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1

Isotope Ratio Mass Spectrometry.  

PubMed

Isotope Ratio Mass Spectrometry (IRMS) is a specialized technique used to provide information about the geographic, chemical, and biological origins of substances. The ability to determine the source of an organic substance stems from the relative isotopic abundances of the elements which comprise the material. Because the isotope ratios of elements such as carbon, hydrogen, oxygen, sulfur, and nitrogen can become locally enriched or depleted through a variety of kinetic and thermodynamic factors, measurement of the isotope ratios can be used to differentiate between samples which otherwise share identical chemical compositions. Several sample introduction methods are now available for commercial isotope ratio mass spectrometers. Combustion is most commonly used for bulk isotopic analysis, whereas gas and liquid chromatography are predominately used for the real-time isotopic analysis of specific compounds within a mixture. Here, highlights of advances in instrumentation and applications within the last three years are provided to illustrate the impact of this rapidly growing area of research. Some prominent new applications include authenticating organic food produce, ascertaining whether or not African elephants are guilty of night-time raids on farmers' crops, and linking forensic drug and soil samples from a crime scene to a suspected point of origin. For the sake of brevity, we focus this Minireview on the isotope ratio measurements of lighter-elements common to organic sources; we do not cover the equally important field of inorganic isotope ratio mass spectrometry. PMID:19173039

Muccio, Zeland; Jackson, Glen P

2009-02-01

2

Isotope dilution mass spectrometry  

NASA Astrophysics Data System (ADS)

In the past isotope dilution mass spectrometry (IDMS) has usually been applied using the formation of positive thermal ions of metals. Especially in calibrating other analytical methods and for the certification of standard reference materials this type of IDMS became a routine method. Today, the progress in this field lies in the determination of ultra trace amounts of elements, e.g. of heavy metals in Antarctic ice and in aerosols in remote areas down to the sub-pg g-1 and sub-pg m-3 levels respectively, in the analysis of uranium and thorium at concentrations of a few pg g-1 in sputter targets for the production of micro- electronic devices or in the determination of sub-picogram amounts of230Th in corals for geochemical age determinations and of226Ra in rock samples. During the last few years negative thermal ionization IDMS has become a frequently used method. The determination of very small amounts of selenium and technetium as well as of other transition metals such as vanadium, chromium, molybdenum and tungsten are important examples in this field. Also the measurement of silicon in connection with a re-determination of Avogadro's number and osmium analyses for geological age determinations by the Re/Os method are of special interest. Inductively-coupled plasma mass spectrometry is increasingly being used for multi-element analyses by the isotope dilution technique. Determinations of heavy metals in samples of marine origin are representative examples for this type of multi-element analysis by IDMS. Gas chromatography-mass spectrometry systems have also been successfully applied after chelation of metals (for example Pt determination in clinical samples) or for the determination of volatile element species in the environment, e.g. dimethyl sulfide. However, IDMS--specially at low concentration levels in the environment--seems likely to be one of the most powerful analytical methods for speciation in the future. This has been shown, up to now, for species of iodine, selenium and some heavy metals in aquatic systems.

Heumann, Klaus G.

1992-09-01

3

Multiple isotopic labels for quantitative mass spectrometry  

PubMed Central

Quantitative mass spectrometry is often performed using isotopically-labeled samples. While the 4-trimethylammoniumbutyryl (TMAB) labels have many advantages over other isotopic tags, only two forms have previously been synthesized (i.e. a heavy form containing 9 deuteriums and a light form without deuterium). In the present report, two additional forms containing 3 and 6 deuteriums have been synthesized and tested. These additional isotopic tags perform identically to the previously reported tags; peptides labeled with the new TMAB reagents co-elute from reverse phase HPLC columns with peptides labeled with the lighter and heavier TMAB reagents. Altogether, these 4 tags allow for multivariate analysis in a single liquid chromatography/mass spectrometry analysis, with each isotopically tagged peptide differing in mass by 3 Da per tag incorporated. The synthetic scheme is described in simple terms so that a biochemist without specific training in organic chemistry can perform the synthesis. The interpretation of tandem mass spectrometry data for the TMAB-labeled peptides is also described in more detail. The additional TMAB isotopic reagents described here, together with the additional description of the synthesis and analysis should allow these labels to be more widely used for proteomics and peptidomics analyses. PMID:19551992

Morano, Cain; Zhang, Xin; Fricker, Lloyd D.

2009-01-01

4

Calcium isotope analysis by mass spectrometry.  

PubMed

The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades. Practically all Ca isotopes suffer from significant isobaric interferences, whereas low-abundant isotopes can be particularly affected by neighboring major isotopes. The extent of natural variations of stable isotopes appears to be relatively limited, and highly precise techniques are required to resolve isotopic effects. Isotope fractionation during sample preparation and measurements and instrumental mass bias can significantly exceed small isotope abundance variations in samples, which have to be investigated. Not surprisingly, a TIMS procedure developed by Russell et al. (Russell et al., 1978. Geochim Cosmochim Acta 42: 1075-1090) for Ca isotope measurements was considered as revolutionary for isotopic measurements in general, and that approach is used nowadays (with small modifications) for practically all isotopic systems and with different mass spectrometric techniques. Nevertheless, despite several decades of calcium research and corresponding development of mass spectrometers, the available precision and accuracy is still not always sufficient to achieve the challenging goals. The present article discusses figures of merits of presently used analytical methods and instrumentation, and attempts to critically assess their limitations. In Sections 2 and 3, mass spectrometric methods applied to precise stable isotope analysis and to the determination of (41)Ca are described. Section 4 contains a short summary of selected applications, and includes tracer experiments and the potential use of biological isotope fractionation in medical studies, paleoclimatic and paleoceanographic, and other terrestrial as well as extraterrestrial investigations. PMID:19551693

Boulyga, Sergei F

2010-01-01

5

O isotopic composition of CaCO3 measured by continuous ow isotope ratio mass spectrometry  

E-print Network

XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction spectrometry (DI-IRMS). A mass spectrometer is used to determine the ratio (R) of the heavy isotoped13 C and d18 O isotopic composition of CaCO3 measured by continuous ¯ow isotope ratio mass

6

Hydrogen isotope analysis by quadrupole mass spectrometry  

Microsoft Academic Search

The analysis of isotopes of hydrogen (H, D, T) and helium (³He, He) and selected impurities using a quadrupole mass spectrometer (QMS) has been investigated as a method of measuring the purity of tritium gas for injection into the Tokamak Fusion Test Reactor (TFTR). A QMS was used at low resolution, m\\/..delta..m < 150, for quantifying impurities from m\\/q =

R. E. Ellefson; W. E. Moddeman; H. F. Dylla

1981-01-01

7

Microbeam titanium isotopic analysis by resonance ionization mass spectrometry  

SciTech Connect

The importance of isotopic anomalies in refractory inclusions in meteorites is well established. Measurements of the anomalies using conventional mass spectrometry are often rendered difficult, however, by isobarically interfering isotopes: for example, {sup 48}Ti and {sup 48}Ca. Resonance ionization mass spectrometry (RIMS) can substantially reduce isobaric interferences in a number of systems. We have employed RIMS for the in situ detection of Ti atoms sputtered from pure Ti metal and from several terrestrial oxides containing both Ti and Ca. Tunable lasers were employed to resonantly ionize neutral Ti atoms. We have chosen Ti specifically because of the importance of Ti isotopic anomalies in cosmochemistry.

Spiegel, D.R.; Davis, A.M.; Clayton, R.N. (Chicago Univ., IL (USA). Enrico Fermi Inst.); Pellin, M.J.; Calaway, W.F.; Burnett, J.W.; Coon, S.R.; Young, C.E.; Gruen, D.M. (Argonne National Lab., IL (USA))

1991-01-01

8

Hydrogen isotope analysis by quadrupole mass spectrometry  

Microsoft Academic Search

The analysis of isotopes of hydrogen (H,D,T) and helium (³He,⁴He) and selected impurities using a quadrupole mass spectrometer (QMS) has been investigated as a method of measuring the purity of tritium gas for injection into the Tokamak Fusion Test Reactor (TFTR). A QMS was used at low resolution, m\\/Dm<150, for quantifying impurities from m\\/q = 2 to 44, and at

R. E. Ellefson; W. E. Moddeman; H. F. Dylla

1981-01-01

9

How to correct for blanks in isotope dilution mass spectrometry  

NASA Astrophysics Data System (ADS)

A general equation for isotope delution mass spectrometry (IDMS) has been developed which considers the correction for blanks from labware and reagents used to dissolve, purify and transform samples in a form suitable for (thermal ionization) mass spectrometric measurement. The equation takes into account that sample, spike and blank may have three diffirent isotopic compositions. It is further shown that the isotopic composition of non-natural unknown samples must be determined independently on a sample of known chemical concentration, or, if this is not possible, on an aliquot of the unknown sample to be determined by IDMS.

Lamberty, A.; Pauwels, J.

1991-01-01

10

Osmium isotope ratio determinations by negative thermal ionization mass spectrometry  

Microsoft Academic Search

A new technique for osmium isotope ratio determinations by negative thermal ionization mass spectrometry using the formation of OsO-3 ions is presented. Different filament materials and chemicals to reduce the electron work function are investigated. With Ba(OH)2 and platinum as filament material an ionization efficiency of more than 1% is obtained for nanogram sample amounts. The isotopic abundances of a

Joachim Völkening; Thomas Walczyk; Klaus G. Heumann

1991-01-01

11

High Resolution Double-Focusing Isotope Ratio Mass Spectrometry  

NASA Astrophysics Data System (ADS)

In recent years isotope ratio mass spectrometry has extended to the capability of quantifying very small isotope signatures related with low abundances and simultaneously detecting molecular masses such as isotopomers and isotopologues containing clumped isotopes. Some of those applications are limited by molecular interferences like different gas molecules with the same nominal mass, e.g. Ar/O2, adducts of the same molecule or of different molecules, and very small isotope abundances. The Thermo Scientific MAT 253 ULTRA is the next generation of high precision gas isotope ratio mass spectrometry, which combines a 10 KV gas ionization source (Thermo Scientific MAT 253) with a double focusing multi-collector mass analyzer (Thermo Scientific Neptune) and reduces those limitations by measuring isotope ratios on a larger dynamic range with high precision. Small ion beam requirements and high sensitivity are achieved by signal-to-noise improvements through enhanced ion beam amplification in faraday cups and ion counters. Interfering backgrounds, e.g. interfering isotopologues or isobaric ions of contaminants, are dramatically decreased by a dynamic range increase combined with high evacuation leading to undisturbed ion transmission through the double-focusing analyser. Furthermore, automated gain calibration for mathematical baseline corrections, switchable detector arrays, ion source control, analyser focusing and full data export is controlled under Isodat data control. New reference/sample strategies are under investigation besides incorporation of the continuous-flow technique and its versatile inlet devices. We are presenting first results and applications of the MAT 253 Ultra.

Radke, J.; Deerberg, M.; Hilkert, A.; Schlüter, H.-J.; Schwieters, J.

2012-04-01

12

Mass spectrometry.  

NASA Technical Reports Server (NTRS)

Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.

Burlingame, A. L.; Johanson, G. A.

1972-01-01

13

Caution on the Use of Liquid Nitrogen Traps in Stable Hydrogen Isotope-Ratio Mass Spectrometry  

E-print Network

other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen to a VG Micromass model 602 dual inlet isotope-ratio mass spectrometer.3,4,6 Gaseous hydrogenCaution on the Use of Liquid Nitrogen Traps in Stable Hydrogen Isotope-Ratio Mass Spectrometry

14

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. PMID:22827593

Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

2012-01-01

15

Quantitating isotopic molecular labels with accelerator mass spectrometry.  

PubMed

Accelerator mass spectrometry (AMS) traces isotopically labeled biochemicals and provides significant new directions for understanding molecular kinetics and dynamics in biological systems. AMS traces low-abundance radioisotopes for high specificity but detects them with MS for high sensitivity. AMS reduces radiation exposure doses to levels safe for use in human volunteers of all ages. Total radiation exposures are equivalent to those obtained in very short airplane flights, a commonly accepted radiation risk. Waste products seldom reach the Nuclear Regulatory Commission (NRC) definition of radioactive waste material for (14)C and (3)H. Attomoles of labeled compounds are quantified in milligram-sized samples, such as 20 microl of blood. AMS is available from several facilities that offer services and new spectrometers that are affordable. Detailed examples of designing AMS studies are provided, and the methods of analyzing AMS data are outlined. PMID:16401517

Vogel, John S; Love, Adam H

2005-01-01

16

Advances in Isotope Ratio Mass Spectrometry and Required Isotope Reference Materials  

PubMed Central

The article gives a condensed version of the keynote lecture held at the International Mass Spectrometry Conference 2012 in Kyoto. Starting with some examples for isotope research the key requirements for metrologically valid procedures enabling traceable and comparable isotope data are discussed. Of course multi-collector mass spectrometers are required which offer sufficiently high isotope ratio precision for the intended research work. Following this, corrections for mass fractionation/discrimination, validation of the analytical procedure including chemical sample preparation and complete uncertainty budgets are the most important issues for obtaining a metrologically valid procedure for isotope ratio determination. Only the application of such metrologically valid procedures enables the generation of traceable and comparable isotope data. To realize this suitable isotope and/or ?-reference materials are required, which currently are not sufficiently available for most isotope systems. Boron is given as an example, for which the situation regarding isotope and ?-reference materials is excellent. Boron may therefore serve as prototype for other isotope systems. PMID:24349939

Vogl, Jochen

2013-01-01

17

A novel isotope analysis of oxygen in uranium oxides: comparison of secondary ion mass spectrometry, glow discharge mass spectrometry and thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

The natural variation of the oxygen isotopic composition is used among geologists to determine paleotemperatures and the origin of minerals. In recent studies, oxygen isotopic composition has been recognized as a possible tool for identification of the origin of seized uranium oxides in nuclear forensic science. In the last 10 years, great effort has been made to develop new direct and accurate n( 18O)/ n( 16O) measurements methods. Traditionally, n( 18O)/ n( 16O) analyses are performed by gas mass spectrometry. In this work, a novel oxygen isotope analysis by thermal ionization mass spectrometry (TIMS), using metal oxide ion species (UO +), is compared to the direct methods: glow discharge mass spectrometry (GDMS) and secondary ion mass spectrometry (SIMS). Because of the possible application of the n( 18O)/ n( 16O) ratio in nuclear forensics science, the samples were solid, pure UO 2 or U 3O 8 particles. The precision achieved using TIMS analysis was 0.04%, which is similar or even better than the one obtained using the SIMS technique (0.05%), and clearly better if compared to that of GDMS (0.5%). The samples used by TIMS are micrograms in size. The suitability of TIMS as a n( 18O)/ n( 16O) measurement method is verified by SIMS measurements. In addition, TIMS results have been confirmed by characterizing the n( 18O)/ n( 16O) ratio of UO 2 sample also by the traditional method of static vacuum mass spectrometry at the University of Chicago.

Pajo, L.; Tamborini, G.; Rasmussen, G.; Mayer, K.; Koch, L.

2001-05-01

18

The Role of Naturally Occurring Stable Isotopes in Mass Spectrometry, Part II: The Instrumentation  

PubMed Central

In the second instalment of this tutorial, the authors explain the instrumentation for measuring naturally occurring stable isotopes, specifically the magnetic sector mass spectrometer. This type of instrument remains unrivalled in its performance for isotope ratio mass spectrometry (IRMS) and the reader is reminded of its operation and its technical advantages for isotope measurements. PMID:23772101

Bluck, Les; Volmer, Dietrich A.

2013-01-01

19

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

NASA Technical Reports Server (NTRS)

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

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

1999-01-01

20

Determination of the H3 Factor in Hydrogen Isotope Ratio Monitoring Mass Spectrometry  

E-print Network

Determination of the H3 Factor in Hydrogen Isotope Ratio Monitoring Mass Spectrometry Alex L spectrometer.1 Since H3 + is not resolved from HD+ by typical isotope ratio mass spectrometers, a correction, is a parameter required in high- precision, mass spectrometric analyses of hydrogen iso- topic abundances. When H

Sessions, Alex L.

21

Quantitative imaging of subcellular metabolism with stable isotopes and multi-isotope imaging mass spectrometry  

PubMed Central

Multi-isotope imaging mass spectrometry (MIMS) is the quantitative imaging of stable isotope labels in cells with a new type of secondary ion mass spectrometer (NanoSIMS). The power of the methodology is attributable to (i) the immense advantage of using non-toxic stable isotope labels, (ii) high resolution imaging that approaches the resolution of usual transmission electron microscopy and (iii) the precise quantification of label down to 1 part-per-million and spanning several orders of magnitude. Here we review the basic elements of MIMS and describe new applications of MIMS to the quantitative study of metabolic processes including protein and nucleic acid synthesis in model organisms ranging from microbes to humans. PMID:23660233

Steinhauser, Matthew L.; Lechene, Claude P.

2014-01-01

22

Advancement and Application of Gas Chromatography Isotope Ratio Mass Spectrometry Techniques for Atmospheric Trace Gas Analysis  

Microsoft Academic Search

The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system

Brian M Giebel

2011-01-01

23

Computer Analysis of Isotope Clusters in Mass Spectrometry  

ERIC Educational Resources Information Center

Describes the application of a computer program designed to produce a formula determination simultaneously accounting for both elemental composition and probable isotopic species for a measured ion mass. (SLH)

Bell, Harold M.

1974-01-01

24

Isotopically Selective Atom Counting Using Photon Burst Mass Spectrometry  

Microsoft Academic Search

Applications in radiochemical dating and environmental monitoring often require measurement of a small number of rare atoms at isotopic abundances in the 10 ^{-10} to 10^{ -15} range. For this level, the abundance sensitivity of conventional mass spectrometers ( ~10^{-5}) is insufficient and some means for providing additional selectivity is needed. One laser-based method that has been proposed is Photon

Robert Dwight Labelle

1993-01-01

25

Heavy stable isotope measurements with thermal ionization mass spectrometry : non mass-dependent fractionation effects between even and uneven isotopes.  

NASA Astrophysics Data System (ADS)

The isotopic composition of elements such as Zn, Cd, Pb can be precisely measured by thermal ionization mass spectrometry technique (TIMS) using the silicagel method [1]. Advantages of TIMS are: 1)- low instrumental isotope fractionation (from percent/amu down to permil/amu) and 2)- high ionization yields. The mass-dependent instrumental fractionation for elements characterized by more than 2 isotopes is generally corrected by employing the multispike method [?]. We will show that non mass-dependent fractionation effects are detected during the ionic thermal emission of Zn, Cd, Pb. In the case of Cd the even isotopes (110Cd, 112Cd, 114Cd) show a << normal >> (mass-dependent) fractionation whereas non mass-dependent fractionation effects are clearly resolved for the uneven isotopes (111Cd, 113Cd) relative to the even isotopes. The deviation from the mass-dependent evolution increases with time and reaches up to 0,1 %. A similar behavior is stated during the thermal emission of Zn. Mass-dependent fractionation occurs between the even isotopes (64Zn, {66}Zn, 68Zn), whereas the fractionation of 67Zn deviates from the mass-dependent evolution of the even isotopes by several permils. (amu??) << Abnormal fractionation >> of 207Pb during thermal emission of Pb in the order of a few 10{-4} relatively to the mass-dependent fractionation between 204Pb, 206Pb, 208Pb was described [2,3]. We consider that the non mass-dependent discrimination effects of the uneven compared to the even isotopes set in evidence for a variety of elements has a common origin. We attribute this effect to the hyperfine interaction between apparied electron and the nucleus of the uneven isotopes, that carries a nuclear magnetic moment. The coupling between electronic spin and nuclear spin occurs inside the silica-glass bead. This non mass-dependent fractionation probably may also be found for other elements when the silicagel loading technique is employed. [1] Akishin P.A. et al. 1957, Geokhimya 5, 425. - [2] Thirwall M.F. 2000, Chem. Geol. 163, 299-322. - [3] Doucelance R. and Manhès G. 2001, Chem. Geol. 176, 361-377.

