Temperatures in the producing zone are estimated to be between 70 and 220°C using the Na/K and chalcedony chemical geothermometers, and show that production of 13C-enriched CO 2 and HCO 3- occurs as temperature decreases during production. This extends the temperature range at which CO 2 is known to be produced from carbonates to lower levels than previously noted. The ? 13C of calcite in the reservoir is enriched in ? 13C, giving values as high as + 17.4%. When the calcite isotopic compositions are combined with temperature data and temperature fractionation equations for calcite, CO 2, and HCO 3-, they show calcite to be the only viable source of CO 2. Bitumen pyrolysis may contribute small amounts of CO 2, probably by decarboxylation, early in the production cycle but cannot contribute significant volumes. The recognition of production of CO 2 by reactive calcite destruction at temperatures between 70 and 220°C suggests that this process may be responsible for the production of large quantities of CO 2 in natural systems, particularly in lithofeldspathic sands and shales with high carbonate content and abundant clays. Organic acids have been suggested to be the source of CO 2 in diagenetic fluids, but the results presented here suggest that this hypothesis requires more complete investigation.

Hutcheon, Ian; Abercrombie, Hugh J.; Krouse, H. R.



Avaliacao do metodo da diluicao isotopica com adicao de fertilizante (sup 15) N ao solo, na quantificacao da FBN de leguminosas. (Evaluation of the isotopic dilution method with addition of (sup 15) N fertilizer to the soil, for quantification of BNF by legumes).  

National Technical Information Service (NTIS)

Two pot experiments were carried out in greenhouse, with the objective of evaluating the isotopic dilution method with the addition of (sup 15) N fertilizer to the soil for evaluation of biological nitrogen fixation (BNF) by legumes. Experiment I: with ad...

E. R. B. Morales



Isotope Analysis. Radiochemical Burn-Up Determination.  

National Technical Information Service (NTIS)

The radiochemical analysis of heavy isotopes (uranium, plutonium, americium, and curium isotopes) and burn-up (Nd148 method) in samples of irradiated nuclear fuels is described. The analysis is based on isotope dilution technique in combination with mass ...

N. Rhod Larsen E. Larsen



Isotope and chemical compositions of meteoric and thermal waters and snow from the greater Yellowstone National Park region  

USGS Publications Warehouse

An intensive hydrogeologic investigation, mandated by U.S. Congress and centered on the Norris-Mammoth corridor was conducted by USGS and other scientists during 1988-90 to determine the effects of using thermal water from a private well located in the Corwin Springs Known Geothermal Resources Area, Montana, on the thermal springs of Yellowstone National Park (YNP), especially Mammoth Hot Springs. As part of this investigation, we carried out a detailed study of the isotopic and chemical compositions of meteoric water from cold springs and wells, of thermal water, especially from the Norris-Mammoth corridor and of snow. Additional sampling of meteoric and thermal waters from YNP and surrounding region in northwest Wyoming, southwest Montana and southeast Idaho was carried out in 1991-92 to characterize the distribution of water isotopes in this mountainous region and to determine the origin and possible recharge locations of thermal waters in and adjacent to the Park. The D and 18O values for 40 snow samples range from ?88 to ?178? and ?12.5 to ?23.9?, respectively, and define a well constrained line given by D = 8.2 18O + 14.7 (r2 = 0.99) that is nearly identical to the Global Meteoric Water Line. The D and 18O values of 173 cold water samples range from ?115 to ?153? and ?15.2 to ?20.2?, respectively, and exhibit a similar relationship although with more scatter and with some shift to heavier isotopes, most likely due to evaporation effects. The spatial distribution of cold-water isotopes shows a roughly circular pattern with isotopically lightest waters centered on the mountains and high plateau in the northwest corner of Yellowstone National Park and becoming heavier in all directions. The temperature effect due to altitude is the dominant control on stable water isotopes throughout the region; however, this effect is obscured in narrow 'canyons' and areas of high topographic relief. The effects due to distance (i.e. 'continental') and latitude on water isotopes probably are relatively minor and difficult to resolve from the major controls. The data indicate that the groundwater are derived predominantly from cold, isotopically light winter precipitation, and that the isotope values of groundwater from elevations above about 2.5-3.0 km in the Gallatin and northern Absaroka Ranges are light enough (The D ?149?) to be the presumed recharge water for the hydrothermal system in the Park. However, estimation of the present-day volume of this recharged, isotopically light water indicates that it is not adequate to supply the high (3-4 m3/s) thermal water discharges from YNP, and cooler temperatures at the time of recharge would be required. The volume of meteoric water with D values lighter than ?145? may be adequate for recharging the hydrothermal system, and this may be a more plausible value than the ?149? originally calculated from data that are subject to moderate uncertainties.

Kharaka, Yousif K.; Thordsen, James J.; White, Lloyd D.



U-Pb dating of Plinian-eruption ashfalls by the isotope dilution method: A reliable and precise tool for time-scale calibration and biostratigraphic correlation  

SciTech Connect

Through a combination of low analytical blanks, clean Pb-205 enriched tracer-solution, and refined procedures of sample preparation, it is possible to isolate and measure minute quantities of radiogenic Pb in concordant zircon, thereby permitting accurate isotopic age determinations of small multigrain samples of Paleozoic zircon with 7--20 ppm radiogenic Pb. Refinement of these procedures, including reduction of laboratory blank, allows for analysis of single grains of Paleozoic zircon with greater than 25 ppm radiogenic Pb with an age precision of better than 1%. Mass spectrometric measurement of all Pb and U isotopes allows for the calculation of three isotopic ages from a single sample. Concordant multigrain and single-grain U-Pb zircon analyses from 13 biostratigraphically dated K-bentonites in Europe and North America define an internally consistent, absolute chronostratigraphy of Middle ordovician to Upper silurian stratotypes. As a test of trans-Atlantic stratigraphic correlation, a volcanic ash from Middle Ordovician (Rocklandian) strata of North America was found to be in excellent age agreement with Caradocian K-bentonites in Britain and Sweden, demonstrating age equivalence of sedimentary sequences lacking directly comparable fauna. In other case, precise dating of single zircons from three Caradocian K-bentonite in Sweden and Virginia was performed to test a hypothesis that a single ultraplinian volcanic eruption deposited airborne debris on both Larentia and Baltica. The ages of these presumed correlative ashes will be shown to provide quantitative information about the depositional rates of their enclosing strata, as well as tectonic events affecting the margins of Iapetus in Ordovician time.

Tucker, R.D. (Washington Univ., St. Louis, MO (United States). Dept. of Earth and Planetary Sciences)



Measurement of the stable carbon isotope ratio of atmospheric volatile organic compounds using chromatography, combustion, and isotope ratio mass spectrometry coupled with thermal desorption  

NASA Astrophysics Data System (ADS)

The isotopic analysis of atmospheric volatile organic compounds (VOCs), and in particular of their stable carbon isotope ratio (?13C), could potentially be used as an effective tool for identifying the sources of VOCs. However, to date, there have been very few such analyses. In this work, we analyze the ?13C values of VOCs using thermal desorption coupled with chromatography, combustion, and isotope ratio mass spectrometry (TD-GC/C/IRMS). The measured peak shapes were of high quality and 36 compounds in a standard gas containing 58 VOCs (C5-C11) were detected. The measured ?13C varied widely, from -49.7‰ to -22.9‰, while the standard deviation of the ?13C values varied from 0.07‰ to 0.85‰ (n = 5). We then measured samples from two passenger cars in hot and cold modes, three gas stations, roadside air, and ambient air. In comparison with existing studies, the analytical precision for the 36 compounds in this study was reasonable. By comparing the ?13C values obtained from the cars and gas stations, we could identify some degree of the sources of VOCs in the roadside and ambient air samples.

Kawashima, Hiroto; Murakami, Mai



Beta-decay half-lives of neutron rich Cu and Ni isotopes produced by thermal fission of (sup 235)U and (sup 239)Pu.  

National Technical Information Service (NTIS)

The half-lives of very neutron rich isotopes of Ni and Cu have been measured. The isotopes are produced in very asymmetric thermal fission of (sup 235)U and (sup 239)Pu at the I.L.L. high flux reactor. They are separated by means of the Lohengrin spectrom...

M. Bernas J. L. Sida J. P. Bocquet H. Faust R. Brissot



Biochemical Fractionation and Stable Isotope Dilution Liquid Chromatography-mass Spectrometry for Targeted and Microdomain-specific Protein Quantification in Human Postmortem Brain Tissue*  

PubMed Central

Synaptic architecture and its adaptive changes require numerous molecular events that are both highly ordered and complex. A majority of neuropsychiatric illnesses are complex trait disorders, in which multiple etiologic factors converge at the synapse via many signaling pathways. Investigating the protein composition of synaptic microdomains from human patient brain tissues will yield valuable insights into the interactions of risk genes in many disorders. These types of studies in postmortem tissues have been limited by the lack of proper study paradigms. Thus, it is necessary not only to develop strategies to quantify protein and post-translational modifications at the synapse, but also to rigorously validate them for use in postmortem human brain tissues. In this study we describe the development of a liquid chromatography-selected reaction monitoring method, using a stable isotope-labeled neuronal proteome standard prepared from the brain tissue of a stable isotope-labeled mouse, for the multiplexed quantification of target synaptic proteins in mammalian samples. Additionally, we report the use of this method to validate a biochemical approach for the preparation of synaptic microdomain enrichments from human postmortem prefrontal cortex. Our data demonstrate that a targeted mass spectrometry approach with a true neuronal proteome standard facilitates accurate and precise quantification of over 100 synaptic proteins in mammalian samples, with the potential to quantify over 1000 proteins. Using this method, we found that protein enrichments in subcellular fractions prepared from human postmortem brain tissue were strikingly similar to those prepared from fresh mouse brain tissue. These findings demonstrate that biochemical fractionation methods paired with targeted proteomic strategies can be used in human brain tissues, with important implications for the study of neuropsychiatric disease.

MacDonald, Matthew L.; Ciccimaro, Eugene; Prakash, Amol; Banerjee, Anamika; Seeholzer, Steven H.; Blair, Ian A.; Hahn, Chang-Gyu



Estimating thermal inflow to El Chichón crater lake using the energy-budget, chemical and isotope balance approaches  

NASA Astrophysics Data System (ADS)

El Chichón crater lake appeared immediately after the 1982 catastrophic eruption in a newly formed, 1-km wide, explosive crater. During the first 2 years after the eruption the lake transformed from hot and ultra-acidic caused by dissolution of magmatic gases, to a warm and less acidic lake due to a rapid "magmatic-to-hydrothermal transition" — input of hydrothermal fluids and oxidation of H 2S to sulfate. Chemical composition of the lake water and other thermal fluids discharging in the crater, stable isotope composition ( ?D and ?18O) of lake water, gas condensates and thermal waters collected in 1995-2006 were used for the mass-balance calculations (Cl, SO 4 and isotopic composition) of the thermal flux from the crater floor. The calculated fluxes of thermal fluid by different mass-balance approaches become of the same order of magnitude as those derived from the energy-budget model if values of 1.9 and 2 mmol/mol are taken for the catchment coefficient and the average H 2S concentration in the hydrothermal vapors, respectively. The total heat power from the crater is estimated to be between 35 and 60 MW and the CO 2 flux is not higher than 150 t/day or ~ 200 gm - 2 day - 1 .

Taran, Yuri; Rouwet, Dmitri



H-isotope retention and thermal/ion-induced release in boronized films  

SciTech Connect

Over the past decade, it has been clearly demonstrated that the composition of the very near surface ({approximately}100nm) of plasma-interactive components plays a determinant role in most processes which occur in the plasma-edge of Tokamaks. Two very successful techniques to effect control of the plasma-wall interaction are (1) in-situ deposition of amorphous carbon or boron-carbon films and (2) the use of He/C conditioning discharges or He glow discharge cleaning to modify the near surface of bulk graphite components. We have deposited boronized layers into Si using plasma-assisted CVD and sputter deposition. The PCVD deposition conditions were as close as possible to those used in TFTR, and some films deposited in TFTR have also been studied. Using these two deposition techniques, B{sub x}CH{sub y} films have been produced with x varying from 1/2 -- 4, and y from {approximately}1 (sputtered) to {approximately}3 (PCVD). Most films also contained significant amounts of 0. Thermal and ion-induced release of H-isotopes from BC films is qualitatively similar to that measured for graphite. Implanted H saturates in these films at a H/host atom ratio of 0.7 which is considerably higher than that of graphite({approximately}0.4). As-deposited PCVD films are already saturated with H, while sputtered films are not. Sputtered BC films therefore possess an inherent H-pumping capability which could prove to be extremely beneficial to TFTR. 16 refs., 5 figs., 1 tab.

Walsh, D.S. (Idaho State Univ., Pocatello, ID (USA)); Doyle, B.L.; Wampler, W.R.; Hays, A.K. (Sandia National Labs., Albuquerque, NM (USA))



Measurement of urinary desmosine by isotope dilution and high performance liquid chromatography. Correlation between elastase-induced air-space enlargement in the hamster and elevation of urinary desmosine  

SciTech Connect

The accuracy of methods employed to measure the elastin-specific crosslinks, desmosine (DES) and isodesmosine (IDES), has been called into question because contaminants in the urine may cause elevated values. In the present study urine samples were spiked with a known amount of (14C)DES and refluxed in 6 N HCl. Sephadex G-15 chromatography of the hydrolyzed urine employed to remove contaminants. DES and IDES were quantified by high performance liquid chromatography (HPLC) as well as by amino acid analysis. The amount of isotope recovered was used to determine losses during the overall procedure and the isotope dilution to calculate the amounts of endogenous DES and IDES originally present in the urine. Because similar values were obtained by both methods, the more rapid HPLC method was used for all succeeding analyses. In one experiment, the DES amounts in urine collected from hamsters for 3 days after intratracheal treatment with human neutrophil elastase (300 micrograms) or porcine pancreatic elastase (300 micrograms) were 0.212 {plus minus} 0.012 (mean {plus minus} SEM, two measurements on a single pool) and 0.816 {plus minus} 0.005 (two measurements) microgram per hamster per day, respectively. Urine from control hamsters had a mean value of 0.074 {plus minus} 0.008 (eight measurements) microgram per hamster per day. The HNE- and PPE-treated hamsters had mean linear intercept values of 119 and 159% of control values, respectively, giving a positive correlation between increase in airspace size and elevation of urinary DES.

Stone, P.J.; Bryan-Rhadfi, J.; Lucey, E.C.; Ciccolella, D.E.; Crombie, G.; Faris, B.; Snider, G.L.; Franzblau, C. (Department of Biochemistry, Boston University School of Medicine, MA (USA))



Determination of pharmaceuticals and antiseptics in water by solid-phase extraction and gas chromatography/mass spectrometry: analysis via pentafluorobenzylation and stable isotope dilution.  


A sensitive yet robust analytical method is presented for the simultaneous determination of 12 human pharmaceuticals (valproic acid, phenytoin, ibuprofen, gabapentin, acetaminophen, gemfibrozil, naproxen, ketoprofen, secobarbital, phenobarbital, 5-fluorouracil, and diclofenac) and 6 antiseptics (biosol, biphenylol, p-chloro-m-cresol, p-chloro-m-xylenol, chlorophene, and triclosan). The method employs solid-phase extraction (SPE) followed by a novel pentafluorobenzylation using a mixture of acetontrile/water (1/1, v/v). The method is simple to perform (derivatization can be completed in a single test tube) and eliminates the need for any solvent/SPE cartridge drying or blow-down. It affords excellent resolution, high sensitivity and reproducibility, and freedom from interference even for matrices as complex as untreated sewage. The method was applied to the analysis of sewage samples using 15 isotopically labeled surrogates, which resulted in the detection of 10 of the 12 pharmaceuticals and all of the antiseptics sought. Ten of 15 surrogates were synthesized from pure analytes by a simple H-D exchange reaction employing D(2)O and D(2)SO(4). Measured recoveries were sensitive to matrix effects and varied substantially among analytes, indicative of the limitations associated with using a single surrogate standard. PMID:22367332

Yu, Jim T; Bisceglia, Kevin J; Bouwer, Edward J; Roberts, A Lynn; Coelhan, Mehmet



Investigation of uranium isotopic signatures in real-life particles from a nuclear facility by thermal ionization mass spectrometry.  


An improved method was recently developed for the isotopic analysis of single-reference uranium oxide particles for nuclear safeguards. This method is a combination of analytical tools including in situ SEM micromanipulation, filament carburization and multiple ion counting (MIC) detection, which is found to improve sensitivity for thermal ionization mass spectrometry (TIMS) isotope ratio analysis. The question was raised whether this method could be applied for the detection of nuclear signatures in real-life particles with unknown isotopic composition. Therefore, environmental dust was collected in different locations within a nuclear facility. The screening of the samples to find the uranium particles of interest was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive X-ray (EDX) detector. The comparison of the measurement results to reference data evaluated by international safeguards authorities was of key importance for data interpretation. For the majority of investigated particles, detection of uranium isotopic signatures provided information on current and past nuclear feed operations that compared well with facility declarations. PMID:21417310

Kraiem, Monia; Richter, Stephan; Kühn, Heinz; Stefaniak, Elzbieta A; Kerckhove, Giovani; Truyens, Jan; Aregbe, Yetunde



Testosterone metabolic clearance and production rates determined by stable isotope dilution/tandem mass spectrometry in normal men: influence of ethnicity and age.  


The metabolic clearance rate (MCRT) and production rate (PRT) of testosterone (T) were measured using constant infusion of trideuterated (d3) T and quantitating serum d3T by liquid chromatography-tandem mass spectrometry (LC-MS-MS). Serum unlabeled T (d0T) was measured by LC-MS-MS, and serum total T (d3T + d0T) was measured by RIA. Mean MCRR (measured by LC-MS-MS) in young white men (1272 +/- 168 liters/d) was not significantly different from young Asian men (1070 +/- 166 liters/d). Mean PRT was also not significantly different between the two ethnic groups (whites, 9.11 +/- 1.11 mg/d; Asians, 7.22 +/- 1.15 mg/d; P = 0.19 using d0T data). Both the mean MCRR (812 +/- 64 liters/d; P < 0.01) and the PRT (3.88 +/- 0.27 mg/d; P < 0.001) were significantly lower in middle-aged white men when compared with their younger counterparts. The mean MCRR and PRR calculated using serum total T or d0T data showed a diurnal variation, with levels at midday significantly higher than those measured in the evening in the young (MCRT, P < 0.01; PRT, P < 0.001) and to a lesser extent in the older men (MCRT, P < 0.05; PRT, P < 0.05 using total T and P < 0.001 using d0T data). We conclude that using LC-MS-MS to detect d3T in serum after constant infusion of stable isotope-labeled T allows the measurements of MCRT and PRT, which can be used to study androgen metabolism repeatedly after physiological or pharmacological interventions. PMID:15181080

Wang, Christina; Catlin, Don H; Starcevic, Borislav; Leung, Andrew; DiStefano, Emma; Lucas, Geraldine; Hull, Laura; Swerdloff, Ronald S



An online method combining a thermal conversion elemental analyzer with isotope ratio mass spectrometry for the determination of hydrogen isotope composition and water concentration in geological samples.  


An online continuous-flow method, combining a thermal conversion elemental analyzer (TC/EA) with isotope ratio mass spectrometry (MS), is evaluated for the determination of both the hydrogen isotope composition and the water concentration of hydrous and nominally anhydrous minerals. The technique involves reduction of hydrous minerals or nominally anhydrous minerals by reaction with glassy carbon at 1450 degrees C in a helium stream. The product gases, H2 and CO, are separated on a gas chromatographic column prior to analysis in the mass spectrometer. Calibration curves for the H concentration analysis were generated from a standard of benzoic acid (C7H6O2) that has an H concentration of 5.0 wt%; the analytical uncertainties were better than +/-0.05% in our runs. Two standards of material with given D values, polyethylene IAEA-CH-7 and biotite NBS-30, were tested for the purpose of calibrating a natural garnet 04BXL02 representing nominally anhydrous minerals. Preheating at 90 degrees C for 12 h was found to be suitable for removing adsorption water on the sample surface. This results in constant D values and total H2O contents for the garnet, with weighted means of -94 +/- 1 and 522 +/- 11 ppm (wt), respectively. The TC/EA-MS technique allows routine analysis of sample sizes as small as 0.01 microL H2O. For natural minerals, absolute reproducibilities for D values are +/-0.5 to +/-2 (1) and relative uncertainties for total H2O concentrations are at levels of +/-1% to +/-3% (1). Therefore, this online method can be used for the quantitative determination of H isotope composition and H2O concentration of either hydrous or anhydrous minerals. PMID:17370247

Gong, Bing; Zheng, Yong-Fei; Chen, Ren-Xu



Speciation analysis of bromine-containing drug metabolites in feces samples from a human in vivo study by means of HPLC/ICP-MS combined with on-line isotope dilution.  


The aim of this work was speciation analysis of metabolites in feces samples collected within a clinical study during which a bromine-containing anti-tuberculosis drug (TMC207) was administered to patients with multi-drug resistant tuberculosis infection. Owing to slow elimination of the drug, no (14)C label was used within this study. Quantification of the bromine species was accomplished using high performance liquid chromatography coupled to inductively coupled plasma-mass spectrometry (HPLC/ICP-MS) in combination with on-line isotope dilution (on-line ID), while structural elucidation of the species was performed using HPLC coupled to electrospray ionization-mass spectrometry. The ICP-MS-based method developed shows a good intra- and inter-day reproducibility (relative standard deviation = 3.5%, N = 9); the limit of detection (1.5 mg TMC207 L(-1)) is of the same order of magnitude as that for HPLC/radiodetection; the dynamic range of the method covers more than two orders of magnitude. Furthermore, the column recovery was demonstrated to be quantitative (recoveries between 90.6% and 99.5%). Based on the excellent figures of merit, the "cold" HPLC/ICP-MS approach could be deployed for the actual human in vivo metabolism study, such that exposure of the human volunteers to the (14)C radiolabel was avoided. PMID:21877185

Meermann, Björn; Bockx, Marc; Laenen, Aline; Van Looveren, Cis; Cuyckens, Filip; Vanhaecke, Frank



A novel reversed-phase HPLC method for the determination of urinary creatinine by pre-column derivatization with ethyl chloroformate: comparative studies with the standard Jaffé and isotope-dilution mass spectrometric assays.  


Creatinine is an important biomarker for renal function diagnosis and normalizing variations in urinary drug/metabolites concentration. Quantification of creatinine in biological fluids such as urine and plasma is important for clinical diagnosis as well as in biomonitoring programs and urinary metabolomics/metabonomics research. Current methods for creatinine determination either are nonselective or involve the use of expensive mass spectrometers. In this paper, a novel reversed-phase high-performance liquid chromatographic (HPLC) method for the determination of creatinine of high hydrophilicity by pre-column derivatization with ethyl chloroformate is presented. N-Ethyloxycarbonylation of creatinine significantly enhanced the hydrophobicity of creatinine, facilitating its chromatographic retention as well as quantification by HPLC. Factors governing the derivatization reaction were studied and optimized. The developed method was validated and applied for the determination of creatinine in rat urine samples. Comparative studies with isotope-dilution mass spectrometric method revealed that the two methods do not yield systematic differences in creatinine concentrations, indicating the HPLC method is suitable for the determination of creatinine in urine samples. PMID:24408302

Leung, Elvis M K; Chan, Wan



Can Edman degradation be used for quantification? Isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry and the long-term stability of 20 phenylthiohydantoin-amino acids.  


Edman degradation is a well-known method for obtaining amino acid (AA) sequences from a peptide by means of sequential reactions that release the N-terminal AAs from the peptide as a phenylthiohydantoin (PTH) derivative. Because of unexpected loss during the reaction and handling, there are few reports of use of this reaction for quantification. This manuscript describes the development of isotope-dilution liquid chromatography-electrospray ionization tandem mass spectrometry for 20 PTH-AA derivatives, and long-term stability testing of PTH-AAs to ensure quantitative quality in the reaction. The 20 corresponding [(13)C6]-PTH-AAs were prepared by use of a one-pot reaction involving a mixture of [(13)C6]-Edman reagent and 20 AAs. Good linearity was observed for standard curves for the PTH-AAs, using the corresponding [(13)C6]-PTH-AAs as internal standards (1-100 pmol per injection, r(2) = 0.989-1.000). Serum albumin (human), pepsin (porcine stomach mucosa), ?-casein (bovine milk), ribonuclease A (bovine), lysozyme (chicken egg white), and insulin (bovine) subjected to Edman degradation were examined as model proteins and peptides for N-terminal AA analysis. The results of the impurity test were satisfactory. Yield from the entire reaction with human serum albumin was estimated to be at least 75%, indicating great potential for absolute quantification of proteins without protein standards. PMID:23545858

Satoh, Ryo; Goto, Takaaki; Lee, Seon Hwa; Oe, Tomoyuki



Stable-isotope dilution gas chromatography-mass spectrometric measurement of 3-hydroxyglutaric acid, glutaric acid and related metabolites in body fluids of patients with glutaric aciduria type 1 found in newborn screening.  


We developed a simple and sensitive stable-isotope dilution method for the quantification of 3-hydroxyglutaric acid (3HGA) and glutaric acid (GA) in body fluids. In our method, tert-butyldimethylsilyl (tBDMS) derivatives of 3HGA and GA were measured with a conventional electron-impact ionization (EI) mode in gas chromatography-mass spectrometry (GC-MS). The control values for 3HGA in nmol/ml were 0.15+/-0.08 (serum; n=10) and 0.07+/-0.03 (CSF; n=10). In addition, glutarylcarnitine and free carnitine were quantified by electrospray tandem mass spectrometry. Using these methods, we monitored 3HGA, GA, and glutarylcarnitine in the body fluids of three patients with glutaric aciduria type 1 found during newborn screening. None of the patients had experienced neurological strokes, which are possibly caused by the accumulation of 3HGA, at 15-24 months of age under a disease-specific treatment, including carnitine supplementation. Our data showed that 3HGA levels were relatively high in some serum samples with lower glutarylcarnitine and carnitine levels, suggesting that carnitine supplementation may play a role in preventing the accumulation of 3HGA in patients with this disease. PMID:16055049

Shigematsu, Yosuke; Hata, Ikue; Tanaka, Yukie; Tajima, Go; Sakura, Nobuo; Naito, Etsuo; Yorifuji, Toru



Automated on-line column-switching high performance liquid chromatography isotope dilution tandem mass spectrometry method for the quantification of bisphenol A, bisphenol F, bisphenol S, and 11 other phenols in urine.  


Human exposure to bisphenol A (BPA) is widespread. However, in recent years, bisphenol analogs such as bisphenol S (BPS) and bisphenol F (BPF) are replacing BPA in the production of some consumer products. Because human exposure to these alternative bisphenols may occur, biomonitoring of these bisphenol analogs is warranted. In the present study, we developed and validated a sensitive and selective method that uses on-line solid phase extraction coupled to high performance liquid chromatography-isotope dilution tandem mass spectrometry with peak focusing to measure BPA, BPF, BPS, and 11 other environmental phenols in urine. The method required a small amount of sample (100?L) and minimal sample pretreatment. The limits of detection were 0.03ng/mL (BPS), 0.06ng/mL (BPF), 0.10ng/mL (BPA), and ranged from 0.1ng/mL to 1.0ng/mL for the other 11 phenols. In 100 urine samples collected in 2009-2012 from a convenience group of anonymous adults in the United States, of the three bisphenols, we detected BPA at the highest frequency and median concentrations (95%, 0.72ng/mL), followed by BPS (78%, 0.13ng/mL) and BPF (55%, 0.08ng/mL). This sensitive, rugged, and labor and cost-effective method could be used for the analysis of large number of samples for epidemiologic studies. PMID:24316527

Zhou, Xiaoliu; Kramer, Joshua P; Calafat, Antonia M; Ye, Xiaoyun



Assay of the set of all Sudan azodye (I, II, III, IV, and Para-Red) contaminating agents by liquid chromatography-tandem mass spectrometry and isotope dilution methodology.  