Manhès, G.; Göpel, C.

2003-04-01

26

Rapid determination of 237 Np and Pu isotopes in water by inductively-coupled plasma mass spectrometry and alpha spectrometry  

Microsoft Academic Search

A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for\\u000a the measurement of 237Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry. 238U can interfere with 239Pu measurement by ICP-MS as 238UH+ mass overlap and 237Np via peak tailing. The method provide enhanced removal of uranium by

Sherrod L. MaxwellBrian; Brian A. Culligan; Vernon D. Jones; Sheldon T. Nichols; Gary W. Noyes

2011-01-01

27

RAPID DETERMINATION OF 237 NP AND PU ISOTOPES IN WATER BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY AND ALPHA SPECTROMETRY  

Microsoft Academic Search

A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of ²³Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. ²³U can interfere with ²³Pu measurement by ICP-MS as ²³UH{sup +} mass overlap and ²³Np via peak tailing. The method provide enhanced

S. Maxwell; V. Jones; B. Culligan; S. Nichols; G. Noyes

2010-01-01

28

Cholesterol efflux analyses using stable isotopes and mass spectrometry.  

PubMed

Cholesterol efflux from macrophages and the vascular wall is the initial step of the cardiovascular protective reverse cholesterol transport process. This study demonstrates a mass spectrometry based assay to measure the cellular and medium content of [d(7)]cholesterol and unlabeled cholesterol that can be used to measure cholesterol efflux from cell lines. Using a triple-quadrupole electrospray ionization-MS instrument in direct infusion mode, product ion scanning for m/z 83, neutral loss (NL) 375.5 scanning, and NL 368.5 scanning were used to detect cholesterol (as an acetylated derivative), [d(7)]cholesteryl ester (CE), and unlabeled CE, respectively. The same mass of [d(7)]cholesterol was substituted for [(3)H]cholesterol under standard efflux assay conditions. At the end of [d(7)]cholesterol loading, the intracellular mass of [d(7)]cholesterol was twofold greater than that of unlabeled cholesterol, and the intracellular [d(7)]CE profile was similar to that of unlabeled CE. Efflux of cholesterol to apolipoprotein A-I and high-density lipoproteins was similar comparing efflux of either [d(7)]cholesterol or [(3)H]cholesterol as measured by following efflux of the tracers only. This technique also can be used to assess the efflux of unlabeled cholesterol to acceptors in medium that are initially cholesterol-free (e.g., apolipoprotein A-I). Taken together, this mass spectrometry-based assay provides new molecular detail to assess cholesterol efflux. PMID:23072980

Brown, Robert J; Shao, Fei; Baldán, Angel; Albert, Carolyn J; Ford, David A

2013-02-01

29

Determination of Amino Acid Isotope Enrichment Using Liquid Chromatography–Mass Spectrometry  

Microsoft Academic Search

The change in amino acid enrichment, an indicator of a change in protein synthesis and\\/or degradation, is usually measured using gas chromatography–mass spectrometry and\\/or (GC–combustion) isotope ratio mass spectrometry. Unfortunately, often a complex and sensitive derivatization procedure and\\/or a large amount of sample is required. Also, these techniques are less suited to study intermediary metabolism, in which the simultaneous application

Hans M. H. van Eijk; Dennis R. Rooyakkers; Peter B. Soeters; Nicolaas E. P. Deutz

1999-01-01

30

Analytical techniques in biomedical stable isotope applications: (isotope ratio) mass spectrometry or infrared spectrometry?  

Microsoft Academic Search

An overview is presented of biomedical applications of stable isotopes in general, but mainly focused on the activities of the Center for Liver, Digestive and Metabolic Diseases of the University Medical Center Groningen. The aims of metabolic studies in the areas of glucose, fat, cholesterol and protein metabolism are briefly explained, as well as the principle of breath testing and

Frans Stellaard; Henk Elzinga

2005-01-01

31

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

PubMed

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

2012-10-20

32

Stable nitrogen isotope analysis of amino Acid enantiomers by gas chromatography/combustion/isotope ratio mass spectrometry.  

PubMed

The analysis of the stable nitrogen isotope compositions of individual amino acid stereoisomers through the use of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) is presented. Nitrogen isotopic compositions of single amino acids or of their enantiomers is possible without the labor-intensive and time-consuming preparative-scale chromatographic procedures required for conventional stable isotope analysis. Following hydrolysis and derivatization, single-component isotope analysis is accomplished on nanomole quantities of each of the stereoisomers of an amino acid, utilizing the effluent stream of gas chromatographic separation. Nitrogen isotope fractionation is minimal during acylation of the amino acid, with no additional nitrogen being added stoichiometrically to the derivative. Thus, the isotopic composition of the nitrogen in the derivative is that of the original compound. Replicate stable nitrogen isotope analyses of 11 amino acids, and their trifluoroacetyl (TFA)/isopropyl (IP) ester derivatives, determined by both conventional isotope ratio mass spectrometry (IRMS) and GC/C/IRMS, indicate that the GC procedure is highly reproducible (standard deviations typically 0.3-0.4‰) and that isotopic differences between the amino acid and its TFA/IP derivative are, in general, less than 0.5‰. PMID:21639229

Macko, S A; Uhle, M E; Engel, M H; Andrusevich, V

1997-03-01

33

Experimental investigations of trimer ion contributions in the low resolution mass spectrometry of hydrogen isotope mixtures.  

PubMed

This paper reports on some preliminary experimental results of a work in progress regarding a problem involving the quantitative analysis of hydrogen isotopes by mass spectrometry of low resolution: the triatomic (trimer) ions interferences with the isotopic hydrogen species having the same mass/charge. These results indicate that, in complex mixtures of hydrogen isotopes, trimer ions are strongly affected by the presence of other species, and a new approach that takes into account the destruction mechanism of trimer ions is necessary for a proper determination of their contributions. PMID:23149602

Bidica, Nicolae

2012-01-01

34

Accuracy and long-term reproducibility of lead isotopic measurements by multiple-collector inductively coupled plasma mass spectrometry using an external method for correction of mass discrimination  

Microsoft Academic Search

The precision of isotopic measurements of Pb by thermal ionization mass spectrometry (TIMS) is limited by the fact that this element does not possess an invariant isotope ratio that can be used for the correction of mass fractionation by internal normalization. Multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS) can overcome this limitation, because with plasma ionization, elements with overlapping mass

Mark Rehkämperab; Alex N. Halliday

1998-01-01

35

High-precision measurement of magnesium isotopes by multiple-collector inductively coupled plasma mass spectrometry  

Microsoft Academic Search

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of variations in the isotopic composition of Mg in a range of materials. The contributions of C?C, C?N, and Mg?H molecular species to the mass spectrum in the Mg mass region are minimised. Variations in sample 26Mg\\/24Mg and 25Mg\\/24Mg ratios are expressed as ?26Mg and ?25Mg units,

Albert Galy; Nick S. Belshaw; Ludwik Halicz; R. Keith O’Nions

2001-01-01

36

Isolation and derivatization of plasma taurine for stable isotope analysis by gas chromatography-mass spectrometry  

Microsoft Academic Search

A method for the isolation and derivatization of plasma taurine is described that allows stable isotope determinations of taurine to be made by gas chromatography-mass spectrometry. The isolation procedure can be applied to 0.1 ml of plasma; the recovery of plasma taurine was 70 to 80%. For gc separation, taurine was converted to its dimethylaminomethylene methyl ester derivative which could

C. S. Irving; P. D. Klein

1980-01-01

37

Liquid chromatography combined with mass spectrometry for 13C isotopic analysis in life science research.  

PubMed

Among the different disciplines covered by mass spectrometry, measurement of (13)C/(12)C isotopic ratio crosses a large section of disciplines from a tool revealing the origin of compounds to more recent approaches such as metabolomics and proteomics. Isotope ratio mass spectrometry (IRMS) and molecular mass spectrometry (MS) are the two most mature techniques for (13)C isotopic analysis of compounds, respectively, for high and low-isotopic precision. For the sample introduction, the coupling of gas chromatography (GC) to either IRMS or MS is state of the art technique for targeted isotopic analysis of volatile analytes. However, liquid chromatography (LC) also needs to be considered as a tool for the sample introduction into IRMS or MS for (13)C isotopic analyses of non-volatile analytes at natural abundance as well as for (13)C-labeled compounds. This review presents the past and the current processes used to perform (13)C isotopic analysis in combination with LC. It gives particular attention to the combination of LC with IRMS which started in the 1990's with the moving wire transport, then subsequently moved to the chemical reaction interface (CRI) and was made commercially available in 2004 with the wet chemical oxidation interface (LC-IRMS). The LC-IRMS method development is also discussed in this review, including the possible approaches for increasing selectivity and efficiency, for example, using a 100% aqueous mobile phase for the LC separation. In addition, applications for measuring (13)C isotopic enrichments using atmospheric pressure LC-MS instruments with a quadrupole, a time-of-flight, and an ion trap analyzer are also discussed as well as a LC-ICPMS using a prototype instrument with two quadrupoles. PMID:17853432

Godin, Jean-Philippe; Fay, Laurent-Bernard; Hopfgartner, Gérard

2007-01-01

38

Profiling of thiol-containing compounds by stable isotope labeling double precursor ion scan mass spectrometry.  

PubMed

Here we developed a novel strategy of isotope labeling in combination with high-performance liquid chromatography-double precursor ion scan mass spectrometry (IL-LC-DPIS-MS) analysis for nontargeted profiling of thiol-containing compounds. In this strategy, we synthesized a pair of isotope labeling reagents (?-bromoacetonylquinolinium bromide, BQB; ?-bromoacetonylquinolinium-d7 bromide, BQB-d7) that contain a reactive group, an isotopically labeled moiety, and an ionizable group to selectively label thiol-containing compounds. The BQB and BQB-d7 labeled compounds can generate two characteristic product ions m/z 218 and 225, which contain an isotope tag and therefore were used for double precursor ion scans in mass spectrometry analysis. The peak pairs with characteristic mass differences can be readily extracted from the two precursor ion scan (PIS) spectra and assigned as potential thiol-containing candidates, which facilitates the identification of analytes. BQB and BQB-d7 labeled thiol-containing compounds can be clearly distinguished by generating two individual ion chromatograms. Thus, thiol-containing compounds from two samples labeled with different isotope reagents are ionized at the same time but recorded separately by mass spectrometry, offering good identification and accurate quantification by eliminating the MS response fluctuation and mutual interference from the two labeled samples. Using the IL-LC-DPIS-MS strategy, we profiled the thiol-containing compounds in beer and human urine, and 21 and 103 thiol candidates were discovered in beer and human urine, respectively. In addition, 9 and 17 thiol candidates in beer and human urine were successfully identified by further comparison with thiol standards or tandem mass spectrometry analysis. Taken together, the IL-LC-DPIS-MS method is demonstrated to be a promising strategy in the profiling of compounds with identical groups in metabolomics study. PMID:25222826

Liu, Ping; Huang, Yun-Qing; Cai, Wen-Jing; Yuan, Bi-Feng; Feng, Yu-Qi

2014-10-01

39

Determination of isotopic ratio of boron in boric acid using laser mass spectrometry.  

PubMed

A reflectron time-of-flight mass spectrometer (RTOFMS) with a laser ablation ion source was used to determine the isotopic ratio of 10B/11B present in boric acid solutions, using graphite as the matrix. The atom % 10B values obtained were within +/-1% of the actual ones. The determination of the boron isotopic ratio using this method is, in comparison to other methods, faster, less expensive and easier to perform. The results are compared with the values determined using thermal ionization mass spectrometry. PMID:16379385

Manoravi, Periasamy; Joseph, Mathew; Sivakumar, Natrajan; Balasubramanian, Rajagopalan

2005-12-01

40

Carbon isotope ratio analysis of steroids by high-temperature liquid chromatography-isotope ratio mass spectrometry.  

PubMed

Generally, compound-specific isotope analysis of steroids is carried out by gas chromatography combined with isotope ratio mass spectrometry. Thus, a derivatization of the steroids prior to the measurement is compulsory, and a correction of the isotopic data is often necessary. To overcome this limitation, we present a new approach of high-temperature liquid chromatography coupled with photodiode array detection and isotope ratio mass spectrometry (HT-LC/PDA/IRMS) for the carbon isotope ratio analysis of unconjugated steroids. A steroid mixture containing 19-norandrosterone, testosterone, epitestosterone, androsterone, and 5?-pregnane-3?,17?,20?-triol was fully separated on a C4 column under high-temperature elution with water as the sole eluent. The accuracy for isotope analysis (±0.5 ‰) was around 20 ?g g(-1) for testosterone, epitestosterone (79 ng steroid absolute on column), and 30 ?g g(-1) for 19-norandrosterone, androsterone, and 5?-pregnane-3?,17?,20?-triol (119 ng steroid absolute on column). The applicability of the method was tested by measuring a pharmaceutical gel containing testosterone. With this work, the scope of LC/IRMS applications has been extended to nonpolar compounds. PMID:24491121

Zhang, Lijun; Thevis, Mario; Piper, Thomas; Jochmann, Maik A; Wolbert, J Benjamin; Kujawinski, Dorothea M; Wiese, Steffen; Teutenberg, Thorsten; Schmidt, Torsten C

2014-03-01

41

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\\/m2.day) 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

1991-01-01

42

Analysis of acrylamide in coffee and cocoa by isotope dilution liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

An accurate and precise method for the quantification of acrylamide using stable isotope dilution liquid chromatography–tandem\\u000a mass spectrometry was developed and used to measure acrylamide in coffee and cocoa samples. The sample preparation involved\\u000a extraction of the analyte and its internal standard, 13C3-acrylamide, into water and subsequent defatting of the aqueous extract with dichloromethane. An aliquot of the resulting\\u000a aqueous

Patricia C. Aguas; Matthew J. Fitzhenry; Georgina Giannikopoulos; Peter Varelis

2006-01-01

43

Application of Uranium Isotope Dilution Mass Spectrometry in the preparation of New Certified Reference Materials  

NASA Astrophysics Data System (ADS)

Proven measurement techniques play a critical role in the preparation of Certified Reference Materials (CRMs) - those requiring high accuracy and precision in the measurement results. Isotope Dilution Mass Spectrometry (IDMS) is one such measurement method commonly used in the quantitative analysis of uranium in nuclear safeguards and isotope geology applications. In this project, we evaluated the possibility of using some of the uranium isotopic and assay CRMs made earlier by the New Brunswick laboratory as IDMS spikes to define the uranium mass fraction in future preparations of CRMs. Uranium solutions prepared from CRM 112-A (a highly pure uranium metal assay standard) and CRM 115 (a highly pure uranium oxide isotopic and assay standard) were used as spikes in the determination of uranium. Two different thermal ionization mass spectrometer instruments (MAT 261 and TRITON) were used for the isotopic measurements. Standard IDMS equation was used for data reduction to yield results for uranium mass fraction along with uncertainties, the latter calculated according to GUM. The results show that uranium mass fraction measurements can be made with the required accuracy and precision for defining the uranium concentration in new CRMs as well as in routine samples analyses.

Hasözbek, A.; Mathew, K. J.; Orlowicz, G.; Srinivasan, B.; Narayanan, U.

2012-04-01

44

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.

2011-01-01

45

Laser ablation inductively coupled plasma mass spectrometry measurement of isotope ratios in depleted uranium contaminated soils.  

PubMed

Laser ablation of pressed soil pellets was examined as a means of direct sample introduction to enable inductively coupled plasma mass spectrometry (ICP-MS) screening of soils for residual depleted uranium (DU) contamination. Differentiation between depleted uranium, an anthropogenic contaminant, and naturally occurring uranium was accomplished on the basis of measured 235U/238U isotope ratios. The amount of sample preparation required for laser ablation is considerably less than that typically required for aqueous sample introduction. The amount of hazardous laboratory waste generated is diminished accordingly. During the present investigation, 235U/238U isotope ratios measured for field samples were in good agreement with those derived from gamma spectrometry measurements. However, substantial compensation was required to mitigate the effects of impaired pulse counting attributed to sample inhomogeneity and sporadic introduction of uranium analyte into the plasma. PMID:14611049

Seltzer, Michael D

2003-09-01

46

Towards compound-independent calibration for organic compounds using online isotope dilution mass spectrometry.  

PubMed

Isotope dilution mass spectrometry (IDMS) can be considered a primary measurement method directly traceable to the International System of Units (SI). This measurement technique is increasingly employed in routine laboratories, owing to its unequalled analytical performance, precision and ease of accreditation. Unfortunately, for the adequate application of IDMS, several isotopically labelled standards, corresponding to the compounds of interest, are required. Additionally, when the enriched isotope is continuously added after a chromatographic separation, and an elemental ion source is used, it allows quantification of the different analytes being eluted from the column without requiring specific standards for each compound (online IDMS). In this article, we discuss how the traditional applicability of online IDMS for elemental speciation can be dramatically expanded by using carbon isotope tracers, oxidation or combustion reactions and a conventional molecular ion source. With such a strategy every carbon-containing compound being eluted from a chromatography system can be quantified without the need for specific standards as long as quantitative combustion/oxidation and complete elution occur. So far, only gas chromatography-combustion-mass spectrometry applications have been described, but recent results indicate the great possibilities of extending this novel approach to the quantification of organic compounds after separation by liquid chromatography. PMID:22009048

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

2012-01-01

47

A continuous flow mass spectrometry technique of argon isotope measurement for K/Ar geochronology.  

PubMed

A new method for the measurement of argon isotope composition in a continuous flow of helium for potassium/argon geochronology is described. Extraction of argon from geological samples in multiple-sample holders was carried out in a chamber by heating with a continuous Nd-YAG laser. The extracted and pre-concentrated argon is passed through a chromatographic capillary column in a flow of helium. Argon is separated from possible contaminants in the column and is injected through an open split into the ion source of an isotope ratio mass spectrometer. Measurement of the (36)Ar, (38)Ar and (40)Ar isotopes was carried out in dynamic mode, using a triple-collector ion detector. These experiments have shown that continuous flow mass spectrometry can be used for the analysis of radiogenic argon in picogram quantities with an accuracy that is satisfactory for the solution of many geochronological problems. The method of argon isotope measurement in a continuous flow of helium is an alternative to the measurement of argon isotopes in the static mode. The sensitivity and accuracy of argon measurement by this method are comparable with those provided by the classical static method. The measurement of argon isotopes in a continuous flow of helium is simpler and more reliable than measurement in the static mode. PMID:19603475

Ignatiev, Alexander V; Velivetskaya, Tatiana A; Budnitskiy, Sergey Y

2009-08-30

48

Elemental and isotopic analysis of inorganic salts by laser desorption ionization mass spectrometry  

SciTech Connect

Laser desorption ionization mass spectrometry is applied for the analysis of elements as well as their isotopic composition in different inorganic salts. At very low laser energies the inorganic ions are desorbed and ionized from the thin layer of the sample surface. The naturally occurring isotopes of alkali and silver ions are resolved using time of flight mass spectrometer. Further increase in laser energy shows the appearance of Al, Cr, and Fe ions in the mass spectra. This indicates the penetration laser beam beyond the sample surface leading to the ablation of sample target at higher energies. The simultaneous appearance of atomic ions from the sample target at relatively higher laser energies hampers the unambiguous identification of amino acid residues from the biomolecular ions in MALDI-MS.