A high-throughput mass spectrometric method is presented for the simultaneous detection of Sudan I, II, III, IV, and Para-Red azodyes in foodstuff. The method is based on the use of deuterium-labeled internal standards and atmospheric pressure chemical ionization (APCI) in a triple-quadrupole instrument. The gas-phase breakdown pattern of each labeled and unlabeled analogue displays the naphthoic moiety as a common fragment. The search for the parents of this common species (parent ion scans) allows, by flow injection and in a single run, the evaluation of the presence of each polluting species spiked in typical foodstuffs. A detailed assay of each azodye was performed by LC-APCI and isotope dilution method, through the multiple reaction monitoring approach, using deuterium-labeled internal standards. Sudan dyes can be quantified above the threshold of 10 ppb except for Sudan Para-Red, for which the limit of quantification was 20 ppb, likely due to the different ionization efficiency. PMID:18052038

Mazzotti, Fabio; Di Donna, Leonardo; Maiuolo, Loredana; Napoli, Anna; Salerno, Raffaele; Sajjad, Ashiff; Sindona, Giovanni



Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes  

NASA Technical Reports Server (NTRS)

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Socki, Richard A.; Gibson, Everett K., Jr.; Bissada, K. K.



On-line monitoring of benzene air concentrations while driving in traffic by means of isotopic dilution gas chromatography/mass spectrometry.  


There is no shortage of information about the average benzene concentrations in urban air, but there is very little about microenvironmental exposure, such as in-vehicle concentrations while driving in various traffic conditions, while refuelling, or while in a parking garage. The main reason for this lack of data is that no analytical instrumentation has been available to measure on-line trace amounts of benzene in such situations. We have recently proposed a highly accurate, high-speed cryofocusing gas chromatography/mass spectrometry (GC/MS) system for monitoring benzene concentrations in air. Accuracy of the analytical data is achieved by enrichment of the air sample before trapping, with a stable isotope permeation tube system. The same principles have been applied to a new instrument, specifically designed for operation on an electric vehicle (Ducato Elettra, Fiat). The zero emission vehicle and the fully transportable, battery-operated GC/MS system provide a unique possibility of monitoring benzene exposure in real everyday situations such as while driving, refuelling, or repairing a car. All power consumptions have been reduced so as to achieve a battery-operated GC/MS system. Liquid nitrogen cryofocusing has been replaced by a packed, inductively heated, graphitized charcoal microtrap. The instrument has been mounted on shock absorbers and installed in the van. The whole system has been tested in both fixed and mobile conditions. The maximum monitoring period without external power supply is 6 h. The full analytical cycle is 4 min, allowing close to real-time monitoring, and the minimum detectable level is 1 microgram/m3 for benzene. In-vehicle monitoring showed that, when recirculation was off and ventilation on, i.e., air from outside the vehicle was blown inside, concentrations varied widely in different driving conditions: moving from a parking lot into normal traffic on an urban traffic condition roadway yielded an increase in benzene concentration from 17 to 62.3 micrograms/m3 even if the actual distance was small. A larger increase was observed when a car was left with the engine running at a distance 2 m from the zero emission vehicle: We measured an increment of benzene concentrations from 15.2 to 174.4 micrograms/m3 with a car equipped with a catalytic converter, and from 19.1 to 386.3 micrograms/m3 with a car without such a converter. PMID:8738357

Davoli, E; Cappellini, L; Moggi, M; Ferrari, S; Fanelli, R



Helium Isotopes in Geothermal Exploration  

NASA Astrophysics Data System (ADS)

Mantle volatiles, principally water and CO2, play an important role in the production of buoyant fluids that can be injected into the shallow crust. Regional and local trends in the crustal occurrence of mantle volatiles provide insight into the coupling between mantle-crust tectonics, heat and mass exchange between the mantle and crust, and the occurrence and distribution of economic resources such as ore minerals and oil, gas, and geothermal fluids. Mantle-derived volatiles in the crust are traceable through He isotopic compositions of hydrologic fluids. Once injected into a crustal-fluid system, mantle He will be continuously diluted with radiogenic helium-4 (4He) acquired from the U,Th-rich crust, and therefore in addition to providing information regarding the heat source, surface-fluid He isotopic compositions also provide a measure of the mantle He flux and the integrated permeability-fluid pressure gradient (flow rate) through the crust. The application of helium isotopes to geothermal exploration and reservoir characterization will be discussed for four cases: regional He isotope trends in amagmatic regions, He isotope trends at the local or basin scale with no evidence for recent crustal magmatism and two cases (Yellowstone Caldera and the Ohaaki Thermal Area, New Zealand) where helium isotope trends can be misleading. Regional trends across the northern Basin and Range show a correlation between helium isotopes and crustal extension rates and direction. The trends reflect changes in mantle fluid fluxes through the ductile lower crust and can be modeled as a proxy for deep crustal permeability. Local basin scale trends can be used to map the extent of a geothermal resource or its influence on the local hydrology. In some cases, the helium isotope trends can be misleading, in that high 3He/4He ratios (indicative of high mantle input or shallow magmatic activity) do not necessarily identify the location of a high temperature resource.

Kennedy, B. M.; Christenson, B. W.; van Soest, M. C.



Separation processes using expulsion from dilute supercritical solutions  


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

Cochran, Jr., Henry D. (Oak Ridge, TN)



Separation processes using expulsion from dilute supercritical solutions  


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

Cochran, H.D. Jr.



Accurate ab Initio Thermal Rate Constants for Reaction of O((3)P) with H2 and Isotopic Analogues.  


Semiclassical transition state theory, in combination with high accuracy quantum chemistry, is used to compute thermal rate constants from first principles for the O((3)P) + H2 reaction and its isotopic counterparts. In the temperature regime of 298-3500 K (which spans 8 orders of magnitude for rate constants), our theoretical results are in excellent agreement (within 5-15%) with all available experimental data from 298 to 2500 K but are somewhat too low (from 15 to 35%) at higher temperatures. Several possible reasons that might cause the degradation at high temperatures are discussed. Vibrational state-selected rate constants and their correlations with normal thermal rate constant are derived and are given in the Supporting Information. PMID:24914730

Nguyen, Thanh Lam; Stanton, John F



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

USGS Publications Warehouse

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

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



R&D Isotope Separation with Large Thermal Gradients for Ultra-Low Background Experiments  

NASA Astrophysics Data System (ADS)

Seeking an alternative method to obtain enriched 76Ge and 73Ge for planned neutrinoless double-beta decay and dark matter experiments, a cryogenic distillation column is developed in our university laboratory for germane gas. Prior to experimenting with germane gas, which requires significant safety measures in place, the distillation column was tested with CO2. The preliminary analysis shows that 45CO2 was separated and enriched within two hours at room temperature. Exploiting the isotopic gradient within the two-meter length and removing preferentially from top and bottom points, 44CO2, 45CO2, and 46CO2 were bottled for further analysis. Methods of preferential condensation and vaporization used for depletion and enrichment of bottled gases show equal viability for purification and isotope enrichment with CO2 as well as gases with phase changes within the equipment specifications. Potential for purification and isotope enrichment/depletion of gases such as argon and xenon are investigated.

Alanson Chiller, Angela; Chiller, Christopher; Jasinski, Benjamin; Snyder, Nathan; Mei, Dongming



Combining the quick, easy, cheap, effective, rugged and safe approach and clean-up by immunoaffinity column for the analysis of 15 mycotoxins by isotope dilution liquid chromatography tandem mass spectrometry.  


Optimization and validation of a multi-mycotoxin method by LC-MS/MS is presented. The method covers the EU-regulated mycotoxins (aflatoxins, fumonisins, ochratoxin A, deoxynivalenol, zearalenone, T-2 and HT-2), as well as nivalenol and 3- and 15-acetyldeoxynivalenol for analysis of cereals, cocoa, oil, spices, infant formula, coffee and nuts. The proposed procedure combines two clean-up strategies: First, a generic preparation suitable for all mycotoxins based on the QuEChERS (for quick, easy, cheap, effective, rugged and safe) protocol. Second, a specific clean-up devoted to aflatoxins and ochratoxin A using immunoaffinity column (IAC) clean-up. Positive identification of mycotoxins in matrix was conducted according to the confirmation criteria defined in EU Commission Decision 2002/657/EC while quantification was performed by isotopic dilution using (13)C-labeled mycotoxins as internal standards. Limits of quantification were at or below the maximum levels set in the EC/1886/2006 document for all mycotoxin/matrix combinations under regulation. In particular, the inclusion of an IAC step allowed achieving LOQs as low as 0.05 and 0.25?g/kg in cereals for aflatoxins and ochratoxin A, respectively. Other performance parameters like linearity [(r)(2)>0.99], recovery [71-118%], precision [(RSDr and RSDiR)<33%], and trueness [78-117%] were all compliant with the analytical requirements stipulated in the CEN/TR/16059 document. Method ruggedness was proved by a verification process conducted by another laboratory. PMID:24636559

Desmarchelier, Aurélien; Tessiot, Sabine; Bessaire, Thomas; Racault, Lucie; Fiorese, Elisa; Urbani, Alessandro; Chan, Wai-Chinn; Cheng, Pearly; Mottier, Pascal



Certification of butyltins and phenyltins in marine sediment certified reference material by species-specific isotope-dilution mass spectrometric analysis using synthesized 118Sn-enriched organotin compounds  

PubMed Central

A new marine sediment certified reference material, NMIJ CRM 7306-a, for butyltin and phenyltin analysis has been prepared and certified by the National Metrological Institute of Japan at the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). Candidate sediment material was collected at a bay near industrial activity in Japan. After air-drying, sieving, and mixing the material was sterilized with ?-ray irradiation. The material was re-mixed and packaged into 250 glass bottles (15 g each) and these were stored in a freezer at ?30 °C. Certification was performed by use of three different types of species-specific isotope-dilution mass spectrometry (SSID–MS)—SSID–GC–ICP–MS, SSID–GC–MS, and SSID–LC–ICP–MS, with 118Sn-enriched organotin compounds synthesized from 118Sn-enriched metal used as a spike. The 118Sn-enriched mono-butyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) were synthesized as a mixture whereas the 118Sn-enriched di-phenyltin (DPhT) and triphenyltin (TPhT) were synthesized individually. Four different extraction methods, mechanical shaking, ultrasonic, microwave-assisted, and pressurized liquid extraction, were adopted to avoid possible analytical bias caused by non-quantitative extraction and degradation or inter-conversion of analytes in sample preparations. Tropolone was used as chelating agent in all the extraction methods. Certified values are given for TBT 44±3 ?g kg?1 as Sn, DBT 51 ± 2 ?g kg?1 as Sn, MBT 67 ± 3 ?g kg?1 as Sn, TPhT 6.9 ± 1.2 ?g kg?1 as Sn, and DPhT 3.4 ± 1.2 ?g kg?1 as Sn. These levels are lower than in other sediment CRMs currently available for analysis of organotin compounds.

Takatsu, Akiko; Watanabe, Takuro; Aoyagi, Yoshie; Yarita, Takashi; Okamoto, Kensaku; Chiba, Koichi



Quantification of viral proteins of the avian H7 subtype of influenza virus: an isotope dilution mass spectrometry method applicable for producing more rapid vaccines in the case of an influenza pandemic.  


Vaccination is the most effective means to prevent influenza and its serious complications. Influenza viral strains undergo rapid mutations of the surface proteins hemagglutinin (HA) and neuraminidase (NA) requiring vaccines to be frequently updated to include current circulating strains. It is nearly impossible to predict which strains will be circulating in the next influenza season. It is, therefore, imperative that the process of producing a vaccine be streamlined and as swift as possible. We have developed an isotope dilution mass spectrometry (IDMS) method to quantify HA and NA in H7N7, H7N2, and H7N9 influenza. The IDMS method involves enzymatic digestion of viral proteins and the specific detection of evolutionarily conserved target peptides. The four target peptides that were initially chosen for analysis of the HA protein of H7N2 and H7N7 subtypes were conserved and available for analysis of the H7N9 subtype that circulated in China in the spring of 2013. Thus, rapid response to the potential pandemic was realized. Quantification of a protein is performed by employing multiple peptides to ensure that the enzymatic digestion of the protein is efficient in the region of the target peptides, verify the accuracy of the measurement, and provide flexibility in the case of amino acid changes among newly emerging strains. The IDMS method is an accurate, sensitive, and selective method to quantify the amount of HA and NA antigens in primary liquid standards, crude allantoic fluid, purified virus samples, and final vaccine presentations. PMID:24689548

Santana, Wanda I; Williams, Tracie L; Winne, Emily K; Pirkle, James L; Barr, John R



The Absolute Isotopic Composition of Zn in Terrestrial Materials Determined Using Double Spike Thermal Ionization Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Although long suspected to be widespread in nature, until recently, little was known about the extent of the variation of the isotopic composition, or isotopic fractionation, of Zn in natural materials. During the last decade an increasing number of high precision Zn isotopic fractionation data have been reported using MC- ICP-MS (MARECHAL et al., 1999; PETIT et al., 2008; PICHAT et al., 2003), but none have been reported on an absolute scale which is essential for interlaboratory comparison of results. In this work we report sub- permil Zn fractionation in a range of natural materials relative to the internationally proposed absolute Zn isotopic reference material (? zero) (PONZEVERA et al., 2006)using the Thermal Ionization Mass Spectrometry double spike technique. Repeated double spike analysis of the laboratory standard relative to itself demonstrated a long term reproducibility of +0.006 ± 0.039 permil amu-1. The measured isotopic composition of Zn in minerals and igneous rocks SRMs was found to be the same as the proposed absolute (? zero) which makes it possible to consider the proposed absolute Zn isotopic standard as being representative of "bulk earth" Zn. A significant and consistent fractionation of ~+0.3 permil amu-1 was found in 5 sediments from a range of localities. The results obtained for metamorphic SRMs indicate that the fractionation of Zn in these rocks is the same as found in igneous rocks but are different from the Zn found in sedimentary rocks. A clay SRM sample TILL-3 appears to exhibit a consistently Zn fractionation of +0.12 ± 0.10 permil amu-1. The isotopic composition of Zn was also measured in two plant SRMs and one animal SRM sample. The fractionation of (-0.088 ± 0.070 permil amu-1) of Zn in the Rice (a C3 type plant material) sample suggested that Zn may be used to study Zn systematics in plants. The result obtained for MURST-ISS-A2 (Antarctic Krill) was +0.21 ± 0.11 permil amu-1 relative to the laboratory standard which is similar to the average Zn fractionation results of +0.281 ± 0.083 permil amu-1 obtained for marine sediments. The fractionation of Zn in seven ultra pure Zn standard materials was also measured relative to the laboratory standard and found to range from -5.11 ± 0.36 permil amu-1 for AE 10760 to +0.12 ± 0.16 permil amu-1 for Zn IRMM 10440 confirming that that significant care must be exercised in the selection of Zn isotope laboratory standards (TANIMIZU et al., 2002). A pilot study to determine the concentration and the isotopic composition of Zn in river and tap water, and a number of processed materials was also performed. The implications and applications of these results, such as on the atomic weight of Zn will be presented.

Ghidan, O. Y.; Loss, R. D.



The thermal desorption of CO2 from amine carbamate solutions for the 13C isotope enrichment  

NASA Astrophysics Data System (ADS)

The CO2 desorption from amine carbamate in non-aqueous solvents is of major importance for isotopic enrichment of 13C. A series of experiments were carried out in order to set up the conditions for the CO2 desorption. For this purpose, a laboratory- scale plant for 13C isotope separation by chemical exchange between CO2 and amine carbamate was designed and used. The decomposition of the carbamate solution was mostly produced in the desorber and completed in the boiler. Two different-length desorbers were used, at different temperatures and liquid flow rates of the amine-non-aqueous solvent solutions. The residual CO2 was determined by using volumetric and gaschromatographic methods. These results can be used for enrichment of 13C by chemical exchange between CO2 and amine carbamate in nonaqueous solvents.

Dronca, S.; Varodi, C.; Gligan, M.; Stoia, V.; Baldea, A.; Hodor, I.



Stable carbon isotope compositions during the thermal alteration of organic matter  

Microsoft Academic Search

The use of the amount and carbon isotopic composition of methane as a maturation index was tested by pyrolysis of sedimentary organic carbon (kerogen) at 600 C. The parameters used to describe the maturity are CMR (CHâ-C\\/kerogen carbon) and the ι³C (δ¹³C{sub CH4-} δ¹³C{sub OC}). With increasing maturities, smaller amounts of methane are generated and there is a decrease in




Thermal-field propagation in an exocontact zone of a magmatic body and its impact on radiogenic isotope concentrations in minerals.  


In application of radioactive isotope systems (K-Ar, Rb-Sr etc.) during the last decades, experience was gained not only on their geochronometrical uses, but also on estimations of some important parameters of geological processes, especially temperatures and durations of superimposed thermal events. In this paper, the formation of an exocontact thermal field of a magmatic intrusion is considered as a spreading of a thermal source delta-function. Appropriate solutions of the heat-transfer equation are deduced and correlated with diffusion parameters of the radiogenic argon, coupling radioactive, thermal and kinetic parameters in an exocontant zone of a magmatic body. These solutions were used for quantitative reinterpretations of data taken from Hart's classical paper [The petrology and isotopic mineral age relations of a contact zone in the Front Range, Colorado. J. Geol., 1964, v. 72, pp. 493-525]. Theoretic and measured radiogenic argon and strontium concentrations within exocontact aureoles are found to be in good concordance. PMID:12219992

Brandt, I S; Rasskazov, S V; Brandt, S B; Ivanov, A V



Fluid mixing and thermal regimes beneath the PACMANUS hydrothermal field, Papua New Guinea: Helium and oxygen isotope data  

NASA Astrophysics Data System (ADS)

Fluid mixing processes and thermal regimes within the Snowcap and Roman Ruins vent sites of the PACMANUS hydrothermal system, Papua New Guinea, were investigated using 3He/ 4He ratios from fluid inclusions within pyrite and anhydrite and the ?18O signature of anhydrite. Depressed 3He/ 4He ratios of 0.2-6.91R A appear to be caused by significant atmospheric diffusive exchange, whilst He-Ne diffusive fractionation precludes correction using 20Ne. 40Ar/ 36Ar ratios of 295-310 are elevated above seawater, indicating the majority of argon is seawater derived but with a magmatic component. ?18O anhydrite ratios are 6.5‰ to 11‰ for Snowcap and 6.4‰ to 11.9‰ for Roman Ruins. Using oxygen isotope fractionation factors for the anhydrite-water system, the temperatures calculated assuming isotopic equilibrium at depth are up to 100 °C cooler than fluid inclusion trapping temperatures. It is likely that anhydrite is precipitated rapidly, preventing ?18O equilibration. By comparing new ?18O values for anhydrite with corresponding published 87Sr/ 86Sr ratios, seawater is inferred to penetrate deep into the Snowcap system with little conductive heating. A simple fluid mixing model has been constructed whereby the differing venting styles can be explained by a plumbing system at depth which favors delivery of end-member hydrothermal fluid to the high temperature sites.

Webber, A. P.; Roberts, S.; Burgess, R.; Boyce, A. J.



On the optimization of the isotopic neutron source method for measuring the thermal neutron absorption cross section: Advantages and disadvantages of BF 3 and 3He counters  

Microsoft Academic Search

The effect of the detector characteristics on the performance of an isotopic neutron source device for measuring thermal neutron absorption cross section (?) has been examined by means of Monte Carlo simulations. Three specific experimental arrangements, alternately with BF3 counters and 3He counters of the same sizes, have been modelled using the MCNP-4C code. Results of Monte Carlo calculations show

A BOLEWSKIJR; M. Ciechanowski; A. Dydejczyk; A. Kreft



Microfluidic serial dilution ladder.  


Serial dilution is a fundamental procedure that is common to a large number of laboratory protocols. Automation of serial dilution is thus a valuable component for lab-on-a-chip systems. While a handful of different microfluidic strategies for serial dilution have been reported, approaches based on continuous flow mixing inherently consume larger amounts of sample volume and chip real estate. We employ valve-driven circulatory mixing to address these issues and also introduce a novel device structure to store each stage of the dilution process. The dilution strategy is based on sequentially mixing the rungs of a ladder structure. We demonstrate a 7-stage series of 1?:?1 dilutions with R(2) equal to 0.995 in an active device area of 1 cm(2). PMID:24231765

Ahrar, Siavash; Hwang, Michelle; Duncan, Philip N; Hui, Elliot E



The mathematics of dilution.  


The major objection to homeopathic medicine is that the doses of medicine prescribed in some cases are too dilute for any active ingredient to be present. The medicines would hence be rendered inactive, necessitating novel explanations for the action. A further examination of dilution in the light of the Langmuir equation shows that homeopathic medicines may not be as dilute as a simplistic application of Avogadro's Principle suggests, due to surface effects. PMID:24685420

Chatterjee, Barun Kumar



?D and ?13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry.  


This paper describes the establishment of a robust method to determine compound specific ?D and ?(13)C values of volatile organic compounds (VOCs) in a standard mixture ranging between C(6) and C(10) and was applied to various complex emission samples, e.g. from biomass combustion and car exhaust. A thermal desorption (TD) unit was linked to a gas chromatography isotope ratio mass spectrometer (GC-irMS) to enable compound specific isotope analysis (CSIA) of gaseous samples. TenaxTA was used as an adsorbent material in stainless steel TD tubes. We determined instrument settings to achieve a minimal water background level for reliable ?D analysis and investigated the impact of storage time on ?D and ?(13)C values of collected VOCs (176 days and 40 days of storage, respectively). Most of the standard compounds investigated showed standard deviations (SD)<6‰ (?D) when stored for 148 days at 4 °C. However, benzene revealed occasionally D depleted values (21‰ SD) for unknown reasons. ?(13)C analysis demonstrated that storage of 40 days had no effect on VOCs investigated. We also showed that breakthrough (benzene and toluene, 37% and 7%, respectively) had only a negligible effect (0.7‰ and 0.4‰, respectively) on ?(13)C values of VOCs on the sample tube. We established that the sample portion collected at the split flow effluent of the TD unit can be used as a replicate sample for isotope analysis saving valuable sampling time and resources. We also applied TD-GC-irMS to different emission samples (biomass combustion, petrol and diesel car engines exhaust) and for the first time ?D values of atmospheric VOCs in the above range are reported. Significant differences in ?D of up to 130‰ were observed between VOCs in emissions from petrol car engine exhaust and biomass combustion (Karri tree). However, diesel car emissions showed a high content of highly complex unresolved mixtures thus a baseline separation of VOCs was not achieved for stable hydrogen isotope analysis. The ability to analyse ?D by TD-GC-irMS complements the characterisation of atmospheric VOCs and is maybe used for establishing further source(s). PMID:21807368

von Eckstaedt, Christiane Vitzthum; Grice, Kliti; Ioppolo-Armanios, Marisa; Chidlow, Geoff; Jones, Mark



Magnitude of the carbon isotope excursion at the Paleocene Eocene thermal maximum: The role of plant community change  

NASA Astrophysics Data System (ADS)

Carbon-isotope measurements ( ?13C) of leaf-wax n-alkanes from the Paleocene-Eocene Thermal Maximum (PETM) in the Bighorn Basin, Wyoming, reveal a negative carbon isotope excursion (CIE) of 4-5‰, which is 1-2‰ larger than that observed in marine carbonate ?13C records. Reconciling these records requires either that marine carbonates fail to record the full magnitude of the CIE or that the CIE in plants has been amplified relative to the marine. Amplification of the CIE has been proposed to result from an increase in available moisture that allowed terrestrial plants to increase 13C-discrimination during the PETM. Leaf physiognomy, paleopedology and hydrogen isotope ratios of leaf-wax lipids from the Bighorn Basin, however, all suggest that rather than a simple increase in available moisture, climate alternated between wet and dry during the PETM. Here we consider two other explanations and test them quantitatively with the carbon isotopic record of plant lipids. The "marine modification" hypothesis is that the marine carbonate record was modified by chemical changes at the PETM and that plant lipids record the true magnitude of the CIE. Using atmospheric CO 2?13C values estimated from the lipid record, and equilibrium fractionation between CO 2 and carbonate, we estimate the expected CIE for planktonic foraminifera to be 6‰. Instead, the largest excursion observed is about 4‰. No mechanism for altering marine carbonate by 2‰ has been identified and we thus reject this explanation. The "plant community change" hypothesis is that major changes in floral composition during the PETM amplified the CIE observed in n-alkanes by 1-2‰ relative to marine carbonate. This effect could have been caused by a rapid transition from a mixed angiosperm/conifer flora to a purely angiosperm flora. The plant community change hypothesis is consistent with both the magnitude and pattern of CIE amplification among the different n-alkanes, and with data from fossil plants. This hypothesis predicts that the magnitude and pattern of amplification of CIEs among different n-alkanes will vary regionally and systematically depending on the extent of the replacement of conifers by angiosperms during the PETM.

Smith, Francesca A.; Wing, Scott L.; Freeman, Katherine H.



Thermal conductivity of (GaAs)(n)/(AlAs)(n) superlattices and isotopically enriched Si and GaAs  

NASA Astrophysics Data System (ADS)

We present an improved method for making pump-and-probe optical measurements in the picosecond to nanosecond time range and apply the technique to studies of the thermal conductivity ? of thin semiconductor layers. In this type of measurement, a pump light pulse is used to excite the sample and the decay of the excitation is investigated by means of a probe pulse which is time- delayed relative to the pump pulse. In most measurements of this type a mechanical stage is used to introduce the time-delay. As a result of the divergence of the probe beam, it is difficult to make accurate measurements when the time delay is in the range above a few hundred picoseconds. To overcome these difficulties we have developed an apparatus which utilizes a single-mode optical fiber. To determine ? a metallic film is deposited on the semiconductor layer. The absorption of the pump pulse raises the temperature of the metallic film which causes a proportional change in the optical reflectivity. The change in the reflectivity as the film cools into the underlying structure is measured by means of the probe pulse. This change is compared to a change calculated from a numerical simulation of the heat flow which has ? as one of the adjustable parameters. Measurements were made over a temperature range of 100 to 375 K. In the first study, we measure ?(T) of isotopically enriched semiconductors. We have found an increase of ? of isotopically pure Si compared to Si of natural isotopic abundance throughout the entire temperature range. The results are compared to a relaxation time calculation and analyzed by a model which accurately reproduces the phonon dispersion in Si. We also present measurements of ? of a set of GaAs samples in which the concentration of one of the Ga isotopes is varied from 0 to 100%. In the second study we measure ??(T) perpendicular to the interfaces of a family of short period (GaAs)n/(AlAs)n Superlattices. We find a decrease in ?? compared to the bulk constituents which depends on the superlattice period. We discuss the decrease in terms of extrinsic and intrinsic scattering mechanisms.