Jayasekharan, T.; Sahoo, N. K. [Applied Spectroscopy Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India)

2013-02-05

49

Very high resolution saturation spectroscopy of lutetium isotopes via c-w single-frequency laser resonance ionization mass spectrometry  

SciTech Connect

In this paper, we discuss the use of Resonance Ionization Mass Spectrometry (RIMS) to perform isotopically selective saturation spectroscopy of lutetium isotopes. Utilizing this technique, it is shown that accurate measurements of the relative frequencies of hyperfine (HF) components for different isotopes easily can be made without the need for an isotopically enriched sample. The precision with which the HF splitting constants can be determined is estimated to be approx.5 times greater than in previous work.

Fearey, B.L.; Parent, D.C.; Keller, R.A.; Miller, C.M.

1987-01-01

50

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--discrimination of ammonium nitrate sources.  

PubMed

An evaluation was undertaken to determine if isotope ratio mass spectrometry (IRMS) could assist in the investigation of complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. The focus of the research was on ammonium nitrate (AN), a common oxidiser used in improvised explosive mixtures. The potential value of IRMS to attribute Australian AN samples to the manufacturing source was demonstrated through the development of a preliminary AN classification scheme based on nitrogen isotopes. Although the discrimination utilising nitrogen isotopes alone was limited and only relevant to samples from the three Australian manufacturers during the evaluated time period, the classification scheme has potential as an investigative aid. Combining oxygen and hydrogen stable isotope values permitted the differentiation of AN prills from three different Australian manufacturers. Samples from five different overseas sources could be differentiated utilising a combination of the nitrogen, oxygen and hydrogen isotope values. Limited differentiation between Australian and overseas prills was achieved for the samples analysed. The comparison of nitrogen isotope values from intact AN prill samples with those from post-blast AN prill residues highlighted that the nitrogen isotopic composition of the prills was not maintained post-blast; hence, limiting the technique to analysis of un-reacted explosive material. PMID:19606584

Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

2009-06-01

51

The calibration of the intramolecular nitrogen isotope distribution in nitrous oxide measured by isotope ratio mass spectrometry.  

PubMed

Two alternative approaches for the calibration of the intramolecular nitrogen isotope distribution in nitrous oxide using isotope ratio mass spectrometry have yielded a difference in the 15N site preference (defined as the difference between the delta15N of the central and end position nitrogen in NNO) of tropospheric N2O of almost 30 per thousand. One approach is based on adding small amounts of labeled 15N2O to the N2O reference gas and tracking the subsequent changes in m/z 30, 31, 44, 45 and 46, and this yields a 15N site preference of 46.3 +/- 1.4 per thousand for tropospheric N2O. The other involves the synthesis of N2O by thermal decomposition of isotopically characterized ammonium nitrate and yields a 15N site preference of 18.7 +/- 2.2 per thousand for tropospheric N2O. Both approaches neglect to fully account for isotope effects associated with the formation of NO+ fragment ions from the different isotopic species of N2O in the ion source of a mass spectrometer. These effects vary with conditions in the ion source and make it impossible to reproduce a calibration based on the addition of isotopically enriched N2O on mass spectrometers with different ion source configurations. These effects have a much smaller impact on the comparison of a laboratory reference gas with N2O synthesized from isotopically characterized ammonium nitrate. This second approach was successfully replicated and leads us to advocate the acceptance of the site preference value 18.7 +/- 2.2 per thousand for tropospheric N2O as the provisional community standard until further independent calibrations are developed and validated. We present a technique for evaluating the isotope effects associated with fragment ion formation and revised equations for converting ion signal ratios into isotopomer ratios. PMID:17216596

Westley, Marian B; Popp, Brian N; Rust, Terri M

2007-01-01

52

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.

1987-01-01

53

High-resolution quantitative imaging of mammalian and bacterial cells using stable isotope mass spectrometry  

PubMed Central

Background Secondary-ion mass spectrometry (SIMS) is an important tool for investigating isotopic composition in the chemical and materials sciences, but its use in biology has been limited by technical considerations. Multi-isotope imaging mass spectrometry (MIMS), which combines a new generation of SIMS instrument with sophisticated ion optics, labeling with stable isotopes, and quantitative image-analysis software, was developed to study biological materials. Results The new instrument allows the production of mass images of high lateral resolution (down to 33 nm), as well as the counting or imaging of several isotopes simultaneously. As MIMS can distinguish between ions of very similar mass, such as 12C15N- and 13C14N-, it enables the precise and reproducible measurement of isotope ratios, and thus of the levels of enrichment in specific isotopic labels, within volumes of less than a cubic micrometer. The sensitivity of MIMS is at least 1,000 times that of 14C autoradiography. The depth resolution can be smaller than 1 nm because only a few atomic layers are needed to create an atomic mass image. We illustrate the use of MIMS to image unlabeled mammalian cultured cells and tissue sections; to analyze fatty-acid transport in adipocyte lipid droplets using 13C-oleic acid; to examine nitrogen fixation in bacteria using 15N gaseous nitrogen; to measure levels of protein renewal in the cochlea and in post-ischemic kidney cells using 15N-leucine; to study DNA and RNA co-distribution and uridine incorporation in the nucleolus using 15N-uridine and 81Br of bromodeoxyuridine or 14C-thymidine; to reveal domains in cultured endothelial cells using the native isotopes 12C, 16O, 14N and 31P; and to track a few 15N-labeled donor spleen cells in the lymph nodes of the host mouse. Conclusion MIMS makes it possible for the first time to both image and quantify molecules labeled with stable or radioactive isotopes within subcellular compartments. PMID:17010211

Lechene, Claude; Hillion, Francois; McMahon, Greg; Benson, Douglas; Kleinfeld, Alan M; Kampf, J Patrick; Distel, Daniel; Luyten, Yvette; Bonventre, Joseph; Hentschel, Dirk; Park, Kwon Moo; Ito, Susumu; Schwartz, Martin; Benichou, Gilles; Slodzian, Georges

2006-01-01

54

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

PubMed

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp. strain Viet1; and (ii) of TCE to cis-1,2-dichloroethene (cis-DCE) in cultures of Geobacter lovleyi strain SZ were investigated. Compound-average carbon isotope effects were -19.0‰ ± 0.9‰ (PCE) and -12.2‰ ± 1.0‰ (TCE) (95% confidence intervals). Using instrumental advances in chlorine isotope analysis by continuous flow isotope ratio mass spectrometry, compound-average chorine isotope effects were measured for PCE (-5.0‰ ± 0.1‰) and TCE (-3.6‰ ± 0.2‰). In addition, position-specific kinetic chlorine isotope effects were determined from fits of reactant and product isotope ratios. In PCE biodegradation, primary chlorine isotope effects were substantially larger (by -16.3‰ ± 1.4‰ (standard error)) than secondary. In TCE biodegradation, in contrast, the product cis-DCE reflected an average isotope effect of -2.4‰ ± 0.3‰ and the product chloride an isotope effect of -6.5‰ ± 2.5‰, in the original positions of TCE from which the products were formed (95% confidence intervals). A greater difference would be expected for a position-specific reaction (chloride would exclusively reflect a primary isotope effect). These results therefore suggest that both vicinal chlorine substituents of TCE were reactive (intramolecular competition). This finding puts new constraints on mechanistic scenarios and favours either nucleophilic addition by Co(I) or single electron transfer as reductive dehalogenation mechanisms. PMID:24853618

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

2014-01-01

55

Inductively coupled plasma mass spectrometry for stable isotope metabolic tracer studies of living systems  

SciTech Connect

This dissertation focuses on the development of methods for stable isotope metabolic tracer studies in living systems using inductively coupled plasma single and dual quadrupole mass spectrometers. Sub-nanogram per gram levels of molybdenum (Mo) from human blood plasma are isolated by the use of anion exchange alumina microcolumns. Million-fold more concentrated spectral and matrix interferences such as sodium, chloride, sulfate, phosphate, etc. in the blood constituents are removed from the analyte. The recovery of Mo from the alumina column is 82 {+-} 5% (n = 5). Isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS) is utilized for the quantitative ultra-trace concentration determination of Mo in bovine and human blood samples. The average Mo concentration in reference bovine serum determined by this method is 10.2 {+-} 0.4 ng/g, while the certified value is 11.5 {+-} 1.1 ng/g (95% confidence interval). The Mo concentration of one pool of human blood plasma from two healthy male donors is 0.5 {+-} 0.1 ng/g. The inductively coupled plasma twin quadrupole mass spectrometer (ICP-TQMS) is used to measure the carbon isotope ratio from non-volatile organic compounds and bio-organic molecules to assess the ability as an alternative analytical method to gas chromatography combustion isotope ratio mass spectrometry (GC-combustion-IRMS). Trytophan, myoglobin, and {beta}-cyclodextrin are chosen for the study, initial observation of spectral interference of {sup 13}C{sup +} with {sup 12}C{sup 1}H{sup +} comes from the incomplete dissociation of myoglobin and/or {beta}-cyclodextrin.

Luong, E.

1999-05-10

56

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.

2009-01-01

57

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

SciTech Connect

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

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

2010-02-05

58

Simultaneous measurement of 13C- and 15N-isotopic enrichments of threonine by mass spectrometry.  

PubMed

Under conditions of high isotopic dilution, e.g. in a tracer study, the ability to determine accurately and quantitatively small variations in isotopic enrichments of differently labelled chemical compounds (e.g. (13)C and (15)N in threonine) in a single run by gas chromatography/mass spectrometry (GC/MS) is desirable but remains a technological challenge. Here, we report a new, rapid and simple GC/MS method for simultaneously measuring the isotopic enrichments of doubly labelled threonine ([U(13)C] and (15)N) with isotopic enrichment lower than 1.5 Molar Percent Excess (MPE). The long-term reproducibility measured was around 0.09 MPE for both tracers (throughout a 6 week period). The intra-day repeatability was lower than 0.05 and 0.06 MPE for [U(13)C]-Thr and (15)N-Thr, respectively. To calculate both isotopic enrichments, two modes of calculations were used: one based on work by Rosenblatt et al. in 1992 and the other one using a matrix approach. Both methods gave similar results (ANOVA, P >0.05) with close precision for each mode of calculation. The GC/MS method was then used to investigate the differential utilization of threonine in different organs according to its route of administration in minipigs after administration of both tracers. In plasma samples, the lowest isotopic enrichment measured between two successive time points was at 0.01 and 0.02 MPE for [U(13)C]-Thr and (15)N-Thr, respectively. Moreover, the accuracy of GC/MS (13)C-isotopic enrichment measured was validated by analyzing the same plasma samples by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Statistical analysis showed that both techniques gave the same results (ANOVA, P >0.05). This new GC/MS method offers the possibility to measure (13)C- and (15)N-isotopic enrichments with higher throughput, and using a lower amount of sample, than using GC/C/IRMS. PMID:19288537

Godin, Jean-Philippe; Mermoud, Anne-France; Rémond, Didier; Faure, Magali; Breuille, Denis; Williamson, Gary; Peré-Trepat, Emma; Ramadan, Ziad; Fay, Laurent-Bernard; Kochhar, Sunil

2009-04-01

59

Isotope-selective laser photodetachment for 129I accelerator mass spectrometry  

NASA Astrophysics Data System (ADS)

A pulsed injection-locked Ti:Sapphire laser and a negative ion laser ablation source are developed for compact accelerator mass spectrometry assisted by isotope-selective laser photodetachment. An output of about 60 mW at a repetition rate of 1 kHz is available using intracavity second-harmonic generation with a bandwidth of 20 MHz. A negative iodine ion pulse with a width of 100 ns is obtained by laser ablation of a NH4I sample. The negative ion source and the injection-locked Ti:Sapphire laser are suitable for trace analysis of 129I.

Takahashi, Tone; Tomita, Hideki; Nakayama, Motoi; Adachi, Yoshitaka; Sonnenschein, Volker; Iguchi, Tetsuo; Wendt, Klaus

2013-04-01

60

CBNM certification of Cd in polyethylene by isotope dilution mass spectrometry  

NASA Astrophysics Data System (ADS)

Four polyethylene materials have been certified for their cadmium content by isotope dilution mass spectrometry. To do so, a spike (enriched 111Cd) was characterized by reverse IDMS using high purity cadmium metal. The cadmium concentration certified in the polyethylene is 0.363, 0.676, 1.760 and 3.62 mmol kg-1 respectively (40.9, 75.9 197.9 and 407 mg kg-1 respectively). These certified materials can be used in calibrating routine methods and measurements.

Götz, A.; Lamberty, A.; de Biévre, P.

1993-01-01

61

Application of gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to detect the abuse of 17?-estradiol in cattle.  

PubMed

Although the ability to differentiate between endogenous steroids and synthetic homologues on the basis of their (13)C/(12)C isotopic ratio has been known for over a decade, this technique has been scarcely implemented for food safety purposes. In this study, a method was developed using gas chromatography-mass spectrometry/combustion/isotope ratio mass spectrometry (GC-MS/C/IRMS) to demonstrate the abuse of 17?-estradiol in cattle, by comparison of the (13)C/(12)C ratios of the main metabolite 17?-estradiol and an endogenous reference compound (ERC), 5-androstene-3?,17?-diol, in bovine urine. The intermediate precisions were determined as 0.46 and 0.26‰ for 5-androstene-3?,17?-diol and 17?-estradiol, respectively. This is, to the authors' knowledge, the first reported use of GC-MS/C/IRMS for the analysis of steroid compounds for food safety issues. PMID:23815698

Janssens, Geert; Mangelinckx, Sven; Courtheyn, Dirk; Prévost, Stéphanie; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

2013-07-31

62

Isolation and Puification of Uranium Isotopes for Measurement by Mass-Spectrometry (233, 234, 235, 236, 238U) and Alpha Spectrometry (232U)  

SciTech Connect

This report describes a standardized methodology used by researchers from the Center for Accelerator Mass Spectrometry (CAMS) (Energy and Environment Directorate) and the Environmental Radiochemistry Group (Chemistry and Materials Science Directorate) at the Lawrence Livermore National Laboratory (LLNL) for the full isotopic analysis of uranium from solution. The methodology has largely been developed for use in characterizing the uranium composition of selected nuclear materials but may also be applicable to environmental studies and assessments of public, military or occupational exposures to uranium using in-vitro bioassay monitoring techniques. Uranium isotope concentrations and isotopic ratios are measured using a combination of Multi Collector Inductively Coupled Plasma Mass Spectrometry (MC ICP-MS), Accelerator Mass Spectrometry (AMS) and Alpha Spectrometry.

Marinelli, R; Hamilton, T; Brown, T; Marchetti, A; Williams, R; Tumey, S

2006-05-30

63

Nitrogen isotopic analyses by isotope-ratio-monitoring gas chromatography/mass spectrometry  

NASA Technical Reports Server (NTRS)

Amino acids containing natural-abundance levels of 15N were derivatized and analyzed isotopically using a technique in which individual compounds are separated by gas chromatography, combusted on-line, and the product stream sent directly to an isotope-ratio mass spectrometer. For samples of N2 gas, standard deviations of ratio measurement were better than 0.1% (Units for delta are parts per thousand or per million (%).) for samples larger than 400 pmol and better than 0.5% for samples larger than 25 pmol (0.1% 15N is equivalent to 0.00004 atom % 15N). Results duplicated those of conventional, batchwise analyses to within 0.05%. For combustion of organic compounds yielding CO2/N2 ratios between 14 and 28, in particular for N-acetyl n-propyl derivatives of amino acids, delta values were within 0.25% of results obtained using conventional techniques and standard deviations were better than 0.35%. Pooled data for measurements of all amino acids produced an accuracy and precision of 0.04 and 0.23%, respectively, when 2 nmol of each amino acid was injected on column and 20% of the stream of combustion products was delivered to the mass spectrometer.

Merritt, D. A.; Hayes, J. M.

1994-01-01

64

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

NASA Astrophysics Data System (ADS)

We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS) technique for high-precision ?D and ?13C measurements of atmospheric methane on 40 mL air samples. CH4 is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve switching. Chemical agents are avoided. Trace amounts of interfering compounds can be separated by gas chromatography after pre-concentration of the CH4 sample. The fully purified sample is then either combusted to CO2 or pyrolyzed to H2 for stable isotope measurement. Apart from connecting samples and refilling liquid nitrogen as coolant the system is fully automated and allows an unobserved, continuous analysis of samples. The analytical system has been used for analysis of air samples with CH4 mixing ratios between ~100 and ~10000 ppb, for higher mixing ratios samples usually have to be diluted.

Brass, M.; Röckmann, T.

2010-05-01

65

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

NASA Astrophysics Data System (ADS)

We describe a continuous-flow isotope ratio mass spectrometry (CF-IRMS) technique for high-precision ?D and ?13C measurements of atmospheric methane on 40 mL air samples. CH4 is separated from other air components by utilizing purely physical processes based on temperature, time and mechanical valve switching. Chemical agents are avoided. Trace amounts of interfering compounds can be separated by gas chromatography after pre-concentration of the CH4 sample. The purified sample is then either combusted to CO2 or pyrolyzed to H2 for stable isotope measurement. Apart from connecting samples and refilling liquid nitrogen as coolant the system is fully automated and allows an unobserved, continuous analysis of samples. The analytical system has been used for analysis of air samples with CH4 mixing ratios between ~100 and ~10 000 ppb, for higher mixing ratios samples usually have to be diluted.

Brass, M.; Röckmann, T.

2010-12-01

66

Isolation of Pu-isotopes from environmental samples using ion chromatography for accelerator mass spectrometry and alpha spectrometry.  

PubMed

A radiochemical method for the isolation of plutonium-isotopes from environmental samples, based on the use of specific extraction chromatography resins for actinides (TEVA), Eichrom Industries, Inc.), has been set up in our laboratory and optimised for their posterior determination by alpha spectrometry (AS) or accelerator mass spectrometry (AMS). The proposed radiochemical method has replaced in our lab a well-established one based on the use of a relatively un-specific anion-exchange resin (AG) 1X8, Bio-rad Laboratories, Inc.), because it is clearly less time consuming, reduces the amounts and molarities of acid wastes produced, and reproducibly gives high radiochemical yields. In order to check the reliability of the proposed radiochemical method for the determination of plutonium-isotopes in different environmental matrixes, twin aliquots of a set of samples were prepared with TEVA and with AG 1X8 resins and measured by AS. Some samples prepared with TEVA resins were measured as well by AMS. As it is shown in the text, there is a comfortable agreement between AS and AMS, which adequately validates the method. PMID:18082656

Chamizo, E; Jiménez-Ramos, M C; Wacker, L; Vioque, I; Calleja, A; García-León, M; García-Tenorio, R

2008-01-14

67

Using theoretical protein isotopic distributions to parse small-mass-difference post-translational interactions via mass spectrometry  

PubMed Central

Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as 13C that broaden the isotopic distribution of an intact protein. Using a ZipTip™ to remove salt from proteins in preparation for high-resolution mass spectrometry, the theoretical isotopic distribution intensities calculated from the protein’s empirical formula could be fit to experimentally acquired data and used to differentiate between multiple low-mass modifications to proteins. We could readily distinguish copper from zinc bound to a single-metal superoxide dismutase (SOD1) species; copper and zinc only differ by an average mass of 1.8 Daltons and have overlapping stable isotope patterns. In addition, proteins could be directly modified while bound to the ZipTip. For example, washing 11 mM S-methyl methanethiosulfonate over the ZipTip allowed the number of free cysteines on proteins to be detected as S-methyl adducts. Alternatively, washing with the sulfhydryl oxidant diamide could quickly reestablish disulfide bridges. Using these methods, we could resolve the relative contributions of copper and zinc binding, as well as disulfide reduction to intact SOD1 protein present from <100 µg of the lumbar spinal cord of a transgenic, SOD1 overexpressing mouse. Although techniques like ICP-MS can measure total metal in solution, this is the first method able to assess the metal-binding and sulfhydryl reduction of SOD1 at the individual subunit level and is applicable to many other proteins. PMID:23247967

Rhoads, Timothy W.; Williams, Jared R.; Lopez, Nathan I.; Morre, Jeffrey T.; Bradford, C. Samuel; Beckman, Joseph S.

2014-01-01

68

Using Theoretical Protein Isotopic Distributions to Parse Small-Mass-Difference Post-Translational Modifications via Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as 13C that broaden the isotopic distribution of an intact protein. Using a ZipTip (Millipore, Billerica, MA, USA) to remove salt from proteins in preparation for high-resolution mass spectrometry, the theoretical isotopic distribution intensities calculated from the protein's empirical formula could be fit to experimentally acquired data and used to differentiate between multiple low-mass modifications to proteins. We could readily distinguish copper from zinc bound to a single-metal superoxide dismutase (SOD1) species; copper and zinc only differ by an average mass of 1.8 Da and have overlapping stable isotope patterns. In addition, proteins could be directly modified while bound to the ZipTip. For example, washing 11 mM S-methyl methanethiosulfonate over the ZipTip allowed the number of free cysteines on proteins to be detected as S-methyl adducts. Alternatively, washing with the sulfhydryl oxidant diamide could quickly reestablish disulfide bridges. Using these methods, we could resolve the relative contributions of copper and zinc binding, as well as disulfide reduction to intact SOD1 protein present from <100 ?g of the lumbar spinal cord of a transgenic, SOD1 overexpressing mouse. Although techniques like ICP-MS can measure total metal in solution, this is the first method able to assess the metal-binding and sulfhydryl reduction of SOD1 at the individual subunit level and is applicable to many other proteins.

Rhoads, Timothy W.; Williams, Jared R.; Lopez, Nathan I.; Morré, Jeffrey T.; Bradford, C. Samuel; Beckman, Joseph S.

2013-01-01

69

O Isotopic Composition of CaCO3 Measured by Continuous Flow Isotope Ratio Mass Spectrometry: Statistical Evaluation and  

E-print Network

XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3 PO4 ­ CaCO3 reactiond13 C and d18 O Isotopic Composition of CaCO3 Measured by Continuous Flow Isotope Ratio Mass the stable carbon and oxygen isotope ratios of small samples (400±20 µg) of calcium carbonate. This new

70

Carbon isotope determination for separate components of heterogeneous materials using coupled thermogravimetric analysis/isotope ratio mass spectrometry.  

PubMed

A gas-tight thermal analysis system (Netzsch STA 449C Jupiter) has been connected to an isotope ratio mass spectrometer (PDZ Europa 20-20) via an interface containing an oxidizing furnace, water trap, and gas-sampling valve. Using this system, delta(13)C has been measured for CO(2) derived from the thermal decomposition of carbonate and oxalate minerals and organic materials at temperatures that correspond to different decomposition events. There is close agreement between measured and published delta(13)C values for carbonate and oxalate minerals, which have simple decarbonation reactions on heating. Cellulose and lignin-rich materials show much more complex thermal decomposition, reflecting differences in their purity and structure, and measured delta(13)C values vary with the temperature of gas sampling. Provided that measurements are made at temperatures that correspond to the decomposition of cellulose and lignin (indicated by maximum weight loss), internally consistent data can be obtained. However, measurements for cellulose and lignin are systematically enriched in delta(13)C (by up to 1.4 per thousand) with respect to those reported for reference materials, possibly due to the slower combustion kinetics (compared with EA-IRMS). Thermogravimetric analysis/isotope ratio mass spectrometry (TG-IRMS) is ideal for materials and samples for which it is not possible to use other isotopic measurement techniques, for example because of sample heterogeneity. PMID:18348223

Manning, David A C; Lopez-Capel, Elisa; White, Maggie L; Barker, Sam

2008-04-01

71

Discrepancies between isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the  

E-print Network

for the stable isotope analysis of plant and soil waters Adam G. West1,2*, Gregory R. Goldsmith1 , Paul D. Brooks spectroscopy (IRIS) for the stable hydrogen and oxygen isotope analysis of water is increasing. While IRIS has analytical techniques for the stable isotope analysis of water has resulted in the avail- ability of several

West, Adam G.

72

Isotope dilution mass spectrometry for quantitative elemental analysis of powdered samples by radiofrequency pulsed glow discharge time of flight mass spectrometry.  

PubMed

In recent years particular effort is being devoted to the development of pulsed glow discharges (PGDs) for mass spectrometry because this powering operation mode could offer important ionization analytical advantages. However, the capabilities of radiofrequency (RF) PGD coupled to a time of flight mass spectrometry (ToFMS) for accurate isotope ratio measurements have not been demonstrated yet. This work is focused on investigating different time positions along the pulse profile for the accurate measurement of isotope ratios. As a result, a method has been developed for the direct and simultaneous multielement determination of trace elements in powdered geological samples by RF-PGD-ToFMS in combination with isotope dilution mass spectrometry (IDMS) as an absolute measurement method directly traceable to the International System of Units. Optimized operating conditions were 70 W of applied radiofrequency power, 250 Pa of pressure, 2 ms of pulse width and 4 ms of pulse period, being argon the plasma gas used. To homogeneously distribute the added isotopically-enriched standards, lithium borate fusion of powdered solid samples was used as sample preparation approach. In this way, Cu, Zn, Ba and Pb were successfully determined by RF-PGD-ToF(IDMS) in two NIST Standard Reference Materials (SRM 2586 and SRM 2780) representing two different matrices of geological interest (soil and rock samples). Cu, Zn, Ba and Pb concentrations determined by RF-PGD-ToF(IDMS) were well in agreement with the certified values at 95% confidence interval and precisions below 12% relative standard deviation were observed for three independent analyses. Elemental concentrations investigated were in the range of 81-5770 mg/kg, demonstrating the potential of RF-PGD-ToF(IDMS) for a sensitive, accurate and robust analysis of powdered samples. PMID:24054645

Alvarez-Toral, Aitor; Fernandez, Beatriz; Malherbe, Julien; Claverie, Fanny; Molloy, John L; Pereiro, Rosario; Sanz-Medel, Alfredo

2013-10-15

73

Assessment of Non-traditional Isotopic Ratios by Mass Spectrometry for Analysis of Nuclear Activities: Annual Report Year 2  

SciTech Connect

The objective of this work is to identify isotopic ratios suitable for analysis via mass spectrometry that distinguish between commercial nuclear reactor fuel cycles, fuel cycles for weapons grade plutonium, and products from nuclear weapons explosions. Methods will also be determined to distinguish the above from medical and industrial radionuclide sources. Mass spectrometry systems will be identified that are suitable for field measurement of such isotopes in an expedient manner. Significant progress has been made with this project within the past year: (1) Isotope production from commercial nuclear fuel cycles and nuclear weapons fuel cycles have been modeled with the ORIGEN and MCNPX codes. (2) MCNPX has been utilized to calculate isotopic inventories produced in a short burst fast bare sphere reactor (to approximate the signature of a nuclear weapon). (3) Isotopic ratios have been identified that are good for distinguishing between commercial and military fuel cycles as well as between nuclear weapons and commercial nuclear fuel cycles. (4) Mass spectrometry systems have been assessed for analysis of the fission products of interest. (5) A short-list of forensic ratios have been identified that are well suited for use in portable mass spectrometry systems.

Biegalski, S; Buchholz, B

2009-08-26

74

Scientific note A scientific note of an application of isotope ratio mass spectrometry  

E-print Network

methods [1, 2]. Stable isotope analysis was performed with an isotope ratio mass spectrometer (Europa with a stable isotope (D-glucose-1-13C, 99 atom % enrichment) for a period of approximately 24 h. A control cage Scien- tific, Crewe, UK) operated at the Stable Isotope Research Unit (Department of Crop and Soil Sci

Paris-Sud XI, Université de

75

Isotope pattern deconvolution-tandem mass spectrometry for the determination and confirmation of diclofenac in wastewaters.  

PubMed

Isotope dilution mass spectrometry (IDMS) based on isotope pattern deconvolution (IPD) has been applied here to MS/MS (QqQ) in order to carry out the quantification and confirmation of organic compounds in complex matrix water samples without the use of a methodological IDMS calibration graph. In this alternative approach, the isotope composition of the spiked sample is measured after fragmentation by SRM and deconvoluted into its constituting components (molar fractions of natural abundance and labeled compound) by multiple linear regression (IPD). The procedure has been evaluated for the determination of the pharmaceutical diclofenac in effluent and influent urban wastewaters and fortified surface waters by UHPLC (ESI) MS/MS using diclofenac-d(4) as labeled compound. Calculations were performed acquiring a part and the whole fragment cluster ion, achieving in all cases recoveries within 90-110% and coefficients of variation below 5% for all water samples tested. In addition, potential false negatives arising from the presence of diclofenac-d(2) impurities in the labeled compound were avoided when the proposed approach was used instead of the most usual IDMS calibration procedure. The number of SRM transitions measured was minimized to three to make possible the application of this alternative technique in routine multi-residue analysis. PMID:23410629

Castillo, Angel; Gracia-Lor, Emma; Roig-Navarro, Antoni Francesc; Vicente Sancho, Juan; Rodríguez-González, Pablo; García Alonso, J Ignacio

2013-02-26

76

A stable-isotope mass spectrometry-based metabolic footprinting approach to analyze exudates from phytoplankton.  

PubMed

Phytoplankton exudates play an important role in pelagic ecology and biogeochemical cycles of elements. Exuded compounds fuel the microbial food web and often encompass bioactive secondary metabolites like sex pheromones, allelochemicals, antibiotics, or feeding attractants that mediate biological interactions. Despite this importance, little is known about the bioactive compounds present in phytoplankton exudates. We report a stable-isotope metabolic footprinting method to characterise exudates from aquatic autotrophs. Exudates from (13)C-enriched alga were concentrated by solid phase extraction and analysed by high-resolution Fourier transform ion cyclotron resonance mass spectrometry. We used the harmful algal bloom forming dinoflagellate Alexandrium tamarense to prove the method. An algorithm was developed to automatically pinpoint just those metabolites with highly (13)C-enriched isotope signatures, allowing us to discover algal exudates from the complex seawater background. The stable-isotope pattern (SIP) of the detected metabolites then allowed for more accurate assignment to an empirical formula, a critical first step in their identification. This automated workflow provides an effective way to explore the chemical nature of the solutes exuded from phytoplankton cells and will facilitate the discovery of novel dissolved bioactive compounds. PMID:24172212

Weber, Ralf J M; Selander, Erik; Sommer, Ulf; Viant, Mark R

2013-01-01

77

A Stable-Isotope Mass Spectrometry-Based Metabolic Footprinting Approach to Analyze Exudates from Phytoplankton  

PubMed Central

Phytoplankton exudates play an important role in pelagic ecology and biogeochemical cycles of elements. Exuded compounds fuel the microbial food web and often encompass bioactive secondary metabolites like sex pheromones, allelochemicals, antibiotics, or feeding attractants that mediate biological interactions. Despite this importance, little is known about the bioactive compounds present in phytoplankton exudates. We report a stable-isotope metabolic footprinting method to characterise exudates from aquatic autotrophs. Exudates from 13C-enriched alga were concentrated by solid phase extraction and analysed by high-resolution Fourier transform ion cyclotron resonance mass spectrometry. We used the harmful algal bloom forming dinoflagellate Alexandrium tamarense to prove the method. An algorithm was developed to automatically pinpoint just those metabolites with highly 13C-enriched isotope signatures, allowing us to discover algal exudates from the complex seawater background. The stable-isotope pattern (SIP) of the detected metabolites then allowed for more accurate assignment to an empirical formula, a critical first step in their identification. This automated workflow provides an effective way to explore the chemical nature of the solutes exuded from phytoplankton cells and will facilitate the discovery of novel dissolved bioactive compounds. PMID:24172212

Weber, Ralf J. M.; Selander, Erik; Sommer, Ulf; Viant, Mark R.

2013-01-01

78

Advancement and application of gas chromatography isotope ratio mass spectrometry techniques for atmospheric trace gas analysis  

NASA Astrophysics Data System (ADS)

The use of gas chromatography isotope ratio mass spectrometry (GC-IRMS) for compound specific stable isotope analysis is an underutilized technique because of the complexity of the instrumentation and high analytical costs. However stable isotopic data, when coupled with concentration measurements, can provide additional information on a compounds production, transformation, loss, and cycling within the biosphere and atmosphere. A GC-IRMS system was developed to accurately and precisely measure delta13C values for numerous oxygenated volatile organic compounds having natural and anthropogenic sources. The OVOCs include methanol, ethanol, acetone, methyl ethyl ketone, 2-pentanone, and 3-pentanone. Guided by the requirements for analysis of trace components in air, the GC-IRMS system was developed with the goals of increasing sensitivity, reducing dead-volume and peak band broadening, optimizing combustion and water removal, and decreasing the split ratio to the IRMS. The technique relied on a two-stage preconcentration system, a low-volume capillary reactor and water trap, and a balanced reference gas delivery system. Measurements were performed on samples collected from two distinct sources (i.e. biogenic and vehicle emissions) and ambient air collected from downtown Miami and Everglades National Park. However, the instrumentation and the method have the capability to analyze a variety of source and ambient samples. The measured isotopic signatures that were obtained from source and ambient samples provide a new isotopic constraint for atmospheric chemists and can serve as a new way to evaluate their models and budgets for many OVOCs. In almost all cases, OVOCs emitted from fuel combustion were enriched in 13C when compared to the natural emissions of plants. This was particularly true for ethanol gas emitted in vehicle exhaust, which was observed to have a uniquely enriched isotopic signature that was attributed to ethanol's corn origin and use as an alternative fuel or fuel additive. Results from this effort show that ethanol's unique isotopic signature can be incorporated into air chemistry models for fingerprinting and source apportionment purposes and can be used as a stable isotopic tracer for biofuel inputs to the atmosphere on local to regional scales.

Giebel, Brian M.

79

Using Punnett Squares to Facilitate Students' Understanding of Isotopic Distributions in Mass Spectrometry  

ERIC Educational Resources Information Center

The isotopic distribution in mass spectroscopy is described for identifying pure compounds, being able to distinguish molecular fragments by masses. Punnett squares are familiar, easy to compute, and often graphical which makes helpful to students and the relative distribution of isotopic combination is easily generated for even isotopic…

Sein, Lawrence T., Jr.

2006-01-01

80

Determination of iodine in oyster tissue by isotope dilution laser resonance ionization mass spectrometry  

SciTech Connect

The technique of laser resonance ionization mass spectrometry has been combined with isotope dilution analysis to determine iodine in oyster tissue. The long-lived radioisotope, 129I, was used to spike the samples. Samples were equilibrated with the 129I, wet ashed under controlled conditions, and iodine separated by coprecipitation with silver chloride. The analyte was dried as silver ammonium iodide upon a tantalum filament from which iodine was thermally desorbed in the resonance ionization mass spectrometry instrument. A single-color, two-photon resonant plus one-photon ionization scheme was used to form positive iodine ions. Long-lived iodine signals were achieved from 100 ng of iodine. The precision of 127I/129I measurement has been evaluated by replicate determinations of the spike, the spike calibration samples, and the oyster tissue samples and was 1.0%. Measurement precision among samples was 1.9% for the spike calibration and 1.4% for the oyster tissue. The concentration of iodine determined in SRM 1566a, Oyster Tissue, was 4.44 micrograms/g with an estimate of the overall uncertainty for the analysis of +/- 0.12 microgram/g.

Fassett, J.D.; Murphy, T.J. (National Institute of Standards and Technology, Gaithersburg, MD (USA))

1990-02-15

81

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/m2.day) 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))

1991-01-01

82

Stable isotope analysis of fatty acids by gas chromatography–isotope ratio mass spectrometry  

Microsoft Academic Search

Compound-specific isotope analysis (CSIA) of fatty acids is a relatively young analytical method. However, CSIA of fatty acids has increasingly become the method of choice in areas where accurate and precise knowledge of isotopic composition at natural abundance level is important. CSIA of fatty acids at natural abundance level provides information on biogenetic and geographic origin of lipids and oils

Wolfram Meier-Augenstein

2002-01-01

83

Steroid hormone levels in pregnancy and 1 year postpartum using isotope dilution tandem mass spectrometry  

PubMed Central

Objective To establish normal, trimester-specific reference intervals for serum 17?-estradiol, progesterone (P), 17?-hydroxyprogesterone, cortisol, 11-deoxycortisol, androstenedione, DHEA, and DHEAS, measured simultaneously using isotope dilution tandem mass spectrometry. Design Sequential cohort study. Patient(s) Healthy women undergoing a normal pregnancy (age, 25–38 years; mean, 30 years) attending a prenatal well clinic at gestation weeks 12, 22, and 32 and approximately 1 year postpartum. Main Outcome Measure(s) Trimester-specific reference intervals of endogenous steroid hormones analyzed using an isotope dilution tandem mass spectrometer equipped with an atmospheric pressure photoionization source with deuterium-labeled internal standards. Result(s) Serum estradiol, P, 17?-hydroxyprogesterone, and 11-deoxycortisol increased throughout pregnancy; cortisol increased up to the second trimester and then remained steady, while androstenedione increased by 80 percent by gestation week 12, then remained constant. Serum DHEA-S decreased by 50% by the third trimester. Conclusion(s) Trimester-specific reference intervals are reported for eight serum steroids. The ratios of individual serum hormone concentrations during pregnancy relative to their 1-year postpartum concentrations illustrate the expected normal trends of changes in hormone concentrations during pregnancy. PMID:16169406

Soldin, Offie P.; Guo, Tiedong; Weiderpass, Elisabete; Tractenberg, Rochelle E.; Hilakivi-Clarke, Leena; Soldin, Steven J.

2013-01-01

84

Accelerator mass spectrometry measurement of 240Pu\\/ 239Pu isotope ratios in Novaya Zemlya and Kara Sea sediments  

Microsoft Academic Search

Generally low levels of plutonium in environmental samples, often combined with limited sample sizes, necessitate reliable low-level techniques for determination of Pu isotopes. Accelerator mass spectrometry (AMS) has proved to be a powerful method for measuring low-level Pu activity concentrations and Pu isotope ratios. Based on procedural blanks, detection limits for AMS were below 1fg Pu (equivalent to ca. 2?Bq

Deborah H Oughton; Lindis Skipperud; L. Keith Fifield; Richard G Cresswell; Brit Salbu; Philip Day

2004-01-01

85

Quantification of ferritin bound iron in human serum using species-specific isotope dilution mass spectrometry.  