Capinski, William Scott



Evidence for rapid climate change in North America during the latest Paleocene thermal maximum: oxygen isotope compositions of biogenic phosphate from the Bighorn Basin (Wyoming)  

NASA Astrophysics Data System (ADS)

Oxygen isotope records of Cenozoic sea water temperatures indicate that a rapid warming event known as the Latest Paleocene Thermal Maximum (LPTM) occurred during the otherwise gradual increase in world temperatures during the Late Paleocene and Early Eocene. Oxygen isotope analysis of the carbonate and phosphate components of hydroxyapatite found in mammalian tooth enamel and body scales of river-dwelling fish from the Bighorn Basin in Wyoming were made to investigate corresponding changes in the terrestrial climate. A comparison of carbonate and phosphate isotope data from modern and fossil material indicates that some diagenetic alteration of the fossil material has occurred, although systematically larger intra-tooth ranges in the oxygen isotope composition of carbonate indicate that it is more likely to have been affected than phosphate. Carbonate and phosphate from the ecologically diverse mammals and fishes both record a shift to higher oxygen isotope ratios at the same time and of the same duration as the LPTM. These shifts reflect a change in the isotopic composition of regional precipitation, which in turn provides the first evidence for continental climate change during the LPTM. Assuming the present-day relation between the oxygen isotope composition of precipitation and temperature applies to conditions in the past, and that animal physiology and behavior is relatively invariant over time, the isotopic shift is equivalent to an increase of surface temperature in western North America of several degrees. This result is consistent with the magnitude of high-latitude ocean warming, and provides a basis for relating marine and terrestrial oxygen isotope records to records of terrestrial biotic change.

Fricke, Henry C.; Clyde, William C.; O'Neil, James R.; Gingerich, Philip D.



Separation of Selected Stable Isotopes by Liquid-Phase Thermal Diffusion and by Chemical Exchange.  

National Technical Information Service (NTIS)

Useful applications of enriched stable nuclides are unduly restricted by high cost and limited availability. Recent research on liquid phase thermal diffusion (LTD) has resulted in practical processes for separating exp 34 S, exp 35 Cl, and exp 37 Cl in s...

W. M. Rutherford B. E. Jepson E. D. Michaels



Determination of oxygen self-diffusion in akermanite, anorthite, diopside, and spinel: Implications for oxygen isotopic anomalies and the thermal histories of Ca-Al-rich inclusions  

SciTech Connect

Oxygen self-diffusion coefficients have been measured for three natural diopsidic clinopyroxenes, a natural anorthite, a synthetic magnesium aluminate spinel, and a synthetic akermanite for oxygen fugacities ranging from the NNO to IW buffers. The oxygen diffusion data are used to evaluate the effects of three different types of thermal histories upon the oxygen isotopic compositions of minerals found in Type B Ca-Al-rich inclusions (CAIBs) in carbonaceous chondrites: (1) gas-solid exchange during isothermal heating, (2) gas-solid exchange as a function of cooling rate subsequent to instantaneous heating, and (3) isotopic exchange with a gaseous reservoir during partial melting and recrystallization. With the assumptions that the mineral compositions within a CAIB were uniformly enriched in [sup 16]O prior to any thermal processing, that effective diffusion dimensions may be estimated from observed grain sizes, and that diffusion in diopside is similar to that in fassaitic clinopyroxene, none of the above scenarios can reproduce the relative oxygen isotopic anomalies observed in CAIBs without improbably long or unrealistically intense thermal histories relative to current theoretical models of nebular evolution. The failure of these simple models, coupled with recent observations of disturbed magnesium isotopic abundances and correlated petrographic features in anorthite and melilite indicative of alteration and recrystallization, suggests that the oxygen isotopic compositions of these phases may have also been modified by alteration and recrystallization possibly interspersed with multiple melting events. Because the modal abundance of spinel remains relatively constant for plausible melting scenarios, and its relatively sluggish diffusion kinetics prevent substantial equilibration, Mg-Al spinel is the most reliable indicator of the oxygen isotopic composition of precursor material which formed Type B CAIs.

Ryerson, F.J. (Lawrence Livermore National Lab., CA (United States)); McKeegan, K.D. (Univ. of California, Los Angeles, CA (United States))



Stable Chlorine Isotopes and Elemental Chlorine by Thermal Ionization Mass Spectrometry and Ion Chromatography; Martian Meteorites, Carbonaceous Chondrites and Standard Rocks  

NASA Technical Reports Server (NTRS)

Recently significantly large mass fractionation of stable chlorine isotopes has been reported for terrestrial and lunar samples [1,2]. In addition, in view of possible early solar system processes [3] and also potential perchlorate-related fluid/microbial activities on the Martian surface [4,5], a large chlorine isotopic fractionation might be expected for some types of planetary materials. Due to analytical difficulties of isotopic and elemental analyses, however, current chlorine analyses for planetary materials are controversial among different laboratories, particularly between IRMS (gas source mass spectrometry) and TIMS (Thermal Ionization Mass Spectrometry) groups [i.e. 1,6,7] for isotopic analyses, as well as between those doing pyrohydrolysis and other groups [i.e. 6,8]. Additional careful investigations of Cl isotope and elemental abundances are required to confirm real chlorine isotope and elemental variations for planetary materials. We have developed a TIMS technique combined with HF-leaching/ion chromatography at NASA JSC that is applicable to analysis of small amounts of meteoritic and planetary materials. We present here results for several standard rocks and meteorites, including Martian meteorites.

Nakamura, N.; Nyquist, L. E.; Reese, Y.; Shih, C.-Y.; Fujitani, T.; Okano, O.



Yields and isomeric ratio of xenon and krypton isotopes from thermal neutron fission of 235U  

Microsoft Academic Search

The experimental cumulative yields of 85Krm, 87Kr, 88Kr, 133Xeg, 135Xem, and 135Xeg and the independent isomeric yield of 133Xem in the thermal neutron fission of 235U have been measured by the gas chromatographic method. The independent yields of 133Xeg, 135Xem, and 135Xeg were deduced with the aid of 133I and 135I data. The isomeric yield ratios of 133Xe and 135Xe

S. S. Hsu; J. T. Lin; C. M. Yang; Y. W. Yu



Dilution of cosmological densities by saxino decay  

NASA Astrophysics Data System (ADS)

Saxino decay can generate significant cosmological entropy, and hence dilute theoretical estimates of the present mass density of a given particle species. The dilution factor depends on the saxino and axion masses, and is constrained by the requirement that saxino decay should not affect nucleosynthesis, as well as by the usual requirement that the axion density be less than the critical density. The latter constraint is evaluated carefully, under both the Harari-Sikivie and Davis proposals about the emission spectrum from axionic strings. Uncertainties are carefully evaluated, points of principle are addressed, and with an eye to future numerical simulation the spacing and typical oscillation wavelength of the strings are represented by parameters varying in the range 1 to 3. Within the constraints, the entropy dilution varies from 1 to 10-4. Only saxinos originating from thermal equilibrium are considered, so that more dilution might arise from nonthermal saxinos.

Lyth, David H.




SciTech Connect

The objective of this task was to demonstrate that metal hydrides could be produced by mechanical alloying in the quantities needed to support production-scale hydrogen isotope separations. Three starting compositions (ratios of elemental Zr and Fe powders) were selected and attritor milled under argon for times of 8 to 60 hours. In general, milling times of at least 24 hours were required to form the desired Zr{sub 2}Fe and Zr{sub 3}Fe phases, although a considerable amount of unalloyed Zr and Fe remained. Milling in liquid nitrogen does not appear to provide any advantages over milling in hexane, particularly due to the formation of ZrN after longer milling times. Carbides of Zr formed during some of the milling experiments in hexane. Elemental Zr was present in the as-milled material but not detected after annealing for milling times of 48 and 60 hours. It may be that after intimate mixing of the powders in the attritor mill the annealing temperature was sufficient to allow for the formation of a Zr-Fe alloy. Further investigation of this conversion is necessary, and could provide an opportunity for reducing the amount of unreacted metal powder after milling.

Fox, K.



Retention, isotope exchange, and thermal release of hydrogen in candidate materials for TFTR  

SciTech Connect

The materials studied included TiC, TiB/sub 2/, VB/sub 2/, B/sub 4/C, B, Si, graphite, and the metals Ti, V, and 304L stainless steel. The TiC and TiB/sub 2/ were formed by chemical vapor deposition on a graphite substrate. The C/Ti ratio of the TiC was measured to be 1.0 +- .05 by ion backscattering analysis. The Ti and V were explosively bonded to copper substrates, and the VB/sub 2/ was made by borodizing vanadium. Carbon (compression annealed pyrolytic graphite from Union Carbide and Papyex graphite ribbon from Le Carbone) and single crystal silicon samples were included in the study as reference materials. The hydrogen retention and isotope exchange behavior for these materials were studied by measuring the amount of H or D retained as a function of incident fluence using the D(/sup 3/He,P)/sup 4/He nuclear reaction analysis techniques for D and H(/sup 15/N,..cap alpha gamma..) profiling for H.

Wampler, W. R.; Doyle, B. L.; Brice, D. K.; Picraux, S. T.



Comparison of thermal ionization mass spectrometry and Multiple Collector Inductively Coupled Plasma Mass Spectrometry for cesium isotope ratio measurements  

Microsoft Academic Search

In the nuclear domain, precise and accurate isotopic composition determination of elements in spent nuclear fuels is mandatory to validate neutron calculation codes and for nuclear waste disposal. The present study presents the results obtained on Cs isotope ratio by mass spectrometric measurements. Natural cesium is monoisotopic (133Cs) whereas cesium in spent fuels has 4 isotopes (133Cs, 134Cs, 135Cs, and

H. Isnard; M. Granet; C. Caussignac; E. Ducarme; A. Nonell; B. Tran; F. Chartier



Dilution air dispensing apparatus  

SciTech Connect

This patent describes a dilution air dispensing apparatus for a double dome combustor. It comprises: a first dome combustor having an inlet opening and an exhaust opening, a first fuel nozzle operatively arranged in the inlet opening to dispense fuel to the first dome combustor, a second dome combustor having an inlet opening and an exhaust opening, a second fuel nozzle operatively arranged in the inlet opening to dispense fuel to the second dome combustor. The first and second dome combustor being joined towards their inlet ends to form a dilution air dispensing cavity therebetween. The dilution air dispensing cavity being formed by the inner adjacent walls of the first and second dome combustors. The dilution air dispensing cavity having a rearward portion which is located approximately one-third of the dome length from the inlets to the first and second dome combustors.

King, R.C.



Rhenium-osmium isotope systematics of ordinary chondrites and iron meteorites  

NASA Technical Reports Server (NTRS)

Using negative thermal ionization mass spectrometry, Re and Os abundances were determined by isotope dilution and Os-187/Os-186 measured in 11 ordinary chondrites, and also in 1 IIB and 3 IIIB irons. In addition, Os-186/Os-188 and Os-189/Os-188 ratios were precisely determined for 3 unspiked ordinary chondrites as a means of constraining the intensity of any neutron irradiation these meteorites may have experienced.

Walker, R. J.; Morgan, J. W.; Horan, M. F.; Grossman, J. N.



Thermal-hydraulic system simulation of the HFIR (high-flux isotope reactor) with RELAP5/MOD2  

SciTech Connect

A model of the high-flux isotope reactor (HFIR) in Oak Ridge has been developed to simulate loss-of-coolant accidents and operational transients using the RELAP5/MOD2 program. This work constitutes a portion of the analytical studies being performed to update the HFIR thermal-hydraulic safety analysis. RELAP5 permits the determination of the survivability of the core through various transients based on the critical heat flux criteria rather than the more conservative incipient boiling criteria, which have been used previously. Preliminary simulations for small-diameter breaks have been completed, and results are discussed in this paper. These preliminary results indicate that (a) no incipient boiling within the fuel will occur for small-diameter breaks, so (b) the reactor should survive such transients with no fuel damage. Fuel damage is currently assumed to occur in the existing conservative accident analysis for the HFIR. Larger-diameter break simulations are not yet complete, but are currently being performed.

Wendel, M.W. (Oak Ridge Gaseous Diffusion Plant, TN (USA)); Morris, D.G.



High-resolution, high-fidelity carbon isotope stratigraphy of the Paleocene-Eocene Thermal Maximum in northern Wyoming from cores recovered by the Bighorn Basin Coring Project  

NASA Astrophysics Data System (ADS)

Isotopic records derived from marine core and terrestrial outcrop sediments spanning the Paleocene-Eocene boundary reveal a large (>2.5‰) negative carbon isotope excursion (CIE) in a relatively short period of time (total duration of ~200 Kyr). This event, known as the Paleocene-Eocene thermal maximum or PETM, reflects the geologically rapid release of isotopically light carbon into the atmosphere and is associated with global warming of ~5-8°C. While numerous studies have investigated the timing and magnitude of the PETM CIE, significant uncertainty remains regarding the amount and pacing of the global carbon isotope shift. The Bighorn Basin Coring Project recently collected the first scientific drill cores preserving high-resolution, stratigraphically continuous records of the PETM in continental environments and providing a new suite of data from un-weathered rocks. We report data from pedogenic carbonate nodules sampled at >200 levels within two adjacent drilling locations at Polecat Bench in the Bighorn Basin. These data provide a continuous record of the evolution of carbon isotope ratios in Bighorn Basin paleosols over a period of approximately 500 Kyr spanning the P-E boundary. ?13C data from the nodules reveal a CIE of ~7 ‰ with considerable structured isotopic variability at the onset of the PETM and a smooth recovery back to pre-PETM baseline conditions. Relative to previous studies, this higher-resolution dataset better constrains the pattern and pace of the carbon isotope changes and records higher variability during the onset of the event, but confirms existing results of the general shape and ~7‰ magnitude of the CIE at this locality.

Maibauer, B. J.; Bowen, G. J.; Srinivasaraghavan, V.; VanDeVelde, J. H.; Wing, S. L.; Gingerich, P. D.; Clyde, W. C.