PubMed

Ferritin is a hollow sphere protein composed of 24 subunits that can store up to 4500 iron atoms in its inner cavity. It is mainly found in the liver and spleen but also in serum at trace levels. Serum ferritin is considered as the best single indicator in assessing body iron stores except liver or bone marrow biopsy. However, it is confounded by other disease conditions. Ferritin bound iron (FBI) and ferritin saturation have been suggested as more robust biomarkers. The current techniques for FBI determination are limited by low antibody specificity, low instrument sensitivity and possible analyte losses during sample preparation. The need for a highly sensitive and reliable method is widely recognized. Here we describe a novel technique to detect serum FBI using species-specific isotope dilution mass spectrometry (SS-IDMS). [(57)Fe]-ferritin was produced by biosynthesis and in vitro labeling with the (57)Fe spike in the form of [(57)Fe]-citrate after cell lysis and heat treatment. [(57)Fe]-ferritin for sample spiking was further purified by fast liquid protein chromatography. Serum ferritin and added [(57)Fe]-ferritin were separated from other iron species by ultrafiltration followed by isotopic analysis of FBI using negative thermal ionization mass spectrometry. Repeatability of our assay is 8% with an absolute detection limit of 18 ng FBI in the sample. As compared to other speciation techniques, SS-IDMS offers maximum control over sample losses and species conversion during analysis. The described technique may therefore serve as a reference technique for clinical applications of FBI as a new biomarker for assessing body iron status. PMID:25008269

Ren, Yao; Walczyk, Thomas

2014-09-01

86

In vivo investigation of homocysteine metabolism to polyamines by high-resolution accurate mass spectrometry and stable isotope labeling.  

PubMed

Polyamines are essential polycations, playing important roles in mammalian physiology. Theoretically, the involvement of homocysteine in polyamine synthesis via S-adenosylmethionine is possible; however, to our knowledge, it has not been established experimentally. Here, we propose an original approach for investigation of homocysteine metabolites in an animal model. The method is based on the combination of isotope-labeled homocysteine supplementation and high-resolution accurate mass spectrometry analysis. Structural identity of the isotope-labeled metabolites was confirmed by accurate mass measurements of molecular and fragment ions and comparison of the retention times and tandem mass spectrometry fragmentation patterns. Isotope-labeled methionine, spermidine, and spermine were detected in all investigated plasma and tissue samples. The induction of moderate hyperhomocysteinemia leads to an alteration in polyamine levels in a different manner. The involvement of homocysteine in polyamine synthesis and modulation of polyamine levels could contribute to a better understanding of the mechanisms connected with homocysteine toxicity. PMID:24736325

Ruseva, Silviya; Lozanov, Valentin; Markova, Petia; Girchev, Radoslav; Mitev, Vanio

2014-07-15

87

Natural variations of Se isotopic composition determined by hydride generation multiple collector inductively coupled plasma mass spectrometry  

Microsoft Academic Search

Multiple-collector inductively coupled plasma mass spectrometry has been used for the precise measurement of the isotopic composition of Se in geological samples. Se is chemically purified before analysis by using cotton impregnated with thioglycollic acid. This preconcentration step is required for the removal of matrix-interfering elements for hydride generation, such as transitional metals, and also for the quantitative separation of

Olivier Rouxel; John Ludden; Jean Carignan; Luc Marin; Yves Fouquet

2002-01-01

88

The Determination of the Natural Abundance of the Isotopes of Chlorine: An Introductory Experiment in Mass Spectrometry.  

ERIC Educational Resources Information Center

Describes a laboratory experiment which introduces basic principles and experimental techniques of mass spectrometry for fourth year undergraduate (B.Sc.) students. Laboratory procedures, background information, and discussion of results are provided for the experiment in which the natural isotopic abundance of chlorine is determined. (Author/JN)

O'Malley, Rebecca M.

1982-01-01

89

Quantitative analysis of WRN exonuclease activity by isotope dilution mass spectrometry.  

PubMed

Werner syndrome is a disorder characterized by a premature aging phenotype. The disease is caused by mutations in the WRN gene which encodes a DNA helicase/exonuclease which is involved in multiple aspects of DNA metabolism. Current methods mostly rely on radiometric techniques to assess WRN exonuclease activity. Here we present an alternative, quantitative approach based on non-radioactive isotope dilution mass spectrometry (LC-MS/MS). A oligoduplex substrate mimicking the telomeric sequence was used for method development. Released nucleotides, which correlate with the degree of oligoduplex degradation, were dephosphorylated, purified, and quantified by LC-MS/MS. Heavy-isotope-labeled internal standards were used to account for technical variability. The method was validated in terms of reproducibility, time-course and concentration-dependency of the reaction. As shown in this study, the LC-MS/MS method can assess exonuclease activity of WRN mutants, WRN's substrate and strand specificity, and modulatory effects of WRN interaction partners and posttranslational modifications. Moreover, it can be used to analyze the selectivity and processivity of WRN exonuclease and allows the screening of small molecules for WRN exonuclease inhibitors. Importantly, this approach can easily be adapted to study nucleases other than WRN. This is of general interest, because exonucleases are key players in DNA metabolism and aging mechanisms. PMID:22766507

Mangerich, Aswin; Veith, Sebastian; Popp, Oliver; Fahrer, Jörg; Martello, Rita; Bohr, Vilhelm A; Bürkle, Alexander

2012-08-01

90

Developing new isotope-coded mass spectrometry-cleavable cross-linkers for elucidating protein structures.  

PubMed

Structural characterization of protein complexes is essential for the understanding of their function and regulation. However, it remains challenging due to limitations in existing tools. With recent technological improvements, cross-linking mass spectrometry (XL-MS) has become a powerful strategy to define protein-protein interactions and elucidate structural topologies of protein complexes. To further advance XL-MS studies, we present here the development of new isotope-coded MS-cleavable homobifunctional cross-linkers: d0- and d10-labeled dimethyl disuccinimidyl sulfoxide (DMDSSO). Detailed characterization of DMDSSO cross-linked peptides further demonstrates that sulfoxide-containing MS-cleavable cross-linkers offer robust and predictable MS2 fragmentation of cross-linked peptides, permitting subsequent MS3 analysis for simplified, unambiguous identification. Concurrent usage of these reagents provides a characteristic doublet pattern of DMDSSO cross-linked peptides, thus aiding in the confidence of cross-link identification by MS(n) analysis. More importantly, the unique isotopic profile permits quantitative analysis of cross-linked peptides and therefore expands the capability of XL-MS strategies to analyze both static and dynamic protein interactions. Together, our work has established a new XL-MS workflow for future studies toward the understanding of structural dynamics of protein complexes. PMID:24471733

Yu, Clinton; Kandur, Wynne; Kao, Athit; Rychnovsky, Scott; Huang, Lan

2014-02-18

91

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

PubMed

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

2014-02-21

92

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

PubMed

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

2013-11-15

93

High Precision Osmium Isotope Measurements Using New Generation Thermal Ionization Mass Spectrometry  

NASA Astrophysics Data System (ADS)

The technique for measuring Os isotopes to high precision (e.g. +/-30-50 ppm on the 186/188 ratio, 2 sigma) via negative thermal ionization mass spectrometry (NTIMS) was established a decade ago at the University of Maryland. Recent technical advances have resulted in the production of a new generation of TIMS that allows isotopic measurements with substantial improvement in accuracy and precision. Because of the improved capability, the new generation TIMS holds great potential to examine a variety of problems in geochemistry and cosmochemistry. Over the past 5 years, I have refined the technique for higher precision measurements of Os isotopes using the Triton TIMS from Thermo Electron. The measurements are made in static mode using 7 Faraday collectors. 70 or more nanograms of Os is loaded onto a Pt filament with barium hydroxide, the latter is an electron emitter that promotes efficient production of Os trioxide. Oxygen is bled into the source at constant pressures. Signal intensities of 120-180 mV 186Os trioxide are generated and measured as negative ions. Oxygen corrections to the raw data are made using the oxygen isotopic composition obtained for 2 ng loads of Re tetroxide measured on the Faraday cups. Multiple runs over the course of 3 years for the same lecture bottle used to bleed in oxygen to the source showed no change in the oxygen isotopic composition. Oxygen corrections are followed by instrumental mass fractionation corrections using 189/188, 192/189, or 192/188 using the exponential law. Both the internal and external precision for standard and unknown data are best when using 192/188, by a factor of 1.4 over 189/188, and 1.8 over 192/189. Replicate runs on 100 ng standard loads of a single filament shows no change in corrected values within external precision for all Os isotopic ratios over a wide range of fractionation, confirming adherence to the exponential law during emission. 39 runs for a standard solution gave +/-14 ppm (2 sigma) on the 186/188 ratio when using 192/188 of 3.083 for normalization. Technique development continues, with a goal of reducing the amount of Os measured to generate these precisions. Applications of this technique to ongoing studies include further examination of 186/188-187/188 variations in mantle-derived materials. Samples studied include Archean and Proteozoic komatiites, abyssal peridotites, plume-derived basalts, and Os-rich alloys from ultramafic portions of ophiolites. The origin of nucleosynthetic Os isotopic anomalies in meteorites, and the cosmic ray exposure effects to the Os isotopic composition of extra-terrestrial materials, are being investigated to evaluate the variation identified in a preliminary set of chondrites using the Triton.

Brandon, A.

2006-12-01

94

Testosterone Measurement by Isotope-Dilution Liquid Chromatography-Tandem Mass Spectrometry: Validation of a Method for Routine Clinical Practice  

Microsoft Academic Search

Background: Immunoassay is unsatisfactory for mea- suring the testosterone concentrations typically found in women. Bench-top tandem mass spectrometers are a viable alternative technology for measurements in the clinical laboratory. Methods: We used stable-isotope dilution liquid chro- matography-tandem mass spectrometry (ID\\/LC-MS\\/ MS) to measure testosterone in plasma and serum. The sample volume was 50 L in duplicate; preparation and analysis were

Marion L. Cawood; Helen P. Field; Clive G. Ford; Scott Gillingwater; Andrew Kicman; David Cowan; Julian H. Barth

95

Simultaneous Quantification of Steroids in Rat Intratesticular Fluid by HPLC-Isotope Dilution Tandem Mass Spectrometry  

PubMed Central

An isotope dilution mass spectrometry method has been developed for the simultaneous measurement of picolinoyl derivatives of testosterone (T), dihydrotestosterone (DHT), 17?-estradiol (E2), and 5?-androstan-3?,17?-diol (3?-diol) in rat intratesticular fluid. The method uses reversed-phase high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry. Following derivatization of 10-?L samples of testicular fluid with picolinoyl chloride hydrochloride, the samples were purified by solid phase extraction before analysis. The accuracy of the method was satisfactory for the 4 analytes at 3 concentrations, and both inter- and intraday reproducibility were satisfactory for T, DHT, and E2. Measurements of intratesticular T concentrations in a group of 8 untreated adult rats by this method correlated well with measurements of the same samples by radioimmunoassay. As in men, there was considerable rat-to-rat variability in T concentration, despite the fact that the rats were inbred. Although its levels were more than an order of magnitude lower than those of T, DHT was measured reliably in all 8 intratesticular fluid samples. DHT concentration also varied from rat to rat and was highly correlated with T levels. The levels of E2 and 3?-diol also were measurable. The availability of a sensitive method by which to measure steroids accurately and rapidly in the small volumes of intratesticular fluid obtainable from individual rats will make it possible to examine the effects, over time, of such perturbations as hormone and drug administration and environmental toxicant exposures on the intratesticular hormonal environment of exposed individual males and thereby to begin to understand differences in response between individuals. PMID:22016356

RENNE, ALISSA; LUO, LINDI; JAROW, JONATHAN; WRIGHT, WILLIAM W.; BROWN, TERRY R.; CHEN, HAOLIN; ZIRKIN, BARRY R.; FRIESEN, MARLIN D.

2014-01-01

96

Lambda genomic DNA quantification using ultrasonic treatment followed by liquid chromatography-isotope dilution mass spectrometry.  

PubMed

Quantification of genomic DNA that is traceable to the SI was performed successfully by measuring the individual nucleotides. Specifically, ultrasound was used to shear lambda genomic DNA into fragments of less than 200 base pairs, followed by deoxyribonuclease ? and phosphodiesterase ? digestion and liquid chromatography-isotope dilution mass spectrometry (LC-IDMS) quantification to estimate the mass fraction of the lambda DNA, based on the constituent deoxynucleotide monophosphates (dNMPs) within the molecule. Digital PCR (dPCR) was employed to quantify the same lambda DNA solution to provide independent data for comparing the performance of two quantitative methods. On the basis of the LC-IDMS measurement after ultrasonic treatment of the sample, the concentration of lambda DNA was 273.1 ± 9.8 ?g/g (expanded uncertainty at the 95% confidence interval). This shows good agreement with the data from dPCR. Additionally, the result calculated on the basis of the sum of the concentrations of the four dNMPs is the same as that calculated on the basis of the sequence, which indicates that knowledge of the DNA sequence and length is unnecessary to measure the total DNA concentration when applying ultrasonic treatment-LC-IDMS. PMID:22218463

Dong, Lianhua; Zang, Chao; Wang, Jing; Li, Liang; Gao, Yunhua; Wu, Liqing; Li, Peng

2012-02-01

97

Development of hemoglobin A1c certified reference material by liquid chromatography isotope dilution mass spectrometry.  

PubMed

We report the development of a National Institute of Metrology (NIM) hemoglobin A(1c) (HbA(1c)) certified reference material (CRM). Each CRM unit contains about 10 ?L of hemoglobin. Both hemoglobin and glycated hemoglobin were quantitatively determined by high-performance liquid chromatography (HPLC)-isotope dilution mass spectrometry (IDMS) with synthesized VHLTPE and glycated VHLTPE as standards. The mass fraction of synthesized VHLTPE or glycated VHLTPE was also quantitatively determined by HPLC-IDMS with NIM amino acid CRMs as standards. The homogeneity and stability of the CRMs were examined with a commercial HbA(1c) analyzer based on the HPLC principle. Fifteen units were randomly selected for homogeneity examination, and statistical analysis showed there was no inhomogeneity. Examination of the stability showed that the CRM was stable for at least 6 months at -80 °C. Uncertainty components of the balance, amino acid purity, hydrolysis and proteolysis efficiency, method reproducibility, homogeneity, and stability were taken into consideration for uncertainty evaluation. The certified value of NIM HbA(1c) CRM was expressed as the ratio of HbA(1c) to total hemoglobin in moles, and was (9.6 ± 1.9)%. The CRM can be used as a calibration or validation standard for clinical diagnostics. It is expected to improve the comparability for HbA(1c) measurement in China. PMID:22349405

Bi, Jiaming; Wu, Liqing; Yang, Bin; Yang, Yi; Wang, Jing

2012-04-01

98

Investigation of bn-44 Peptide Fragments Using High Resolution Mass Spectrometry and Isotope Labeling.  

PubMed

An N-terminal deuterohemin-containing hexapeptide (DhHP-6) was designed as a short peptide cytochrome c (Cyt c) mimetic to study the effect of N-terminal charge on peptide fragmentation pathways. This peptide gave different dissociation patterns than normal tryptic peptides. Upon collision-induced dissociation (CID) with an ion trap mass spectrometer, the singly charged peptide ion containing no added proton generated abundant and characteristic bn-44 ions instead of bn-28 (an) ions. Studies by high resolution mass spectrometry (HRMS) and isotope labeling indicate that elimination of 44 Da fragments from b ions occurs via two different pathways: (1) loss of CH3CHO (44.0262) from a Thr side chain; (2) loss of CO2 (43.9898) from the oxazolone structure in the C-terminus. A series of analogues were designed and analyzed. The experimental results combined with Density Functional Theory (DFT) calculations on the proton affinity of the deuteroporphyrin demonstrate that the production of these novel bn-44 ions is related to the N-terminal charge via a charge-remote rather than radical-directed fragmentation pathway. PMID:25280401

Wang, Bing; Yu, Jiayi; Wang, Huixin; Wei, Zhonglin; Guo, Xinhua; Xiao, Zhaohui; Zeng, Zhoufang; Kong, Wei

2014-12-01

99

Accelerator mass spectrometry measurement of 240Pu/239Pu isotope ratios in Novaya Zemlya and Kara Sea sediments.  

PubMed

Generally low levels of plutonium in environmental samples, often combined with limited sample sizes, necessitate reliable low-level techniques for determination of Pu isotopes. Accelerator mass spectrometry (AMS) has proved to be a powerful method for measuring low-level Pu activity concentrations and Pu isotope ratios. Based on procedural blanks, detection limits for AMS were below 1 fg Pu (equivalent to ca. 2 microBq 139Pu), which can compete with both TIMS, high sensitivity ICP-MS, and certainly alpha-spectrometry, while showing less interference, memory and matrix effects as compared to routine ICP-MS techniques. In addition to low detection limits, the technique offers the advantage of giving information on Pu isotope ratios. Measurements of sediments collected from dumping sites at Novaya Zemlya showed deviation from global fallout 240Pu/239Pu ratios. PMID:15177353

Oughton, Deborah H; Skipperud, Lindis; Fifield, L Keith; Cresswell, Richard G; Salbu, Brit; Day, Philip

2004-01-01

100

Isotope-ratio-monitoring gas chromatography-mass spectrometry: methods for isotopic calibration  

NASA Technical Reports Server (NTRS)

In trial analyses of a series of n-alkanes, precise determinations of 13C contents were based on isotopic standards introduced by five different techniques and results were compared. Specifically, organic-compound standards were coinjected with the analytes and carried through chromatography and combustion with them; or CO2 was supplied from a conventional inlet and mixed with the analyte in the ion source, or CO2 was supplied from an auxiliary mixing volume and transmitted to the source without interruption of the analyte stream. Additionally, two techniques were investigated in which the analyte stream was diverted and CO2 standards were placed on a near-zero background. All methods provided accurate results. Where applicable, methods not involving interruption of the analyte stream provided the highest performance (sigma = 0.00006 at.% 13C or 0.06% for 250 pmol C as CO2 reaching the ion source), but great care was required. Techniques involving diversion of the analyte stream were immune to interference from coeluting sample components and still provided high precision (0.0001 < or = sigma < or = 0.0002 at.% or 0.1 < or = sigma < or = 0.2%).

Merritt, D. A.; Brand, W. A.; Hayes, J. M.

1994-01-01

101

Validation of pentaacetylaldononitrile derivative for dual 2H gas chromatography/mass spectrometry and 13C gas chromatography/combustion/isotope ratio mass spectrometry analysis of glucose.  

PubMed

A reference method to accurately define kinetics in response to the ingestion of glucose in terms of total, exogenous and endogenous glucose is to use stable-isotope-labelled compounds such as 2H and 13C glucose followed by gas chromatography/mass spectrometry (GC/MS) and gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) analysis. The use of the usual pentaacetyl (5Ac) derivative generates difficulties in obtaining accurate and reproducible results due to the two chromatographic peaks for the syn and anti isomers, and to the isotopic effect occurring during acetylation. Therefore, the pentaacetylaldononitrile derivative (Aldo) was validated for both isotopes, and compared with the 5Ac derivative. A correction factor including carbon atom dilution (stoichiometric equation) and the kinetic isotopic effect (KIE) was determined. Analytical validation results for the 2H GC/MS and 13C GC/C/IRMS measurements produced acceptable results with both derivatives. When 2H enrichments of plasma samples were < or = 1 mol % excess (MPE), the repeatability (RSD(Aldo Intra assay and Intra day) <0.94%, RSD(5Ac Intra assay and Intra day) <3.29%), accuracy (Aldo <3.4%, 5Ac <29.0%), and stability of the derivatized samples were significantly better when the Aldo derivatives of the plasma samples were used (p < 0.05). When the glucose kinetics were assessed in nine human subjects, after glucose ingestion, the plasma glucose 2H enrichments were identical with both derivatives, whereas the 13C enrichments needed a correction factor to fit together. Due to KIE variation, this correction factor was not constant and had to be calculated for each batch of analyses, to obtain satisfactory results. Mean quantities of exogenous glucose exhibit marked difference (20.9 +/- 1.3g (5Ac) vs. 26.7 +/- 2.5g (Aldo)) when calculated with stoichiometric correction, but fit perfectly when calculated after application of the correction factor (22.1 +/- 1.3g (5Ac) vs. 22.9 +/- 1.9g (Aldo)). Finally, the pentaacetylaldononitrile derivative, used here in GC/C/IRMS for the first time, enables measurement of 2H and 13C enrichments in plasma glucose with a single sample preparation. PMID:19904737

Sauvinet, Valérie; Gabert, Laure; Qin, Du; Louche-Pélissier, Corinne; Laville, Martine; Désage, Michel

2009-12-01

102

An improved measurement of isotopic ratios by high resolution mass spectrometry.  

PubMed

The study of protein kinetics requires an accurate measurement of isotopic ratios of peptides. Although Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometers yield accurate mass measurements of analytes, the isotopologue ratios are consistently lower than predicted. Recently, we demonstrated that the magnitude of the spectral error in the FT-ICR mass spectrometer is proportional to the scan duration of ions. Here, we present a novel isotopic ratio extrapolation (IRE) method for obtaining accurate isotopic ratio measurements. Accuracy is achieved by performing scans with different duration and extrapolation of the data to the initial moment of the ion rotation; IRE minimizes the absolute isotopic ratio error to ?1%. We demonstrate the application of IRE in protein turnover studies using (2)H(2)O-metabolic labeling. Overall, this technique allows accurate measurements of the isotopic ratios of proteolytic peptides, a critical step for enabling routine studies of proteome dynamics. PMID:23283729

Ilchenko, Serguei; Previs, Stephen F; Rachdaoui, Nadia; Willard, Belinda; McCullough, Arthur J; Kasumov, Takhar

2013-02-01

103

An Improved Measurement of Isotopic Ratios by High Resolution Mass Spectrometry  

NASA Astrophysics Data System (ADS)

The study of protein kinetics requires an accurate measurement of isotopic ratios of peptides. Although Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometers yield accurate mass measurements of analytes, the isotopologue ratios are consistently lower than predicted. Recently, we demonstrated that the magnitude of the spectral error in the FT-ICR mass spectrometer is proportional to the scan duration of ions. Here, we present a novel isotopic ratio extrapolation (IRE) method for obtaining accurate isotopic ratio measurements. Accuracy is achieved by performing scans with different duration and extrapolation of the data to the initial moment of the ion rotation; IRE minimizes the absolute isotopic ratio error to ?1 %. We demonstrate the application of IRE in protein turnover studies using 2H2O-metabolic labeling. Overall, this technique allows accurate measurements of the isotopic ratios of proteolytic peptides, a critical step for enabling routine studies of proteome dynamics.

Ilchenko, Serguei; Previs, Stephen F.; Rachdaoui, Nadia; Willard, Belinda; McCullough, Arthur J.; Kasumov, Takhar

2013-02-01

104

Current perspectives of 14C-isotope measurement in biomedical accelerator mass spectrometry.  

PubMed

Accelerator mass spectrometry (AMS) is an extremely sensitive nuclear physics technique developed in the mid-70's for radiocarbon dating of historical artefacts. The technique centres round the use of a tandem Van de Graaff accelerator to generate the potential energy to permit separation of elemental isotopes at the single atom level. AMS was first used in the early 90's for the analysis of biological samples containing enriched 14C for toxicology and cancer research. Since that time biomedical AMS has been used in the study of (1) metabolism of xenobiotics in animals and humans (2) pathways of drug metabolism (3) biomarkers (4) metabolism of endogenous molecules including vitamins (5) DNA and protein binding studies and (6) clinical diagnosis. A new drug development concept which relies on the ultrasensitivity of AMS known as human microdosing (Phase 0) is being used to obtain early human metabolism information of candidate drugs arising out of discovery. These various aspects of AMS are reviewed in this article and a perspective on future applications of AMS provided. PMID:14624324

Lappin, Graham; Garner, R Colin

2004-01-01

105

Potential for using isotopically altered metalloproteins in species-specific isotope dilution analysis of proteins by HPLC coupled to inductively coupled plasma mass spectrometry.  

PubMed

The production and evaluation of an isotopically enriched metalloprotein standard for use as a calibrant in species-specific isotope dilution analysis by HPLC coupled to inductively coupled plasma mass spectrometry is described. Using a model system involving the copper-containing protein rusticyanin (Rc) from the bacterium Acido-thiobacillus ferrooxidans, it was possible to demonstrate the analytical conditions that could be used for the measurement of metalloproteins by on-line IDMS analysis. Rc was chosen because it is a well-characterized protein with an established amino acid sequence and can be produced in suitable quantities using a bacterial recombinant system. Three different forms of the protein were studied by organic and inorganic mass spectrometry: the native form of the protein containing a natural isotopic profile for copper, an isotopically enriched species containing virtually all of its copper as the 65Cu isotope, and the nonmetalated apo form. Incorporation of the copper isotopes into the apo form of the protein was determined using a UV-vis spectrophotometric assay and shown to be complete for each of the copper-containing species. The experimental conditions required to maintain the conformational form of the protein with a nonexchangeable copper center were established using +ve electrospray mass spectrometry. A pH 7.0 buffer was found to afford the most appropriate conditions, and this was then used with HPLC-ICP-MS to verify the stability of the copper center by analysis of mixtures of different isotopic solutions. No exchange of the enriched copper isotope from Rc with an added naturally abundant inorganic copper cation was observed under a neutral pH environment, indicating that species-specific ID-MS analysis of metalloproteins is possible. PMID:15987108

Harrington, Chris F; Vidler, Daniel S; Watts, Michael J; Hall, John F

2005-07-01

106

Quantification of human growth hormone by amino acid composition analysis using isotope dilution liquid-chromatography tandem mass spectrometry  

Microsoft Academic Search

We describe an accurate method for protein quantification based on conventional acid hydrolysis and an isotope dilution–HPLC–mass spectrometry (ID–HPLC–MS) method. Sample purity was confirmed using capillary zone electrophoresis, HPLC and MS. The analyte protein, human growth hormone (hGH), was effectively hydrolyzed by incubation with 8M hydrochloric acid at 130°C for 48h, where at least 1?M of hGH was treated to

Ji-Seon Jeong; Hyuk-Min Lim; Sook-Kyung Kim; Hyung-Keun Ku; Kyung-Hwa Oh; Sang-Ryoul Park

2011-01-01

107

Application of stable isotope dilution assays based on liquid chromatography–tandem mass spectrometry for the assessment of folate bioavailability  

Microsoft Academic Search

A pilot study was performed to prove the suitability of stable isotope dilution assays for assessing the bioavailability of endogenous folates in foods. By using [2H4]folic acid, [2H4]tetrahydrofolate, [2H4]5-methyltetrahydrofolate, [2H4]5-formyltetrahydrofolate and [2H4]10-formylfolic acid as internal standards, folates in spinach, apple juice and blood plasma were quantified by liquid chromatography coupled to tandem mass spectrometry. To liberate the pteroyl monoglutamates, sample

Michael Rychlik; Michael Netzel; Inga Pfannebecker; Thomas Frank; Irmgard Bitsch

2003-01-01

108

State-of-the-Art of Serum Testosterone Measurement by Isotope Dilution Liquid Chromatography Tandem Mass Spectrometry  

Microsoft Academic Search

BACKGROUND: The recent interest of clinical laborato- ries in developing serum testosterone assays based on isotope dilution-liquid chromatography-tandem mass spectrometry (ID-LC-MS\\/MS) stems from the lack of accuracy of direct immunoassays. In this study, we assessed the accuracy and state of standardization (traceability) of 4 published ID-LC-MS\\/MS proce- dures in a method comparison with an ID-gas chro- matography (GC)-MS reference measurement

Linda M. Thienpont; Katleen Van Uytfanghe; Stuart Blincko; Carol S. Ramsay; Hui Xie; Robert C. Doss; Brian G. Keevil; Laura J. Owen; Alan L. Rockwood; Mark M. Kushnir; Kelly Y. Chun; Donald W. Chandler; Helen P. Field; Patrick M. Sluss

109

Quantitation of Red Blood Cell Folates by Stable Isotope Dilution Gas Chromatography-Mass Spectrometry Utilizing a Folate Internal Standard  

Microsoft Academic Search

We report a new gas chromatography-mass spectrometry (GC-MS) method of measurement of red blood cell folates utilizing a stable isotope-labeled bacterial synthesized folate internal standard. The GC-MS method exploits the fact that the common feature of all folate molecules is a p-aminobenzoic acid moiety sandwiched between a pteridine ring and a polyglutamate chain of varying length. In this method, red

C. R. Santhoshkumar; J. C. Deutsch; K. L. Hassell; N. M. Kolhouse; J. F. Kolhouse

1995-01-01

110

Discovering Mercury Protein Modifications in Whole Proteomes Using Natural Isotope Distributions Observed in Liquid Chromatography-Tandem Mass Spectrometry  

SciTech Connect

The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury’s seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate, we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides.

Polacco, Benjamin J.; Purvine, Samuel O.; Zink, Erika M.; LaVoie, Stephen P.; Lipton, Mary S.; Summers, Anne O.; Miller, Susan M.

2011-08-01

111

Discovering mercury protein modifications in whole proteomes using natural isotope distributions observed in liquid chromatography-tandem mass spectrometry.  

PubMed

The identification of peptides that result from post-translational modifications is critical for understanding normal pathways of cellular regulation as well as identifying damage from, or exposures to xenobiotics, i.e. the exposome. However, because of their low abundance in proteomes, effective detection of modified peptides by mass spectrometry (MS) typically requires enrichment to eliminate false identifications. We present a new method for confidently identifying peptides with mercury (Hg)-containing adducts that is based on the influence of mercury's seven stable isotopes on peptide isotope distributions detected by high-resolution MS. Using a pure protein and E. coli cultures exposed to phenyl mercuric acetate, we show the pattern of peak heights in isotope distributions from primary MS single scans efficiently identified Hg adducts in data from chromatographic separation coupled with tandem mass spectrometry with sensitivity and specificity greater than 90%. Isotope distributions are independent of peptide identifications based on peptide fragmentation (e.g. by SEQUEST), so both methods can be combined to eliminate false positives. Summing peptide isotope distributions across multiple scans improved specificity to 99.4% and sensitivity above 95%, affording identification of an unexpected Hg modification. We also illustrate the theoretical applicability of the method for detection of several less common elements including the essential element, selenium, as selenocysteine in peptides. PMID:21532010

Polacco, Benjamin J; Purvine, Samuel O; Zink, Erika M; Lavoie, Stephen P; Lipton, Mary S; Summers, Anne O; Miller, Susan M

2011-08-01

112

Detailed assessment of isotope ratio infrared spectroscopy and isotope ratio mass spectrometry for the stable isotope analysis of plant and soil waters.  

PubMed

As an alternative to isotope ratio mass spectrometry (IRMS), the isotope ratio infrared spectroscopy (IRIS) approach has the advantage of low cost, continuous measurement and the capacity for field-based application for the analysis of the stable isotopes of water. Recent studies have indicated that there are potential issues of organic contamination of the spectral signal in the IRIS method, resulting in incorrect results for leaf samples. To gain a more thorough understanding of the effects of sample type (e.g., leaf, root, stem and soil), sample species, sampling time and climatic condition (dry vs. wet) on water isotope estimates using IRIS, we collected soil samples and plant components from a number of major species at a fine temporal resolution (every 2?h for 24-48?h) across three locations with different climatic conditions in the Heihe River Basin, China. The hydrogen and oxygen isotopic compositions of the extracted water from these samples were measured using both an IRMS and an IRIS instrument. The results show that the mean discrepancies between the IRMS and IRIS approaches for ?(18) O and ?D, respectively, were: -5.6‰ and -75.7‰ for leaf water; -4.0‰ and -23.3‰ for stem water; -3.4‰ and -28.2‰ for root water; -0.5‰ and -6.7‰ for xylem water; -0.06‰ and -0.3‰ for xylem flow; and -0.1‰ and 0.3‰ for soil water. The order of the discrepancy was: leaf > stem ? root > xylem > xylem flow ? soil. In general, species of the same functional types (e.g., woody vs. herbaceous) within similar habitats showed similar deviations. For different functional types, the differences were large. Sampling at nighttime did not remove the observed deviations. PMID:21953962

Zhao, Liangju; Xiao, Honglang; Zhou, Jian; Wang, Lixin; Cheng, Guodong; Zhou, Maoxian; Yin, Li; McCabe, Matthew F

2011-10-30

113

DETERMINATION OF 237NP AND PU ISOTOPES IN LARGE SOIL SAMPLES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY  

SciTech Connect

A new method for the determination of {sup 237}Np and Pu isotopes in large soil samples has been developed that provides enhanced uranium removal to facilitate assay by inductively coupled plasma mass spectrometry (ICP-MS). This method allows rapid preconcentration and separation of plutonium and neptunium in large soil samples for the measurement of {sup 237}Np and Pu isotopes by ICP-MS. {sup 238}U can interfere with {sup 239}Pu measurement by ICP-MS as {sup 238}UH{sup +} mass overlap and {sup 237}Np via {sup 238}U peak tailing. The method provides enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then transferring Pu to DGA resin for additional purification. The decontamination factor for removal of uranium from plutonium for this method is greater than 1 x 10{sup 6}. Alpha spectrometry can also be applied so that the shorter-lived {sup 238}Pu isotope can be measured successfully. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu and {sup 238}Pu were measured by alpha spectrometry.

Maxwell, S.

2010-07-26

114

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

PubMed

Isotope ratio mass spectrometry (IRMS) testing is performed to determine if an atypical steroid profile is due to administration of an endogenous steroid. Androsterone (Andro) and etiocholanolone (Etio), and/or the androstanediols (5?- and 5?-androstane-3?,17?-diol) are typically analyzed by IRMS to determine the (13) C/(12) C ratio. The ratios of these target compounds are compared to the (13) C/(12) C ratio of an endogenous reference compound (ERC) such as 5?-pregnane-3?,20?-diol (Pdiol). Concentrations of Andro and Etio are high so (13) C/(12) C ratios can easily be measured in most urine samples. Despite the potentially improved sensitivity of the androstanediols for detecting the use of some testosterone formulations, additional processing steps are often required that increase labour costs and turnaround times. Since this can be problematic when performing large numbers of IRMS measurements, we established thresholds for Andro and Etio that can be used to determine the need for additional androstanediol testing. Using these criteria, 105 out of 2639 urine samples exceeded the Andro and/or Etio thresholds, with 52 of these samples being positive based on Andro and Etio IRMS testing alone. The remaining 53 urine samples had androstanediol IRMS testing performed and 3 samples were positive based on the androstanediol results. A similar strategy was used to establish a threshold for Pdiol to identify athletes with relatively (13) C-depleted values so that an alternative ERC can be used to confirm or establish a true endogenous reference value. Adoption of a similar strategy by other laboratories can significantly reduce IRMS sample processing and analysis times, thereby increasing testing capacity. PMID:23303562

Ahrens, Brian D; Butch, Anthony W

2013-07-01

115

Development of criteria for the detection of adrenosterone administration by gas chromatography-mass spectrometry and gas chromatography-combustion-isotope ratio mass spectrometry for doping control.  

PubMed

Adrenosterone (androst-4-ene-3,11,17-trione, 11-oxoandrostenedione) is an endogenous steroid hormone that has been promoted as a dietary supplement capable of reducing body fat and increasing muscle mass. It is proposed that adrenosterone may function as an inhibitor of the 11beta-hydroxysteroid dehydrogenase type 1 enzyme (11beta-HSD1), which is primarily responsible for reactivation of cortisol from cortisone. The urinary metabolism of adrenosterone was investigated, after a single oral administration in two male subjects, by gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Substantially increased excretion of 11beta-hydroxyandrosterone, 11beta-hydroxyetiocholanolone, 11-oxoandrosterone and 11-oxoetiocholanolone was observed. Minor metabolites such as 3alpha,17beta-dihydroxy-5beta-androstan-11-one, 3alpha-hydroxyandrost-4-ene-11,17-dione and 3alpha,11beta-dihydroxyandrost-4-en-17-one were also identified. The exogenous origin of the most abundant adrenosterone metabolites was confirmed by GC-C-IRMS according to World Anti-Doping Agency criteria. Through analysis of a reference population data set obtained from urine samples provided by elite athlete volunteers (n = 85), GC-MS doping control screening criteria are proposed: 11beta-hydroxyandrosterone concentration greater than 10 000 ng/mL (specific gravity adjusted to 1.020) or 11beta-hydroxyandrosterone/11beta-hydroxyetiocholanolone ratio greater than 20.Urine samples fulfilling these screening criteria may be subjected to GC-C-IRMS analysis for confirmation of adrenosterone administration. PMID:20355175

Brooker, Lance; Parr, Maria Kristina; Cawley, Adam; Flenker, Ulrich; Howe, Christopher; Kazlauskas, Rymantas; Schänzer, Wilhelm; George, Adrian

2009-11-01

116

Isotopic Tracing of Fuel Components in Particulate Emissions from Diesel Engines using Accelerator Mass Spectrometry (AMS)  

SciTech Connect

Accelerator mass spectrometry (AMS) is an isotope-ratio measurement technique developed in the late 1970s for tracing long-lived radioisotopes (e.g., {sup 14}C half life = 5760 y). The technique counts individual nuclei rather than waiting for their radioactive decay, allowing measurement of more than 100 low-level {sup 14}C samples per day (Vogel et al, 1995). The LLNL AMS system is shown in Fig.1. The contemporary quantity of {sup 14}C in living things ({sup 14}C/C = 1.2 x 10{sup -12} or 110 fmol {sup 14}C/ g C) is highly elevated compared to the quantity of {sup 14}C in petroleum-derived products. This isotopic elevation is sufficient to trace the fate of bio-derived fuel components in the emissions of an engine without the use of radioactive materials. If synthesis of a fuel component from biologically-derived source material is not feasible, another approach is to purchase {sup 14}C-labeled material (e.g., dibutyl maleate (DBM)) and dilute it with petroleum-derived material to yield a contemporary level of {sup 14}C. In each case, the virtual absence of {sup 14}C in petroleum based fuels gives a very low {sup 14}C background that makes this approach to tracing fuel components practical. Regulatory pressure to significantly reduce the particulate emissions from diesel engines is driving research into understanding mechanisms of soot formation. If mechanisms are understood, then combustion modeling can be used to evaluate possible changes in fuel formulation and suggest possible fuel components that can improve combustion and reduce PM emissions. The combustion paradigm assumes that large molecules break down into small components and then build up again during soot formation. AMS allows us to label specific fuel components, including oxygenates, trace the carbon atoms, and test this combustion modeling paradigm. Volatile and non-volatile organic fractions (VOF, NVOF) in the PM can be further separated. The VOF of the PM can be oxidized with catalysts in the exhaust stream to further decrease PM. The effectiveness of exhaust stream catalysts to oxidize products from tracer fuel components can be monitored through AMS measurement of carbon in PM. The objects of this report are: (1) Determine contribution of diesel fuel components and oxygenates to soot formation; (2) Separate volatile and non-volatile fractions of soot; (3) Test combustion paradigm that all carbon and oxygen in fuel is equal; and (4) Produce data to validate combustion modeling.

Buchholz, B A; Mueller, C J; Garbak, J.

2001-08-02

117

Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry  

USGS Publications Warehouse

An anomalous stable hydrogen isotopic fractionation of 4 ??? in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ??2H reproducibility (1?? standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1 ??? to 0.58 ???. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen. ?? This article not subject to U.S. Copyright. Published 2010 by the American Chemical Society.