Strontium isotopes as an indicator of water-rock reaction for the Coupled Thermal-Hydrological-Mechanical-Chemical-Biological (THMCB) Experimental Facility at DUSEL  

Microsoft Academic Search

The Thermal-Hydrological-Mechanical-Chemical-Biological (THMCB) Experimental Facility is a proposed facility at the DUSEL-Homestake that will be used to investigate reactive transport, heat transfer and the resulting biological responses within a natural fractured rock. As part of THMCB facility design we are characterizing the current geochemical conditions and developing geochemical and isotopic indicators for fluid flow paths and reaction rates. The proposed

K. Maher; N. J. Olsen; C. Harris; T. L. Jones; M. E. Conrad; E. L. Sonnenthal; D. Elsworth; N. Uzunlar; B. J. Mailloux; R. P. Lowell



Inorganic origin of carbon dioxide during low temperature thermal recovery of bitumen: Chemical and isotopic evidence  

SciTech Connect

Carbon dioxide, produced at low temperatures, is the dominant gaseous species evolved during steam-assisted thermal recovery of bitumen at the Tucker Lake pilot, Cold Lake, Alberta. Two possible sources for the produced CO{sub 2} are considered: pyrolysis of bitumen and dissolution of carbonate minerals. Data from natural systems and experiments by other authors suggest that clay-carbonate reactions are the dominant source of CO{sub 2}. Bitumen pyrolysis may contribute small amounts of CO{sub 2}, probably by decarboxylation, early in the production cycle but cannot contribute significant volumes. The recognition of production of CO{sub 2} by reactive calcite destruction at temperatures between 70 and 220{degree}C suggests that this process may be responsible for the production of large quantities of CO{sub 2} in natural systems, particularly in lithofeldspathic sands and shales with high carbonate content and abundant clays. Organic acids have been suggested to be the source of CO{sub 2} in diagenetic fluids, but the results presented here suggest that this hypothesis requires more complete investigation.

Hutcheon, I.; Abercrombia, H.J.; Krouse, H.R. (Univ. of Calgary, Alberta (Canada))



Sedimentology and Carbon Isotope in Lower Tertiary Sediments of Rajasthan:Implication to Post Paleocene/Eocene Thermal Maximum Event  

NASA Astrophysics Data System (ADS)

The Paleocene-Eocene thermal maxima (PETM; ~55 My.), identified as the most abrupt and transient climatic events in Cenozoic era, associated with pronounced warming of ocean and atmosphere, change in ocean chemistry, and perturbation of global carbon cycle. Catastrophic (~5° -6° C) rise in the deep sea temperature and oxygen deficiency might cause 30-50% extinction of benthic foraminifera, increase in sea surface temperature by ~8° C at high latitude (lesser amount towards equator) affected the planktonic biota, and this global warming event led to a pulse of speciation or migration of mammal. PETM is characterized by a prominent drop in carbon isotope values by ~3-4 per mil in both marine and terrestrial sediments in less than 10 ka. The source and triggering mechanism of PETM event are still raging debate. Input of massive amount of greenhouse gas from the dissociation of 13C poor methane hydrate from the continental slop as well as from the terrestrial biosphere is currently the most acceptable explanation for the warming and the negative carbon isotope excursion (CIE). Like other catastrophic events the post-PETM recovery was gradual. Interestingly, ?13C of both carbonate and organic matter shifted towards positive during the recovery period possibly as a combined effect of increased organic burial and silicate weathering. Compared to most studied PETM and post-PETM sections of subtropical to high latitudes, data for equatorial regions and marginal marine are scanty. The marginal marine are important as the effect of silicate weathering or increased burial of shallow marine organic matter will be more pronounced here. The lower Tertiary marginal marine successions of Rajasthan (Akli formation; Giral lignite mine) (paleolatitude ~5° S) shed light on the PETM and post-PETM events and the response of the events on equatorial marginal marine environment. Sedimentological studies suggest that the Akli formation was deposited in a lagoonal environment occasionally inundated by marine incursions. High resolution ?13C Bulk organic matter profile in these lignitic beds and its comparison with the oceanic foraminiferal carbonate ?13C profile reveals that the upper part of the Akli formation was deposited during Early Eocene or recovery phase of PETM. This inference is also supported by the presence of larger benthic foraminifera Nummulites burdigalensis (~52My) in the sand beds. The preliminary data (presence of lignites and C/N Values) suggest that substantial organic carbon burial in shallow seas world over could have been responsible for atmospheric CO2 reduction and enriched ?13C values during the early Eocene period.

Samanta, A.; Sarkar, A.; Bera, M.



Determination of Pu and U isotopes in safeguard swipe sample with extraction chromatographic techniques.  


A simple and reliable separation method of plutonium and uranium was developed using extraction chromatographic techniques. Using the separation method of plutonium and uranium developed in this study, recoveries of plutonium and uranium were compared with those by commercial separation methods of Pu and U. The redox reactions of hydrogen peroxide with plutonium in a nitric acid medium were investigated by UV-vis-NIR absorption spectroscopic techniques. The separation method of Pu and U isotopes with the UTEVA resin updated in this study could be effective to measure quantitatively nano- and picogram amounts of uranium and plutonium in swipe samples using isotope dilution thermal ionization mass spectrometry (ID-TIMS). PMID:22063516

Lee, M H; Park, J H; Oh, S Y; Ahn, H J; Lee, C H; Song, K; Lee, M S



Constraining groundwater discharge in a large watershed: Integrated isotopic, hydraulic, and thermal data from the Canadian shield  

NASA Astrophysics Data System (ADS)

The objective of this study is to evaluate the pattern and rate of groundwater discharge in a large, regulated fractured rock watershed using novel and standard methods that are independent of base flow recession. Understanding the rate and pattern of groundwater discharge to surface water bodies is critical for watershed budgets, as a proxy for recharge rates, and for protecting the ecological integrity of lake and river ecosystems. The Tay River is a low-gradient, warm-water river that flows over exposed and fractured bedrock or a thin veneer of coarse-grained sediments. Natural conservative (?2H, ?18O, Cl, and specific conductance), radioactive (222Rn), and thermal tracers are integrated with streamflow measurements and a steady state advective model to delimit the discharge locations and quantify the discharge fluxes to lakes, wetlands, creeks, and the Tay River. The groundwater discharge rates to most surface water body types are low, indicating that the groundwater and surface water system may be largely decoupled in this watershed compared to watersheds underlain by porous media. Groundwater discharge is distributed across the watershed rather than localized around lineaments or high-density zones of exposed brittle fractures. The results improve our understanding of the rate, localization, and conceptualization of discharge in a large, fractured rock watershed. Applying hydraulic, isotopic, or chemical hydrograph separation techniques would be difficult because the groundwater discharge "signal" is small compared to the "background" surface water inflows or volumes of the surface water bodies. Although this study focuses on a large watershed underlain by fractured bedrock, the methodology developed is transferable to any large regulated or unregulated watershed. The low groundwater discharge rates have significant implications for the ecology, sustainability, and management of large, crystalline watersheds.

Gleeson, Tom; Novakowski, Kent; Cook, Peter G.; Kyser, T. Kurt



Extraction chromatographic methods in the sample preparation sequence for thermal ionization mass spectrometric analysis of plutonium isotopes.  


A sample preparation sequence for actinide isotopic analysis by thermal ionization mass spectrometry (TIMS) is described that includes column-based extraction chromatography as the first separation step, followed by anion-exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA resin and DGA resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple monoisotopic spikes applied sequentially throughout the separation sequence. Pu recoveries were 87% and 86% for TEVA and DGA resin separations, respectively. The Pu recoveries from 400 ?L anion-exchange column separation sequences were 89% and 93% for trial sequences incorporating TEVA and DGA resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion-exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73% ± 0.77% (2?) for the DGA resin trials and 2.67% ± 0.54% for the TEVA resin trials, compared to 3.41% and 2.37% (average 2.89%) for two control trials. These compare with an average measurement efficiency of 2.78% ± 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion-exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS sample preparation. PMID:22004461

Grate, Jay W; O'Hara, Matthew J; Farawila, Anne F; Douglas, Matthew; Haney, Morgan M; Petersen, Steven L; Maiti, Tapas C; Aardahl, Christopher L



Improvement in Thermal-Ionization Mass Spectrometry (TIMS) using Total Flash Evaporation (TFE) method for lanthanides isotope ratio measurements in transmutation targets  

SciTech Connect

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)

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)



Characterization of Volatile Nylon 6.6 Thermal-Oxidative Degradation Products by Selective Isotopic Labeling and Cryo-GC/MS  

NASA Astrophysics Data System (ADS)

Aged materials, such as polymers, can exhibit modifications to their chemical structure and physical properties, which may render the material ineffective for its intended purpose. Isotopic labeling was used to characterize low-molecular weight volatile thermal-oxidative degradation products of nylon 6.6 in an effort to better understand and predict changes in the aged polymer. Headspace gas from aged (up to 243 d at 138 °C) nylon 6.6 monomers (adipic acid and 1,6-hexanediamine) and polymer were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). Observations regarding the relative concentrations observed in each chromatographic peak with respect to aging time were used in conjunction with mass spectra for samples aged under ambient air to determine the presence and identity of 18 degradation products. A comparison of the National Institute of Standards and Technology (NIST) library, unlabeled, and isotopically labeled mass spectra (C-13 or N-15) and expected fragmentation pathways of each degradation product were used to identify the location of isotopically labeled atoms within the product's chemical structure, which can later be used to determine the exact origin of the species. In addition, observations for unlabeled nylon 6.6 aged in an O-18 enriched atmosphere were used to determine if the source of oxygen in the applicable degradation products was from the gaseous environment or the polymer. Approximations for relative isotopic ratios of unlabeled to labeled products are reported, where appropriate.

Smith, Jonell N.; V. White, Gregory; White, Michael I.; Bernstein, Robert; Hochrein, James M.



Helium dilution refrigeration system  


A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation is disclosed. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains [sup 3]He and [sup 4]He liquids which are precooled by a coupled container containing [sup 3]He liquid, enabling the phase separation of a [sup 3]He rich liquid phase from a dilute [sup 3]He-[sup 4]He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the [sup 3]He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute [sup 3]He-[sup 4]He liquid phase. 2 figs.

Roach, P.R.; Gray, K.E.



Dilution, Concentration, and Flotation  

ERIC Educational Resources Information Center

As both classroom teaching practice and literature show, many students have difficulties learning science concepts such as density. Here are some investigations that identify the relationship between density and floating through experimenting with successive dilution of a liquid, or the systematic change of concentration of a saltwater solution.…

Liang, Ling; Schmuckler, Joseph S.



Helium dilution refrigeration system  


A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains .sup.3 He and .sup.4 He liquids which are precooled by a coupled container containing .sup.3 He liquid, enabling the phase separation of a .sup.3 He rich liquid phase from a dilute .sup.3 He-.sup.4 He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the .sup.3 He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute .sup.3 He-.sup.4 He liquid phase.

Roach, Patrick R. (Darien, IL) [Darien, IL; Gray, Kenneth E. (Naperville, IL) [Naperville, IL



?13C of volatile organic compounds (VOCS) in airborne samples by thermal desorption-gas chromatography-isotope ratio-mass spectrometry (TD-GC-IR-MS)  

NASA Astrophysics Data System (ADS)

This paper is a preliminary investigation into the use of a thermal desorption-gas chromatography-isotope ratio mass spectrometry (TD-GC-IR-MS) method to determine stable carbon isotopic compositions ( ?13C) of low molecular-weight volatile organic compounds (VOCs) in airborne samples (e.g. industrial and car exhaust emissions) as a means of differentiating their sources in the environment. A TD-GC-IR-MS method for obtaining ?13C of VOCs (benzene, toluene, chlorobenzene, ethylbenzene, m-xylene and propylbenzene) in air samples has been optimised, and is proven to be both reproducible and linear. The ?13C of the VOC standards was found to be comparable (within analytical error) to that obtained from direct GC-IR-MS analysis. This novel method of VOC analysis is valuable in environmental and forensic investigations.

Turner, Nicole; Jones, Mark; Grice, Kliti; Dawson, Daniel; Ioppolo-Armanios, Marisa; Fisher, Steven J.


Isotopically controlled semiconductors  

SciTech Connect

Semiconductor bulk crystals and multilayer structures with controlled isotopic composition have attracted much scientific and technical interest in the past few years. Isotopic composition affects a large number of physical properties, including phonon energies and lifetimes, bandgaps, the thermal conductivity and expansion coefficient and spin-related effects. Isotope superlattices are ideal media for self-diffusion studies. In combination with neutron transmutation doping, isotope control offers a novel approach to metal-insulator transition studies. Spintronics, quantum computing and nanoparticle science are emerging fields using isotope control.

Haller, Eugene E.



The effect of steam-heating processes on the chemical and isotopic composition of the shallow thermal aquifer in Vulcano Island (Aeolian Arc, Sicily).  

NASA Astrophysics Data System (ADS)

We report on a comprehensive study of major-ion chemistry, dissolved gases, and stable isotopes measured in water wells at Vulcano Island since 1988. Particularly, we focus on chemical and hydrological modifications of groundwaters observed in the last two decades, interpreted according to a quantitative model describing steam condensation and boiling phenomena in shallow water bodies (Federico et al., 2010). According to this model, we infer that (i) strong isotope enrichment observed in some shallow thermal waters can result from an increasing mass rate of condensing deep vapor, even in water being meteoric in origin; (ii) the high pCO2 measured in the coldest and peripheral waters are explained by the progressive CO2 enrichment in the vapor phase during multistep boiling; and (iii) the high Cl- and SO4-- contents in the hottest waters can be attributed to the direct condensation (single-step) of volcanic vapor. The model also takes into account both the mass fluxes and the compositions of the involved endmembers (steam and shallow groundwater), which provides important inferences on the modifications observed during the periods of increasing mass and heat input from depth occurred at Vulcano Island. The volcanic crisis that occurred in 1988-1993 profoundly affected the composition of some thermal wells that were more-directly affected by ascending vapour. In particular, higher Cl-, SO4--, and HCO3- contents, temperature, and pCO2 values were measured. These variations are all explained by a different composition of the vapor entering the aquifer paralleled by a higher mass rate relative to the shallow meteoric endmember. Minor effects on the shallow thermal aquifer are observed during the following periods of increasing heat and mass flux from depth, mostly recorded in the crater area. This implies that the shallow thermal aquifer is affected by magmatic fluids ascending along central conduits only when there is a significant increase in the heat and mass fluxes from depth, which are able to vaporize the deep hydrothermal aquifer and modify the chemical and isotopic compositions of a larger portion of the volcanic edifice. Otherwise, the shallow thermal aquifer is chiefly affected by the vapor separating from the 400°C- hydrothermal system and, therefore, by its P-T conditions. On these grounds, once apportioned the effect of rainwater, we tentatively evaluate the effect of variations of physico-chemical conditions of the hydrothermal aquifer on both the water level and the composition of sampled thermal waters.