Coplen, T.B.; Qi, H.

2010-01-01

118

Caution on the use of liquid nitrogen traps in stable hydrogen isotope-ratio mass spectrometry  

USGS Publications Warehouse

An anomalous stable hydrogen isotopic fractionation of 4 ‰ in gaseous hydrogen has been correlated with the process of adding liquid nitrogen (LN2) to top off the dewar of a stainless-steel water trap on a gaseous hydrogen-water platinum equilibration system. Although the cause of this isotopic fractionation is unknown, its effect can be mitigated by (1) increasing the capacity of any dewars so that they do not need to be filled during a daily analytic run, (2) interspersing isotopic reference waters among unknowns, and (3) applying a linear drift correction and linear normalization to isotopic results with a program such as Laboratory Information Management System (LIMS) for Light Stable Isotopes. With adoption of the above guidelines, measurement uncertainty can be substantially improved. For example, the long-term (months to years) ?2H reproducibility (1& sigma; standard deviation) of nine local isotopic reference waters analyzed daily improved substantially from about 1‰ to 0.58 ‰. This isotopically fractionating mechanism might affect other isotope-ratio mass spectrometers in which LN2 is used as a moisture trap for gaseous hydrogen

Coplen, Tyler B.; Qi, Haiping

2010-01-01

119

Ion microscopy with resonant ionization mass spectrometry : time-of-flight depth profiling with improved isotopic precision.  

SciTech Connect

There are four generally mutually exclusive requirements that plague many mass spectrometric measurements of trace constituents: (1) the small size (limited by the depth probed) of many interesting materials requires high useful yields to simply detect some trace elements, (2) the low concentrations of interesting elements require efficient discrimination from isobaric interferences, (3) it is often necessary to measure the depth distribution of elements with high surface and low bulk contributions, and (4) many applications require precise isotopic analysis. Resonant ionization mass spectrometry has made dramatic progress in addressing these difficulties over the past five years.

Pellin, M. J.; Veryovkin, I. V.; Levine, J.; Zinovev, A.; Davis, A. M.; Stephan, T.; Tripa, C. E.; King, B. V.; Savina, M. R. (Materials Science Division); (Chicago Center Cosmochemistry); (Univ. of Chicago); (Univ.of Newcastle)

2010-01-01

120

Evaluation of the 34S/32S ratio of Soufre de Lacq elemental sulfur isotopic reference material by continuous flow isotope-ratio mass spectrometry  

USGS Publications Warehouse

Soufre de Lacq elemental sulfur reference material (IAEA-S-4) isotopically is homogeneous in amounts as small as 41 ??g as determined by continuous flow isotope-ratio mass spectrometry. The ??34S value for this reference material is +16.90 ?? 0.12??? (1??) on a scale (Vienna Can??on Diablo troilite, VCDT) where IAEA-S-1 Ag2S is -0.3??? and IAEA-S-2 Ag2S is +22.67???. Published by Elsevier Science B.V.

Qi, H.P.; Coplen, T.B.

2003-01-01

121

Oxygen isotopic measurements by secondary ion mass spectrometry in uranium oxide microparticles: a nuclear forensic diagnostic.  

PubMed

To exploit oxygen isotopic measurement by SIMS as a diagnostic tool in nuclear forensics, the magnitude and reproducibility of 0-isotope instrumental mass discrimination for O-isotope standards in the SIMS laboratory at the Institute for Transuranium Elements has been evaluated. Tests for matrix-dependent discrimination effects on three different O-isotope standards with substantially different matrix compositions have been performed. The results were checked by an interlaboratory comparison of O-isotope discrimination with those obtained in the SIMS laboratory at the Lawrence Livermore National Laboratory on two standards. The results from the two laboratories are in very good agreement, indicating statistically indistinguishable instrumental mass discrimination factors for 180/160 ratios on the Cameca 6f and 3f, when the analyses are performed under the experimental conditions described. The 2sigma(mean) uncertainties of these factors are in the range of 0.3-0.9%. In accordance with the tested methodology, 0-isotope compositions were measured in three particulate uranium oxide samples of nuclear forensics interest. PMID:12498207

Tamborini, G; Phinney, D; Blidstein, O; Betti, M

2002-12-01

122

Improved isotope ratio measurement performance in liquid chromatography/isotope ratio mass spectrometry by removing excess oxygen.  

PubMed

A low dead volume oxygen scrubbing system was introduced in a commercially available liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) interface to enhance the analytical capability of the system. In the LC/IRMS interface carbon from organic samples is converted into CO(2) inside the mobile phase by wet chemical oxidation using peroxodisulfate (Na(2)S(2)O(8)). After passing the hot reaction zone, surplus oxygen (O(2)) remains dissolved in the liquid phase. Both CO(2) and O(2) diffuse through a transfer membrane into the helium carrier and are transferred to the mass spectrometer. The presence of O(2) in the ion source may have detrimental effects on measurement accuracy and precision as well as on filament lifetime. As a remedy, a new on-line O(2)-removing device has been incorporated into the system. The new O(2) scrubber consists of two parallel hot copper reduction reactors (0.8 mm i.d., active length 120 mm) and a switch-over valve between them. One reactor is regenerated using He/H(2) while the other is actively scavenging O(2) from the gas stream. The capacity of each reduction reactor, expressed as usage time, is between 40 and 50 min. This is sufficient for a single LC run for sugars and organic acids. A further increase of the reduction capacity is accompanied by a peak broadening of about 100%. After switching to a freshly reduced reactor the oxygen background and the delta(13)C values of the reference gas need up to 500 s to stabilize. For repeated injections the delta(13)C values of sucrose remain constant (+/-0.1 per thousand) for about 3000 s. The long-term stability for measurements of sucrose was 0.11 per thousand without the reduction oven and improved slightly to 0.08 per thousand with the reduction oven. The filament lifetime improved by more than 600%, thereby improving the long-term system stability and analytical efficiency. In addition the costs per analysis were reduced considerably. PMID:18041012

Hettmann, Elena; Brand, Willi A; Gleixner, Gerd

2007-01-01

123

Innovations in Mass Spectrometry for Precise and Accurate Isotope Ratio Determination from Very Small Analyte Quantities (Invited)  

NASA Astrophysics Data System (ADS)

This presentation describes progress in mass spectrometry for analysing very small analyte quantities, illustrated by example applications from nuclear forensics. In this challenging application, precise and accurate (‰) uranium isotope ratios are required from 1 - 2 µm diameter uranium oxide particles, which comprise less than 40 pg of uranium. Traditionally these are analysed using thermal ionisation mass spectrometry (TIMS), and more recently using secondary ionisation mass spectrometry (SIMS). Multicollector inductively-coupled plasma mass spectrometry (MC-ICP-MS) can offer higher productivity compared to these techniques, but is traditionally limited by low efficiency of analyte utilisation (sample through to ion detection). Samples can either be introduced as a solution, or sampled directly from solid using laser ablation. Large multi-isotope ratio datasets can help identify provenance and intended use of anthropogenic uranium and other nuclear materials [1]. The Thermo Scientific NEPTUNE Plus (Bremen, Germany) with ‘Jet Interface’ option offers unparalleled MC-ICP-MS sensitivity. An analyte utilisation of c. 4% has previously been reported for uranium [2]. This high-sensitivity configuration utilises a dry high-capacity (100 m3/h) interface pump, special skimmer and sampler cones and a desolvating nebuliser system. Coupled with new acquisition methodologies, this sensitivity enhancement makes possible the analysis of micro-particles and small sample volumes at higher precision levels than previously achieved. New, high-performance, full-size and compact discrete dynode secondary electron multipliers (SEM) exhibit excellent stability and linearity over a large dynamic range and can be configured to simultaneously measure all of the uranium isotopes. Options for high abundance-sensitivity filters on two ion beams are also available, e.g. for 236U and 234U. Additionally, amplifiers with high ohm (1012 - 1013) feedback resistors have been developed to optimise signal to noise ratios from low ion beam intensities on Faraday cups [2,3]. Data will be presented from the Thermo Scientific NEPTUNE Plus MC-ICP-MS, sampling sub-nanogram quantities of analyte from solution and by laser ablation. Faraday only measurements of sub-microgram analyte quantities will also be presented, using a 1012 ? amplifier for the minor isotope 234U. These data are compared to a dataset collected by a first generation MC-ICP-MS instrument, reported by Lloyd et al. [1]. [1] N. S. Lloyd, R. R. Parrish, M. S. A. Horstwood & S. R. N. Chenery, Journal of Analytical Atomic Spectrometry 24 (6), 752 (2009). [2] C. Bouman, J.B. Schwieters, M. Deerberg & D. Tuttas, Geochimica et Cosmochimica Acta 73 (13, Supplement 1) (2009). [3] D. Tuttas, J.B. Schwieters, & N.S. Lloyd, Geochimica et Cosmochimica Acta 74 (11, Supplement 1) (2010).

Lloyd, N. S.; Bouman, C.; Horstwood, M. S.; Parrish, R. R.; Schwieters, J. B.

2010-12-01

124

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

USGS Publications Warehouse

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

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

2011-01-01

125

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

SciTech Connect

Resonance Ionization Mass Spectrometry (RIMS) has been developed as a method to measure relative uranium isotope abundances. In this approach, RIMS is used as an element-selective ionization process to provide a distinction between uranium atoms and potential isobars without the aid of chemical purification and separation. We explore the laser parameters critical to the ionization process and their effects on the measured isotope ratio. Specifically, the use of broad bandwidth lasers with automated feedback control of wavelength was applied to the measurement of {sup 235}U/{sup 238}U ratios to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a 3-color, 3-photon ionization process from a bandwidth of 1.8 GHz to about 10 GHz, the variation in sequential relative isotope abundance measurements decreased from >10% to less than 0.5%. This procedure was demonstrated for the direct interrogation of uranium oxide targets with essentially no sample preparation. A rate equation model for predicting the relative ionization probability has been developed to study the effect of variation in laser parameters on the measured isotope ratio. This work demonstrates that RIMS can be used for the robust measurement of uranium isotope ratios.

Isselhardt, B H

2011-09-06

126

Simplified absolute metabolite quantification by gas chromatography-isotope dilution mass spectrometry on the basis of commercially available source material.  

PubMed

In the field of metabolomics, GC-MS has rather established itself as a tool for semi-quantitative strategies like metabolic fingerprinting or metabolic profiling. Absolute quantification of intra- or extracellular metabolites is nowadays mostly accomplished by application of diverse LC-MS techniques. Only few groups have so far adopted GC-MS technology for this exceptionally challenging task. Besides numerous and deeply investigated problems related to sample generation, the pronounced matrix effects in biological samples have led to the almost mandatory application of isotope dilution mass spectrometry (IDMS) for the accurate determination of absolute metabolite concentrations. Nevertheless, access to stable isotope labeled internal standards (ILIS), which are in many cases commercially unavailable, is quite laborious and very expensive. Here we present an improved and simplified gas chromatography-isotope dilution mass spectrometry (GC-IDMS) protocol for the absolute determination of intra- and extracellular metabolite levels. Commercially available (13)C-labeled algal cells were used as a convenient source for the preparation of internal standards. Advantages as well as limitations of the described method are discussed. PMID:22100557

Vielhauer, Oliver; Zakhartsev, Maksim; Horn, Thomas; Takors, Ralf; Reuss, Matthias

2011-12-15

127

Quantitative biomedical mass spectrometry  

NASA Astrophysics Data System (ADS)

The scope of this contribution is an illustration of the capabilities of isotope dilution mass spectrometry (IDMS) for quantification of target substances in the biomedical field. After a brief discussion of the general principles of quantitative MS in biological samples, special attention will be paid to new technological developments or trends in IDMS from selected examples from the literature. The final section will deal with the use of IDMS for accuracy assessment in clinical chemistry. Methodological aspects considered crucial for avoiding sources of error will be discussed.

de Leenheer, Andrép; Thienpont, Linda M.

1992-09-01

128

The use of stable isotopes and gas chromatography/mass spectrometry in the identification of steroid metabolites in the equine  

SciTech Connect

Stable isotope gas chromatography/mass spectrometry has been used successfully in the elucidation of structures of urinary steroid metabolites in the horse and in the identification of metabolites isolated from in vivo perfusion and in vitro incubation studies using equine tissue preparations. Deuterium-labeled steroids, testosterone, dehydroepiandrosterone, and 5-androstene-3 beta,17 beta-diol have been synthesized by base-catalyzed isotope exchange methods and the products characterized by gas chromatography/mass spectrometry. (16,16(-2)H2)Dehydroepiandrosterone (plus radiolabeled dehydroepiandrosterone) was perfused into a testicular artery of a pony stallion and was shown to be metabolized into 2H2-labeled testosterone, 4-androstenedione, isomers of 5-androstene-3,17-diol, 19-hydroxytestosterone, and 19-hydroxy-4-androstenedione. In further studies, equine testicular minces have been incubated with 2H2-labeled and radiolabeled dehydroepiandrosterone and 5-androstene-3 beta, 17 beta-diol. The metabolites, whose identity was confirmed by stable isotope gas chromatography/mass spectrometry, proved the interconversion of the two substrates, as well as formation of testosterone and 4-androstenedione. The aromatization of dehydroepiandrosterone was also confirmed, together with the formation of an isomer of 5(10)-estrene-3,17-diol from both substrates showing 19-demethylation without concomitant aromatization. In studies of the feto-placental unit, the allantochorion was shown to aromatize (2H5)testosterone to (2H4)estradiol, the loss of one 2H from the substrate being consistent with aromatization of the A ring. The formation of 6-hydroxyestradiol was also confirmed in this study. The same technique has been valuable in determining the structure of two metabolites of nandrolone isolated from horse urine.

Houghton, E.; Dumasia, M.C.; Teale, P.; Smith, S.J.; Cox, J.; Marshall, D.; Gower, D.B. (Horseracing Forensic Laboratory, Newmarket, Suffolk (England))

1990-10-01

129

Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry  

SciTech Connect

The isotopic composition of nanogram quantities of osmium was measured by using an inductively coupled plasma source mass spectrometer. Sensitivity was enhanced a factor of approx.100 by the use of an osmium tetraoxide vapor generator rather than nebulization of solution. For samples less than or equal to5 ng, the ratios /sup 190/Os//sup 192/Os, /sup 189/Os//sup 192/Os, and /sup 188/Os//sup 192/Os were determined to better than +/- 0.5% (1sigma/sub m/) precision. For the minor isotopes, the ratios /sup 187/Os//sup 192/Os and /sup 186/Os//sup 192/Os were determined to +/-1%, and /sup 184/Os//sup 192/Os (4 x 10/sup -4/) was determined to approx.10%. Isotope ratios for common osmium are reported.

Russ, G.P. III; Bazan, J.M.; Date, A.R.

1987-04-01

130

Stable Isotope Analyses of water and Aqueous Solutions by Conventional Dual-inlet Mass Spectrometry  

SciTech Connect

The foundation of various analytical methods for the stable isotope composition of water and other aqueous samples (natural abundance, {sup 1}H : {sup 2}H (D) = 99.985 : 0.015 atom%, and {sup 16}O : {sup 17}O : {sup 18}O = 99.762 : 0.038 : 0.200 atom%) was established during the Manhatten Project in the U.S.A., when large amounts of heavy water were produced for nuclear reactors (see Kirshenbaum, 1951, for a detailed account). From early on, there was great interest in the oxygen and hydrogen isotopic compositions of water, because they are the ideal tracers of water sources and reactions. The increased analytical precisions made possible by the subsequent development of modern gas-source isotope-ratio mass spectrometers with dual-inlets and multi-collectors, have caused the proliferation of new analytical methods and applications for the oxygen and hydrogen isotopic compositions of water. These stable isotopes have found wide applications in basic as well as applied sciences (chemistry, geology, hydrology, biology, medical sciences, and food sciences). This is because water is ubiquitous, is an essential and predominant ingredient of living organisms, and is perhaps the most reactive compound in the Earth.

Horita, Juske [ORNL; Kendall, C. [U.S. Geological Survey, Menlo Park, CA

2004-01-01

131

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--preliminary study on TATP and PETN.  

PubMed

The application of isotopic techniques to investigations requiring the provision of evidence to a Court is limited. The objective of this research was to investigate the application of light stable isotopes and isotope ratio mass spectrometry (IRMS) to solve complex forensic cases by providing a level of discrimination not achievable utilising traditional forensic techniques. Due to the current threat of organic peroxide explosives, such as triacetone triperoxide (TATP), research was undertaken to determine the potential of IRMS to differentiate samples of TATP that had been manufactured utilising different starting materials and/or manufacturing processes. In addition, due to the prevalence of pentaerythritoltetranitrate (PETN) in detonators, detonating cord, and boosters, the potential of the IRMS technique to differentiate PETN samples from different sources was also investigated. Carbon isotope values were measured in fourteen TATP samples, with three definite groups appearing in the initial sample set based on the carbon data alone. Four additional TATP samples (in a second set of samples) were distinguishable utilising the carbon and hydrogen isotopic compositions individually, and also in combination with the oxygen isotope values. The 3D plot of the carbon, oxygen and hydrogen data demonstrated the clear discrimination of the four samples of TATP. The carbon and nitrogen isotope values measured from fifteen PETN samples, allowed samples from different sources to be readily discriminated. This paper demonstrates the successful application of IRMS to the analysis of explosives of forensic interest to assist in discriminating samples from different sources. This research represents a preliminary evaluation of the IRMS technique for the measurement of stable isotope values in TATP and PETN samples, and supports the dedication of resources for a full evaluation of this application in order to achieve Court reportable IRMS results. PMID:19606585

Benson, Sarah J; Lennard, Christopher J; Maynard, Philip; Hill, David M; Andrew, Anita S; Roux, Claude

2009-06-01

132

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

Microsoft Academic Search

Determination of zinc involved spiking with 68Zn enriched solution, digestion by HNO3+H2O2 in microwave decomposition unit, off-line separation of zinc on Chelex-100 column and measurement of (64Zn+66Zn)\\/68Zn 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 ?g g?1 for the

Oto Mestek; Jana Kom??nková; Richard Kopl??k; Miloslav Suchánek

2001-01-01

133

Application of Inductively Coupled Plasma Mass Spectrometry to the determination of uranium isotope ratios in individual particles for nuclear safeguards  

NASA Astrophysics Data System (ADS)

The capability of inductively coupled plasma mass spectrometry (ICP-MS) for the determination of uranium isotope ratios in individual particles was determined. For this purpose, we developed an experimental procedure including single particle transfer with a manipulator, chemical dissolution and isotope ratio analysis, and applied to the analysis of individual uranium particles in certified reference materials (NBL CRM U050 and U350). As the result, the 235U/ 238U isotope ratio for the particle with the diameter between 0.5 and 3.9 ?m was successfully determined with the deviation from the certified ratio within 1.8%. The relative standard deviation (R.S.D.) of the 235U/ 238U isotope ratio was within 4.2%. Although the analysis of 234U/ 238U and 236U/ 238U isotope ratios gave the results with inferior precision, the R.S.D. within 20% was possible for the measurement of the particle with the diameter more than 2.1 ?m. The developed procedure was successfully applied to the analysis of a simulated environmental sample prepared from a mixture of indoor dust (NIST SRM 2583) and uranium particles (NBL CRM U050, U350 and U950a). From the results, the proposed procedure was found to be an alternative analytical tool for nuclear safeguards.