Capasso, G.; Federico, C.; Madonia, P.; Paonita, A.



Body composition in adults with cerebral palsy by dual-energy X-ray absorptiometry, bioelectrical impedance analysis, and skinfold anthropometry compared with the 18O isotope-dilution technique.  


The aim of this study was to determine in adults with cerebral palsy the accuracy and practicality of standard methods used to estimate body composition. The sample consisted of 20 adults (13 men and 7 women) aged 20-55 y with various degrees of cerebral palsy. Percentage body fat was estimated from skinfold thickness, bioelectrical impedance analysis (BIA), and dual-energy X-ray absorptiometry (DXA), and compared with the reference measure of percentage body fat from total body water by 18O dilution. Values derived from use of BIA and skinfold thickness, estimated by using the Jackson-Pollock equation, were significantly different from those derived with use of 18O dilution (P < 0.001 and P < 0.001, respectively). There was no significant difference between percentage body fat measured with DXA and that measured with 18O. There was favorable agreement between DXA and 18O (mean difference: 0.06 +/- 9.6%), but not between skinfold thickness (mean difference: 6.33 +/- 12.3%) or BIA (mean difference: -6.55 +/- 13.6%) and 18O. Although DXA was the best measure for predicting percentage body fat in the sample, its high cost prohibits its use as a practical method. The best-fitting regression equation specific for this sample by using anthropometric measures to predict percentage body fat was as follows: 8.76 - (7.34 x sex) + (0.32 x weight) + (0.38 x biceps skinfold) (R2 = 0.84, P < 0.001, SEE = 4.85). This equation needs to be cross-validated in an independent sample of adults with cerebral palsy. PMID:9394697

Hildreth, H G; Johnson, R K; Goran, M I; Contompasis, S H



Thermal conductivity reduction through isotope substitution in nanomaterials: predictions from an analytical classical model and nonequilibrium molecular dynamics simulations  

Microsoft Academic Search

We introduce an analytical model to rapidly determine the thermal conductivity reduction due to mass disorder in nanomaterials. Although this simplified classical model depends only on the masses of the different atoms, it adequately describes the changes in thermal transport as the concentrations of these atoms vary. Its predictions compare satisfactorily with nonequilibrium molecular dynamics simulations of the thermal conductivity

Ganesh Balasubramanian; Ishwar K. Puri; Michael C. Böhm; Frédéric Leroy



Effects of steam-heating processes on a stratified volcanic aquifer: Stable isotopes and dissolved gases in thermal waters of Vulcano Island (Aeolian archipelago)  

NASA Astrophysics Data System (ADS)

We report on a comprehensive study of major-ion chemistry, dissolved gases, and stable isotopes measured in water wells at Vulcano Island since 1988. The work focuses on a quantitative model describing steam condensation and boiling phenomena in shallow water bodies. The model is based on the differences in partition coefficients between liquid water and vapor characterizing oxygen and hydrogen isotopes, as well as volcanic gases (CO 2, S species, and HCl). Based on both physical conditions of aquifers identified during drilling campaigns and the composition of the volcanic vapor, mass and enthalpy balances are applied in a multistep process of steam separation and condensation in shallower aquifers. By comparing the model results with measured data, we infer that (i) strong isotope enrichment observed in some shallow thermal waters can result from an increasing mass rate of condensing deep vapor, even in water meteoric in origin; (ii) the high CO 2 content measured in the fumarolic vapor during 1988-1993 affected the ?18O value of the steam-heated water due to CO 2-H 2O isotope exchange; (iii) the high pCO 2 measured in the coldest and peripheral waters are explained by the progressive enrichment of this gas in the vapor phase during multistep boiling; and (iv) the high Cl - and SO 42-contents in the hottest waters can be attributed to the direct condensation (single-step) of volcanic vapor. The model also takes into account both the mass fluxes and the compositions of the involved endmembers (steam and shallow groundwater), which provides important inferences on the modifications observed or expected during periods of increasing mass and heat input from depth.

Federico, C.; Capasso, G.; Paonita, A.; Favara, R.



Diluted magnetic semiconductors  

Microsoft Academic Search

Diluted magnetic semiconductors (DMSs), i.e. semiconducting crystals whose lattice is made up in part of substitutional magnetic ions (e.g. Cd1-xMnxTe, Hg1-xFex Se, Zn1-xCoxS), are reviewed. The focus is on materials of the type A1-xII MnxB VI, which are the most thoroughly understood. However, the similarities and differences between these materials and the A1-x IIFexBVI and A1-IICoxBVI systems are discussed wherever

Nitin Samarth; J. K. Furdyna



Mass-dependent and Mass-independent Sulphur Isotope Fractionation Accompanying Thermal- and Photo-chemical Decomposition of Sulphur Bearing Organic Compounds  

NASA Astrophysics Data System (ADS)

The bimodal S-isotope record, specifically the transition from mass independent (MIF) to mass dependent fractionation (MDF), is perhaps the most widely cited line of evidence for an irreversible rise in atmospheric oxygen at ca. 2.4Ga. The production and preservation of S-MIF, manifested in both ?33S and ?36S, within the geological record are linked to atmospheric O2 via a number of arguments. However, to date, the only mechanism capable of generating S-MIF consistent with the Archaean sedimentary records involves gas-phase ultraviolet irradiation of SO21 photolysis. More recently, ?33S S-MIF trends have been reported from en vitro thermochemical sulphate reduction (TSR) experiments, prompting authors to question the importance of S-MIF as a proxy for Earth oxidation2. Importantly, whilst emerging TSR experiments3,4 affirm the reported ?33S trends2, these experiments fail to identify correlated S-MIF between ?33S and ?36S values3,4. Realization that S-MIF is confined to ?33S during TSR, precludes TSR as a mechanism responsible for the origin of the Archaean S-MIF record but strongly suggests the effect originating from a magnetic isotope effect (MIE) associated with 33S nucleus3,4. Clearly, photochemical and thermochemical processes impart different ?36S/?33S trends with significant variation in ?34S; however, a complete experimental elucidation of mechanisms responsible for the S-MIF and S-MIE signatures is lacking. Interestingly, a complete understanding of the S-isotope chemistry during thermal- and photo-chemical decomposition may reveal wavelength and thermal dependence archived in the sedimentary record. Here we extend the experimental database to explore the magnitude and sign of ?36S/?33S and ?34S produced during both photo- and thermochemical processes. Here the organic sulphur compounds (OSC) utilized in these experiments carries diagnostic ?36S/?33S patterns that differ from those reported from photolysis experiment SO2 and from the Archaean sedimentary record. Further thermal decomposition of several sulphur containing compounds with; 1) an aliphatic-S (e.g., diphenyl disulphide), 2) tri-substituted aromatic-S (trithiane), and S-amino acids (e.g., cysteine, methionine, taurine, and glutathionine) were tested for four S-isotope fractionation under vacuum. Among these, aromatic trithiane produced anomalous 33S up to 1.3‰, indicating thermal decomposition through radical chemistry, producing S-MIE. While taurine with sulphonic acid (R-SO2OH) functional groups yielded S-MDF up to 15‰ (between the AVS and the residual OSC), which is consistent with estimated zero-point energy shifts for thiol (R-SH), and thiyl (R-S-CH3) groups of cysteine and methionine, respectively. These results suggest that OSC might undergo either thermal or photochemical decomposition and the S-MIF, S-MDF, and S-MIE signatures may be archived in the geologic record. The emerging mechanisms responsible for these isotope signals and their implications will be discussed in more detail. Ultimately this work offers a framework where these signals can be used as a diagnostic marker to distinguish between thermo- and photochemical processes. References: 1. Farquhar et al., Science 2000 2. Watanabe et al., Science 2010; 3. Oduro et al., PNAS 2011; 4. Kopf and Ono, GCA 2012.

Oduro, Harry; Izon, Gareth; Ono, Shuhei



Extraction Chromatographic Methods in the Sample Preparation Sequence for Thermal Ionization Mass Spectrometric Analysis of Plutonium Isotopes  

Microsoft Academic Search

A sample preparation sequence for actinide isotopic analysis by TIMS is described that includes column-based extraction chromatography as the first separation step, followed by anion exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or

Jay W. Grate; Matthew J. OHara; Anne F. Farawila; Matthew Douglas; Morgan M. Haney; Steve L. Peterson; Tapas C. Maiti; Christopher L. Aardahl



A Novel Approach to Investigate Soil Organic Matter Development Using Isotopes and Thermal Analysis: C Sourcing from Various Plant Materials and Mineral Influence on Stability  

NASA Astrophysics Data System (ADS)

Biomolecular input quality and mineral constituents are important factors that regulate turnover and stabilization of natural organic matter. The complexity and variability of natural soil systems might shadow basic mechanisms occurring between organic and mineral components. Utilizing an in vitro model decomposition system allows for control over inputs and turnover time. We created a model soil system with composted plant litter that was enriched with 13-C in order to investigate C use during the formation of stabilized SOM. The litter was subjected to microbially-mediated, aerobic decomposition before pure clays were added and allowed to incubate further. Isotopically labeled organic inputs allowed us to focus on C derived from known plant sources as a qualitative assessment of SOM formation. Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) has been used successfully to quantify thermochemical properties of SOM reactivity/stability in three regions of exothermic activity corresponding generally to carbohydrates and lipids (Exo 1; 150-350 C), aromatic and condensed polymers (Exo 2; 400-460 C) and refractory/mineral associated C (Exo 3; 500-550 C). Thermal separation of the organics allows for in-line evolved gas analysis via Isotope Ratio Mass Spectrometry (IRMS) to measure 13-C isotopic values of those thermally separated organic compound classes. This coupled analysis is ideal in that it is fast, reproducible, and requires no sample pretreatment other than drying/grinding and it provides stability, mass loss, and isotopic data from a single sample. DSC results show the development of a higher temperature, energetically recalcitrant C pool over the course of decomposition in mineral-free litters and its absence in clay-litter mixtures, implicating the influence of mineral surfaces on soil organic matter energetic stability. Preliminary IRMS results indicate that mineral presence influences C sourcing from particular plant materials in some SOM compound classes. For example, in mineral-free treatments containing 13-C enriched woody material, gas evolution from Exo 3 that was enriched in 13-C and was therefore derived from the woody material. However, the presence of montmorillonite clay minerals resulted in gas evolution that was depleted in 13-C and was therefore derived from the non-woody plant inputs present (grass and leaves). This shows a change in mechanism: either the microbial sourcing of C from woody material to produce Exo 3 compounds changed in the presence of the mineral or mineral interaction with the organics altered the thermal reactivity of those wood-derived compounds, causing them to thermally separate differently. We are also exploring the effect of bridging metal interaction with minerals and plant litter as SOM develops. We are able to show that this analytical method is useful for probing mineral influence on SOM stability and differentiation in litter C utilization during decomposition in a single sample. TG-DSC-IRMS analysis can be used for any soil-organic matter investigation, with isotopically enriched or natural abundance materials: applications range from measuring terrestrial C sequestration efforts and organic waste management efficacy to sustainable agricultural practices.

Bower, J.; Horwath, W. R.



A new series of uranium isotope reference materials for investigating the linearity of secondary electron multipliers in isotope mass spectrometry  

NASA Astrophysics Data System (ADS)

A new series of gravimetrically prepared uranium isotope reference materials, the so-called IRMM-074 series, with the n(235U)/n(238U) isotope ratio held constant at unity and the n(233U)/n(238U) isotope ratios varying from 1.0 to 10-6 has been prepared and certified. This series is suited for calibration of secondary electron multipliers used widely in isotope mass spectrometry, in particular for techniques such as thermal ionization mass spectrometry (TIMS), inductively coupled plasma mass spectrometry (ICPMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS). The new IRMM-074 was prepared as a replacement for the already exhausted IRMM-072 predecessor series. Uranium materials with high isotopic enrichments of 233U, 235U and 238U were purified using identical methods involving separation on anion and cation column followed by a precipitation as peroxide. The oxides were calcined to convert them to U3O8 simultaneously, in an oven installed in a glove-box that provided a controlled low-humidity environment. The oxides of 235U and 238U were weighed and mixed with a mole ratio n(235U)/n(238U) = 1.0 and then dissolved. The 233U oxide was dissolved to form a separate solution with the same concentration and 6rom this primary solution three dilutions were made by weighing. A weighed amount of the n(235U)/n(238U) solution and weighed amounts of the 233U solutions were mixed in various proportions in order to achieve n(233U)/n(238U) isotope ratios varying from 1.0 to 10-6. The methods for the preparation, the mixing and the mixing calculations are described. The expanded uncertainties (coverage factor k = 2) of the certified isotope ratios for the IRMM-074 series are 0.015% for the n(235U)/n(238U) ratio and 0.025% for the n(233U)/n(238U) ratios, which constitutes an improvement compared to those of the predecessor IRMM-072 series. In addition, recent observations regarding the linearity response of secondary electron multipliers (SEMs) and suitable reference materials for investigating detector linearity are reviewed. Two measurement procedures for applying the IRMM-072 and IRMM-073 (diluted from the remaining fraction of IRMM-072) series as well as the new IRMM-074 series for assessing SEM linearity are suggested. The procedures are tailor-made for the specific instrumental characteristics of thermal ionization mass spectrometers (TIMS) and multiple-collector inductively coupled plasma mass spectrometers (MC-ICPMS) but can be adapted also for further types of isotope ratio mass spectrometers.

Richter, S.; Alonso, A.; Aregbe, Y.; Eykens, R.; Kehoe, F.; Kühn, He; Kivel, N.; Verbruggen, A.; Wellum, R.; Taylor, P. D. P.



Sequential separation of light rare-earth elements, thorium and uranium by miniaturized extraction chromatography: Application to isotopic analyses of silicate rocks  

Microsoft Academic Search

A new method for the concomitant separation of the light rare-earth elements (LREEs), thorium and uranium is described, and applied to the determination of 143Nd144Nd ratios, and concentrations of Sm, Nd, Th and U in silicate rocks, using isotope dilution and thermal ionization mass spectrometry. The proposed scheme is based on two recently introduced extraction chromatographic materials, referred to as

Christian Pin; JoséFrancisco Santos Zalduegui



Evaluation of two gas-dilution methods for instrument calibration  

NASA Technical Reports Server (NTRS)

Two gas dilution methods were evaluated for use in the calibration of analytical instruments used in air pollution studies. A dual isotope fluorescence carbon monoxide analyzer was used as the transfer standard. The methods are not new but some modifications are described. The rotary injection gas dilution method was found to be more accurate than the closed loop method. Results by the two methods differed by 5 percent. This could not be accounted for by the random errors in the measurements. The methods avoid the problems associated with pressurized cylinders. Both methods have merit and have found a place in instrument calibration work.

Evans, A., Jr.



Dilution jet mixing program  

NASA Technical Reports Server (NTRS)

Parametric tests were conducted to quantify the mixing of opposed rows of jets (two-sided injection) in a confined cross flow. Results show that jet penetrations for two sided injections are less than that for single-sided injections, but the jet spreading rates are faster for a given momentum ratio and orifice plate. Flow area convergence generally enhances mixing. Mixing characteristics with asymmetric and symmetric convergence are similar. For constant momentum ratio, the optimum S/H(0) with in-line injections is one half the optimum value for single sided injections. For staggered injections, the optimum S/H(0) is twice the optimum value for single-sided injection. The correlations developed predicted the temperature distributions within first order accuracy and provide a useful tool for predicting jet trajectory and temperature profiles in the dilution zone with two-sided injections.

Srinivasan, R.; Coleman, E.; Johnson, K.



Isotopic Ages from Some Spitsbergen Rocks  

Microsoft Academic Search

ISOTOPIC ages by potassium - argon and rubidium - strontium methods have been measured on some Spitsbergen rocks, in the hope of contributing to the Mid-Palægeozoic time-scale and to the understanding of local geological history1. Rubidium, strontium and argon measurements were made by stable isotope dilution analysis, except for York's figure, which was by total volume (argon) measurement. The potassium




Thermal desorption studies of isotopically-labeled oxygen-induced superconductivity in La sub 2 CuO sub 4+. delta  

SciTech Connect

Isotopically-labeled oxygen enrichment and thermal desorption mass spectroscopy (TDMS) have been combined to study interstitial oxygen desorption from superconducting La{sub 2}CuO{sub 4+{delta}} ({delta} {le} 0.032). Single crystal samples of magnetic insulating La{sub 2}CuO{sub 4.00} were annealed at 860K under 1--3 kbar oxygen pressure for 12--100 hours to yield hole-doped, superconducting La{sub 2}CuO{sub 4+{delta}} samples with 35K < {Tc} < 40K. Whereas no TDMS signals were observed for the insulator, rapid bursts (FWHM < 0.5 sec) of molecular oxygen were observed above 350K while heating the superconductor at less than 1 K sec{sup {minus}1} in high vacuum. A kinetic model is proposed in which the interstitial oxygen diffuses to internal grain boundaries and defects during heating, thereby inducing stress in the lattice as it attempts to revert to the LaCuO{sub 4.00} crystal structure. This stress is relieved by lattice fracture at grain boundaries during the TDMS experiment, releasing the trapped oxygen from the sample as micro-cracks are formed. In addition, the facile oxygen exchange between interstitial and lattice oxygen sites has been discovered by TDMS and weight gain measurements from isotopically-enriched crystals, supporting the structural model of Chaillout, et al. in which the interstitial oxygen atom dimerizes with a lattice oxygen ion.

Shinn, N.D.; Bartram, M.E.; Schirber, J.E.; Overmyer, D.L.; Rogers, J.W. Jr. (Sandia National Labs., Albuquerque, NM (USA)); Fisk, Z.; Cheong, S.W. (Los Alamos National Lab., NM (USA))



Geothermal investigations in Idaho. Part 12. Stable isotopic evaluation of thermal water occurrences in the Weiser and Little Salmon River drainage basins and adjacent areas, west-central Idaho with attendant gravity and magnetic data on the Weiser area  

SciTech Connect

Fifteen thermal springs, two thermal wells, and eight cold springs in the Weiser and Little Salmon river drainages were sampled for deuterium and oxygen-18 analysis during the fall of 1981. The straight-line fit of delta D and delta /sup 18/O versus latitude and longitude observed in the data is what would be expected if the recharge areas for the thermal and non-thermal waters were in close proximity to their respective discharge points. The discrete values of delta D and delta /sup 18/O for each thermal discharge suggest that none of the sampled thermal systems have common sources. The depleted deuterium and oxygen-18 contents of most thermal relative to non-thermal waters sampled suggests that the thermal waters might be Pleistocene age precipitation. The isotopic data suggest little or no evidence for mixing of thermal and non-thermal water for the sampled discharges. Thermal waters from Weiser, Crane Creek, Cove Creek, and White Licks hot springs show enrichment in oxygen-18 suggesting that these waters have been at elevated temperatures relative to other sampled thermal discharges in the area. Gravity and magnetic data gathered by the Idaho State University Geology Department in the Weiser Hot Springs area suggest that southeastward plunging synclinal-anticlinal couples, which underlie the hot springs, are cut south of the springs by a northeast trending boundary fault.

Mitchell, J.C.; Bideganeta, K.; Palmer, M.A.



Isotope dilution ESI-LC-MS/MS for quantification of free and total N?-(1-Carboxymethyl)-L-Lysine and free N?-(1-Carboxyethyl)-L-Lysine: comparison of total N?-(1-Carboxymethyl)-L-Lysine levels measured with new method to ELISA assay in gruel samples.  


ESI-LC-MS/MS method with isotope dilution and SPE based on cation-exchange was developed for determination of free and total N?-(1-Carboxymethyl)-L-Lysine (CML) and free N?-(1-Carboxyethyl)-L-Lysine (CEL). The use of nonafluoropentanoic acid in mobile phase was omitted, SPE recoveries of 82±3% and 91±10% (n=6) for CML and CEL respectively and, calibration curves (R(2)>0.9985) were attained. The method was applied to gruel samples and LoQ for the method was 5 ng/ml, RSD <10% and accuracy was 115%. Total CML levels in the gruel samples varied from 103-408 mg/kg protein. Free CML levels which were 1000 times lower than total CML were three times higher than free CEL levels. CML in a gruel sample was 127±7, 84±9 and 253±28 mg/kg using the current ESI-LC-MS/MS, ELISA and GC-MS respectively. The described method has advantages over ELISA with respect to reproducibility and specificity and over GC-MS with respect to reproducibility. PMID:23993613

Tareke, E; Forslund, A; Lindh, C H; Fahlgren, C; Östman, E



Separated Isotopes as Internal Standards in Spark Source Mass Spectrometry  

Microsoft Academic Search

The use of separated stable isotopes as internal standards in spark source mass spectrometry is described. This method is useful for solution samples and complements the more classical isotope dilution technique. For powdered or insoluble samples, the isotopes are dried onto a conducting matrix material-usually high purity silver powder-followed by homogenization of the sample with this «spiked’ matrix. The resulting

D. L. Donohue; J. A. Carter; J. C. Franklin



Uranium-lead Isotope Evidence in the Shelyabinsk LL5 Chondrite Meteorite for Ancient and Recent Thermal Events  

NASA Technical Reports Server (NTRS)

The impact histories on chondrite parent bodies can be deduced from thermochronologic analyses of materials and isotope systems with distinct apparent closure temperatures. It is especially critical to better understand the geological histories and physical properties of potenally hazardous near-Earth asteroids. Chelyabinsk is an LL5 chondrite meteorite that was dispersed over a wide area tens of kilometers south of the town of Chelyabinsk, Russia by an explosion at an altitude of 27 km at 3:22 UT on 15 Feb 2013 [1,2]. The explosion resulted in significant damage to surrounding areas and over 1500 injuries along with meteorite fragments being spread over a wide area [1].

Lapen, T. J.; Kring, D. A.; Zolensky, M. E.; Andreasen, R.; Righter, M.; Swindle, T. D.; Beard, S. P.; Swindle, T. D.



Stress in dilute suspensions  

NASA Technical Reports Server (NTRS)

Generally, two types of theory are used to describe the field equations for suspensions. The so-called postulated equations are based on the kinetic theory of mixtures, which logically should give reasonable equations for solutions. The basis for the use of such theory for suspensions is tenuous, though it at least gives a logical path for mathematical arguments. It has the disadvantage that it leads to a system of equations which is underdetermined, in a sense that can be made precise. On the other hand, the so-called averaging theory starts with a determined system, but the very process of averaging renders the resulting system underdetermined. A third type of theory is proposed in which the kinetic theory of gases is used to motivate continuum equations for the suspended particles. This entails an interpretation of the stress in the particles that is different from the usual one. Classical theory is used to describe the motion of the suspending medium. The result is a determined system for a dilute suspension. Extension of the theory to more concentrated systems is discussed.

Passman, Stephen L.



Extinction of diffusion flames burning diluted methane and diluted propane in diluted air  

Microsoft Academic Search

A theoretical and experimental investigation of the extinction limits of counterflow diffusion flames burning methane and propane is outlined. A diffusion flame is stabilized between counterflowing streams of a fuel diluted with nitrogen and air diluted with nitrogen. Extinction limits for such flames were measured over a wide parametric range. Results for methane and propane were found to be in

I.K. Puri; K. Seshadri



Sedimentology and Carbon Isotope in Lower Tertiary Sediments of Rajasthan:Implication to Post Paleocene\\/Eocene Thermal Maximum Event  

Microsoft Academic Search

The Paleocene-Eocene thermal maxima (PETM; ~55 My.), identified as the most abrupt and transient climatic events in Cenozoic era, associated with pronounced warming of ocean and atmosphere, change in ocean chemistry, and perturbation of global carbon cycle. Catastrophic (~5° -6° C) rise in the deep sea temperature and oxygen deficiency might cause 30-50% extinction of benthic foraminifera, increase in sea

A. Samanta; A. Sarkar; M. Bera



Hydrogen isotope inventory in the graphite divertor tiles of ASDEX Upgrade as measured by thermal desorption spectroscopy  

Microsoft Academic Search

The hydrogen and deuterium inventories of the ASDEX Upgrade divertor tiles were measured after the experimental period from December 1994 to July 1995 by thermal desorption spectroscopy (TDS) of samples cut out of the divertor tiles. The samples were heated by electron bombardment up to 2100 K; the released gases were measured by means of a calibrated quadrupole mass spectrometer.

P. Franzen; R. Behrisch; C. Garcia-Rosales; D. Schleussner; D. Rosler; J. Becker; W. Knapp; C. Edelmann



Extraction Chromatographic Methods in the Sample Preparation Sequence for Thermal Ionization Mass Spectrometric Analysis of Plutonium Isotopes  

SciTech Connect

A sample preparation sequence for actinide isotopic analysis by TIMS is described that includes column-based extraction chromatography as the first separation step, followed by anion exchange column separations. The sequence is designed to include a wet ashing step after the extraction chromatography to prevent any leached extractant or oxalic acid eluent reagents from interfering with subsequent separations, source preparation, or TIMS ionization. TEVA-resin and DGA-resin materials, containing extractants that consist only of C, N, O, and H atoms, were investigated for isolation of plutonium. Radiotracer level studies confirmed expected high yields from column-based separation procedures. Femtogram-level studies were carried out with TIMS detection, using multiple isotopic spikes through the separation sequence. Pu recoveries were 87% and 86% for TEVA- and DGA-resins separations respectively. The Pu recoveries from 400 {mu}L anion-exchange column separations were 89% and 93% for trial sequences incorporating TEVA and DGA-resin. Thus, a prior extraction chromatography step in the sequence did not interfere with the subsequent anion exchange separation when a simple wet ash step was carried out in between these column separations. The average measurement efficiency, for Pu, encompassing the chemical separation recoveries and the TIMS ionization efficiency, was 2.73 {+-} 0.77% (2-sigma) for the DGA-resin trials and 2.67 {+-} 0.54% for the TEVA-resin trials, compared to 3.41% and 2.37% (average 2.89%) for two spikes in the experimental set. These compare with an average measurement efficiency of 2.78 {+-} 1.70%, n = 33 from process benchmark analyses using Pu spikes processed through a sequence of oxalate precipitation, wet ash, iron hydroxide precipitation, and anion exchange column separations. We conclude that extraction chromatography can be a viable separation procedure as part of a multistep sequence for TIMS sample preparation.

Grate, Jay W.; O'Hara, Matthew J.; Farawila, Anne F.; Douglas, Matthew; Haney, Morgan M.; Peterson, Steve L.; Maiti, Tapas C.; Aardahl, Christopher L.



Dilution refrigeration for space applications  

NASA Technical Reports Server (NTRS)

Dilution refrigerators are presently used routinely in ground based applications where temperatures below 0.3 K are required. The operation of a conventional dilution refrigerator depends critically on the presence of gravity. To operate a dilution refrigerator in space many technical difficulties must be overcome. Some of the anticipated difficulties are identified in this paper and possible solutions are described. A single cycle refrigerator is described conceptually that uses forces other than gravity to function and the stringent constraints imposed on the design by requiring the refrigerator to function on the earth without using gravity are elaborated upon.

Israelsson, U. E.; Petrac, D.