Zhang, Xiao Zhi; Esaka, Fumitaka; Esaka, Konomi T.; Magara, Masaaki; Sakurai, Satoshi; Usuda, Shigekazu; Watanabe, Kazuo

2007-10-01

134

Acquisition and processing of data for isotope-ratio-monitoring mass spectrometry  

NASA Technical Reports Server (NTRS)

Methods are described for continuous monitoring of signals required for precise analyses of 13C, 18O, and 15N in gas streams containing varying quantities of CO2 and N2. The quantitative resolution (i.e. maximum performance in the absence of random errors) of these methods is adequate for determination of isotope ratios with an uncertainty of one part in 10(5); the precision actually obtained is often better than one part in 10(4). This report describes data-processing operations including definition of beginning and ending points of chromatographic peaks and quantitation of background levels, allowance for effects of chromatographic separation of isotopically substituted species, integration of signals related to specific masses, correction for effects of mass discrimination, recognition of drifts in mass spectrometer performance, and calculation of isotopic delta values. Characteristics of a system allowing off-line revision of parameters used in data reduction are described and an algorithm for identification of background levels in complex chromatograms is outlined. Effects of imperfect chromatographic resolution are demonstrated and discussed and an approach to deconvolution of signals from coeluting substances described.

Ricci, M. P.; Merritt, D. A.; Freeman, K. H.; Hayes, J. M.

1994-01-01

135

Water-induced errors in continuous-flow carbon isotope ratio mass spectrometry.  

PubMed

Formation of HCO2+ from CO2 and background H2O in isotope ratio mass spectrometers has been examined in detail. The process is troublesome because its product is not resolved from 13C16O2+. The resulting, artifactual enhancement of the mass 45 ion current (and analogous enhancement of the mass 46 ion current by transfer of hydrogen to mass 45 species) can cause systematic errors in analyses of 13C based on measurement of ion current ratios in the mass spectrum of CO2. Such errors are neutralized when isotopic analyses are based on differential comparisons in which ion currents and background water levels are precisely equal during admission and ionization of both sample and standard gases. In continuous-flow systems, however, that requirement is generally not met. The resulting systematic error is proportional to the 18/44 ion current ratio. When the widely used MAT252 mass spectrometer is tuned to yield maximum sensitivity, the constant of proportionality is 26 +/- 2/1000 (i.e., the error will be 0.26/1000 if the mass 18 ion current is 100 times smaller than that at mass 44). Errors can be reduced 5-fold when the ion-source residence time of CO2+ is decreased by use of stronger ion-extraction potential gradients. Under those same conditions, sensitivity is decreased by 60%. For operation at highest sensitivity, carrier gas dew points on the order of -70 degrees C are required to obtain errors < or = 0.1/1000 for samples yielding mass 44 ion currents of 10 nA. Carrier gas dew points < or = -80 degrees C are conveniently reached by use of a Nafion dryer operated at approximately 0 degree C. PMID:9666739

Leckrone, K J; Hayes, J M

1998-07-01

136

Performance and optimization of a combustion interface for isotope ratio monitoring gas chromatography/mass spectrometry  

NASA Technical Reports Server (NTRS)

Conditions and systems for on-line combustion of effluents from capillary gas chromatographic columns and for removal of water vapor from product streams were tested. Organic carbon in gas chromatographic peaks 15 s wide and containing up to 30 nanomoles of carbon was quantitatively converted to CO2 by tubular combustion reactors, 200 x 0.5 mm, packed with CuO or NiO. No auxiliary source of O2 was required because oxygen was supplied by metal oxides. Spontaneous degradation of CuO limited the life of CuO reactors at T > 850 degrees C. Since NiO does not spontaneously degrade, its use might be favored, but Ni-bound carbon phases form and lead to inaccurate isotopic results at T < 1050 degrees C if gas-phase O2 is not added. For all compounds tested except CH4, equivalent isotopic results are provided by CuO at 850 degrees C, NiO + O2 (gas-phase mole fraction, 10(-3)) at 1050 degrees C and NiO at 1150 degrees C. The combustion interface did not contribute additional analytical uncertainty, thus observed standard deviations of 13C/12C ratios were within a factor of 2 of shot-noise limits. For combustion and isotopic analyses of CH4, in which quantitative combustion required T approximately 950 degrees C, NiO-based systems are preferred, and precision is approximately 2 times lower than that observed for other analytes. Water must be removed from the gas stream transmitted to the mass spectrometer or else protonation of CO2 will lead to inaccuracy in isotopic analyses. Although thresholds for this effect vary between mass spectrometers, differential permeation of H2O through Nafion tubing was effective in both cases tested, but the required length of the Nafion membrane was 4 times greater for the more sensitive mass spectrometer.

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

1995-01-01

137

Stable isotope dilution gas chromatography-mass spectrometry for quantification of thymoquinone in black cumin seed oil.  

PubMed

Black cumin seed (Nigella sativa L.) is a widely used spice and herb, where thymoquinone (2-isopropyl-5-methyl-1,4-benzoquinone) is the major bioactive compound. Here, a stable isotope dilution (SID) gas chromatography-mass spectrometry (GC-MS) technique was developed for the quantification of thymoquinone. A doubly deuterated thymoquinone ([(2)H2]-thymoquinone) was synthesized for the first time with more than 93% deuteration degree shown by mass spectrometry and proton nuclear magnetic resonance ((1)H NMR). This compound was used as an internal standard for the quantification of thymoquinone using a SID GC-MS method. The validation experiment showed a recovery rate of 99.1 ± 1.1% relative standard deviation (RSD). Standard addition and external calibration methods have also been used to quantify thymoquinone, which cross-validated the developed stable isotope dilution assay (SIDA). In comparison to external calibration and standard addition methods, the SIDA method is robust and accurate. The concentration of thymoquinone in five marketed black cumin seed oils ranged between 3.34 and 10.8 mg/mL by use of SID GC-MS. PMID:24871868

Johnson-Ajinwo, Okiemute Rosa; Li, Wen-Wu

2014-06-18

138

Rapid determination of (237)Np and plutonium isotopes in urine by inductively-coupled plasma mass spectrometry and alpha spectrometry.  

PubMed

A new rapid separation method was developed for the measurement of plutonium and neptunium in urine samples by inductively-coupled plasma mass spectrometry (ICP-MS) and/or alpha spectrometry with enhanced uranium removal. This method allows separation and preconcentration of plutonium and neptunium in urine samples using stacked extraction chromatography cartridges and vacuum box flow rates to facilitate rapid separations. There is an increasing need to develop faster analytical methods for emergency response samples. There is also enormous benefit to having rapid bioassay methods in the event that a nuclear worker has an uptake (puncture wound, etc.) to assess the magnitude of the uptake and guide efforts to mitigate dose (e.g., tissue excision and chelation therapy). This new method focuses only on the rapid separation of plutonium and neptunium with enhanced removal of uranium. For ICP-MS, purified solutions must have low salt content and low concentration of uranium due to spectral interference of (238)U(1)H(+) on m/z 239. Uranium removal using this method is enhanced by loading plutonium and neptunium initially onto TEVA resin, then moving plutonium to DGA resin where additional purification from uranium is performed with a decontamination factor of almost 1×10(5). If UTEVA resin is added to the separation scheme, a decontamination factor of ~3 × 10(6) can be achieved. PMID:21709507

Maxwell, Sherrod L; Culligan, Brian K; Jones, Vernon D; Nichols, Sheldon T; Noyes, Gary W; Bernard, Maureen A

2011-08-01

139

Comparison of liquid chromatography-isotope ratio mass spectrometry (LC/IRMS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) for the determination of collagen amino acid ?13C values for palaeodietary and palaeoecological reconstruction.  

PubMed

Results are presented of a comparison of the amino acid (AA) ?(13)C values obtained by gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) and liquid chromatography-isotope ratio mass spectrometry (LC/IRMS). Although the primary focus was the compound-specific stable carbon isotope analysis of bone collagen AAs, because of its growing application for palaeodietary and palaeoecological reconstruction, the results are relevant to any field where AA ?(13)C values are required. We compare LC/IRMS with the most up-to-date GC/C/IRMS method using N-acetyl methyl ester (NACME) AA derivatives. This comparison involves the analysis of standard AAs and hydrolysates of archaeological human bone collagen, which have been previously investigated as N-trifluoroacetyl isopropyl esters (TFA/IP). It was observed that, although GC/C/IRMS analyses required less sample, LC/IRMS permitted the analysis of a wider range of AAs, particularly those not amenable to GC analysis (e.g. arginine). Accordingly, reconstructed bulk ?(13)C values based on LC/IRMS-derived ?(13)C values were closer to the EA/IRMS-derived ?(13)C values than those based on GC/C/IRMS values. The analytical errors for LC/IRMS AA ?(13)C values were lower than GC/C/IRMS determinations. Inconsistencies in the ?(13)C values of the TFA/IP derivatives compared with the NACME- and LC/IRMS-derived ?(13)C values suggest inherent problems with the use of TFA/IP derivatives, resulting from: (i) inefficient sample combustion, and/or (ii) differences in the intra-molecular distribution of ?(13)C values between AAs, which are manifested by incomplete combustion. Close similarities between the NACME AA ?(13)C values and the LC/IRMS-derived ?(13)C values suggest that the TFA/IP derivatives should be abandoned for the natural abundance determinations of AA ?(13)C values. PMID:21953954

Dunn, Philip J H; Honch, Noah V; Evershed, Richard P

2011-10-30

140

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.

1989-01-01

141

Peptide production and decay rates affect the quantitative accuracy of protein cleavage isotope dilution mass spectrometry (PC-IDMS).  

PubMed

No consensus has been reached on the proper time to add stable-isotope labeled (SIL) peptides in protein cleavage isotope dilution mass spectrometry workflows. While quantifying 24 monolignol pathway enzymes in the xylem tissue of Populus trichocarpa, we compared the protein concentrations obtained when adding the SIL standard peptides concurrently with the enzyme or after quenching of the digestion (i.e. postdigestion) and observed discrepancies for nearly all tryptic peptides investigated. In some cases, greater than 30-fold differences were observed. To explain these differences and potentially correct for them, we developed a mathematical model based on pseudo-first-order kinetics to account for the dynamic production and decay (e.g. degradation and precipitation) of the native peptide targets in conjunction with the decay of the SIL peptide standards. A time course study of the digests confirmed the results predicted by the proposed model and revealed that the discrepancy between concurrent and postdigestion introduction of the SIL standards was related to differential decay experienced by the SIL peptide and the native peptide in each method. Given these results, we propose concurrent introduction of the SIL peptide is most appropriate, though not free from bias. Mathematical modeling of this method reveals that overestimation of protein quantities would still result when rapid peptide decay occurs and that this bias would be further exaggerated by slow proteolysis. We derive a simple equation to estimate the bias for each peptide based on the relative rates of production and decay. According to this equation, nearly half of the peptides evaluated here were estimated to have quantitative errors greater than 10% and in a few cases over 100%. We conclude that the instability of peptides can often significantly bias the protein quantities measured in protein cleavage isotope dilution mass spectrometry-based assays and suggest peptide stability be made a priority when selecting peptides to use for quantification. PMID:22595788

Shuford, Christopher M; Sederoff, Ronald R; Chiang, Vincent L; Muddiman, David C

2012-09-01

142

Factors controlling precision and accuracy in isotope-ratio-monitoring mass spectrometry  

NASA Technical Reports Server (NTRS)

The performance of systems in which picomole quantities of sample are mixed with a carrier gas and passed through an isotope-ratio mass spectrometer system was examined experimentally and theoretically. Two different mass spectrometers were used, both having electron-impact ion sources and Faraday cup collector systems. One had an accelerating potential of 10kV and accepted 0.2 mL of He/min, producing, under those conditions, a maximum efficiency of 1 CO2 molecular ion collected per 700 molecules introduced. Comparable figures for the second instrument were 3 kV, 0.5 mL of He/min, and 14000 molecules/ion. Signal pathways were adjusted so that response times were <200 ms. Sample-related ion currents appeared as peaks with widths of 3-30 s. Isotope ratios were determined by comparison to signals produced by standard gases. In spite of rapid variations in signals, observed levels of performance were within a factor of 2 of shot-noise limits. For the 10-kV instrument, sample requirements for standard deviations of 0.1 and 0.5% were 45 and 1.7 pmol, respectively. Comparable requirements for the 3-kV instrument were 900 and 36 pmol. Drifts in instrumental characteristics were adequately neutralized when standards were observed at 20-min intervals. For the 10-kV instrument, computed isotopic compositions were independent of sample size and signal strength over the ranges examined. Nonlinearities of <0.04%/V were observed for the 3-kV system. Procedures for observation and subtraction of background ion currents were examined experimentally and theoretically. For sample/ background ratios varying from >10 to 0.3, precision is expected and observed to decrease approximately 2-fold and to depend only weakly on the precision with which background ion currents have been measured.

Merritt, D. A.; Hayes, J. M.

1994-01-01

143

Algorithms for Peptide Mass Spectrometry  

E-print Network

Algorithms for Peptide Mass Spectrometry Ole Schulz-Trieglaff Max Planck Research School;Why bother ? · Clinical studies but also basic research rely on an accurate quantification of peptides. Stability analysis: can we detect distorted isotopic pattern, too ? Add uniformly distributed noise

Spang, Rainer

144

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

PubMed

A procedure to detect whether carbon dioxide was added to French ciders has been developed. For this purpose, an optimised and simplified method is proposed to determine (13)C/(12)C isotope ratio of carbon dioxide (?(13)C) in ciders. Three critical steps were checked: (1) influence of atmospheric CO2 remaining in the loaded vial, (2) impact of helium flush, (3) sampling speed. This study showed that atmospheric CO2 does not impact the measurement, that helium flush can lead to isotopic fractionation and finally, that a fractionation occurs only 5h after bottle opening. The method, without any other preparation, consists in sampling 0.2 mL of cold (4 °C) cider in a vial that is passed in an ultrasonic bath for 10 min at room temperature to enhance cider de-carbonation. The headspace CO2 is then analysed using the link Multiflow®-isotope ratio mass spectrometer. Each year, a data bank is developed by fermenting authentic apples juices in order to control cider authenticity. Over a four year span (2008-2011), the CO2 produced during the fermentation step was studied. This set of 61 authentic ciders, from various French production areas, was used to determine a ?(13)C value range of -22.59±0.92‰ for authentic ciders CO2 bubbles. 75 commercial ciders were analysed with this method. Most of the samples analysed present a gas ?(13)C value in the expected range. Nevertheless, some ciders have ?(13)C values outside the 3? limit, revealing carbonation by technical CO2. This practice is not allowed for organic, "Controlled Appellation of Origin" ciders and ciders specifying natural carbonation on the label. PMID:23870934

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

2013-12-01

145

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?  

Microsoft Academic Search

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4mm to gain a high-resolution 230Thexcess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got

A. Bollhöfer; A. Eisenhauer; N. Frank; D. Pech; A. Mangini

1996-01-01

146

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?  

Microsoft Academic Search

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal\\u000a ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain\\u000a a high-resolution230Thexcess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We\\u000a got

A. Bollhöfer; A. Eisenhauer; N. Frank; D. Pech; A. Mangini

1996-01-01

147

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

PubMed

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

2001-06-21

148

Fast methodology for the reliable determination of nonylphenol in water samples by minimal labeling isotope dilution mass spectrometry.  

PubMed

In this work we have developed and validated an accurate and fast methodology for the determination of 4-nonylphenol (technical mixture) in complex matrix water samples by UHPLC-ESI-MS/MS. The procedure is based on isotope dilution mass spectrometry (IDMS) in combination with isotope pattern deconvolution (IPD), which provides the concentration of the analyte directly from the spiked sample without requiring any methodological calibration graph. To avoid any possible isotopic effect during the analytical procedure the in-house synthesized (13)C1-4-(3,6-dimethyl-3-heptyl)phenol was used as labeled compound. This proposed surrogate was able to compensate the matrix effect even from wastewater samples. A SPE pre-concentration step together with exhaustive efforts to avoid contamination were included to reach the signal-to-noise ratio necessary to detect the endogenous concentrations present in environmental samples. Calculations were performed acquiring only three transitions, achieving limits of detection lower than 100ng/g for all water matrix assayed. Recoveries within 83-108% and coefficients of variation ranging from 1.5% to 9% were obtained. On the contrary a considerable overestimation was obtained with the most usual classical calibration procedure using 4-n-nonylphenol as internal standard, demonstrating the suitability of the minimal labeling approach. PMID:23746647

Fabregat-Cabello, Neus; Castillo, Ángel; Sancho, Juan V; González, Florenci V; Roig-Navarro, Antoni Francesc

2013-08-01

149

Surfactant protein C metabolism in human infants and adult patients by stable isotope tracer and mass spectrometry.  

PubMed

Surfactant protein C (SP-C) is deemed as the surfactant protein most specifically expressed in type II alveolar epithelial cells and plays an important role in surfactant function. SP-C turnover in humans and its meaning in the clinical context have never been approached. In this study, we used mass spectrometry to investigate SP-C turnover in humans. We studied four infants and eight adults requiring mechanical ventilation. All patients had no lung disease. Patients received a 24-h continuous infusion of (13)C-leucine as precursor of SP-C, and serial tracheal aspirates and plasma samples were obtained every 6 h till 48 h. SP-C was isolated from tracheal aspirates by sorbent-phase chromatography. (13)C-leucine SP-C enrichment could be successfully measured in three infant and in four adult samples by using mass spectrometry coupled with a gas chromatographer. Median SP-C fractional synthesis rate, secretion time, and peak time were 15.7 (14.1-27.5)%/day, 6.0 (4.7-11.5) h, and 24 (20-27) h. In conclusion, this study shows that it is feasible to accurately determine SP-C turnover in humans by stable isotopes. PMID:25182966

Simonato, Manuela; Baritussio, Aldo; Pioselli, Barbara; Ori, Carlo; Catinella, Silvia; Carnielli, Virgilio P; Cogo, Paola E

2014-10-01

150

Precise determination of dissolved silica in seawater by ion-exclusion chromatography isotope dilution inductively coupled plasma mass spectrometry.  

PubMed

Ion exclusion chromatograph (IEC) isotope dilution (ID) inductively coupled plasma mass spectrometry (ICP-MS) (IEC-ID-ICP-MS) was developed for measurement of dissolved silica in seawater, which was applied to production of certified reference materials (CRMs) of three concentration levels of nutrients (high, medium and low levels). IEC-ICP-MS has been employed to separate dissolved silica from seawater matrix. In the present study, in order to solve substantial problems due to spectral interference in ICP-MS and to improve the accuracy of IEC-ICP-MS beyond standard addition or conventional calibration methods, ID method was coupled with ICP-sector field mass spectrometry (operated under medium resolution,i.e., m/?m=4000). In addition, effects of various operating parameters in ICP-MS on a silicon background level were also investigated to obtain lower background equivalent concentration (BEC). As a result, 3 ng g(-1) of the BEC and 0.5 % of relative standard uncertainties were achieved in the analyses of dissolved silica in seawater samples at concentration levels from 4.0 mg kg (-1) to 0.8 mg kg(-1) as silicon. The developed method was successfully validated by analyses of an artificial seawater containing a known amount of silicate and the seawater certified reference material MOOS-2 produced by the National Research Council Canada. PMID:25086888

Nonose, Naoko; Cheong, Chikako; Ishizawa, Yukari; Miura, Tsutomu; Hioki, Akiharu

2014-08-20

151

Accuracy of some routine method used in clinical chemistry as judged by isotope dilution-mass spectrometry  

SciTech Connect

Serum from patients was pooled, filtered, dispensed, and frozen. This pooled specimen was used for accuracy control in 64 participating laboratories in Sweden. Mean values (state-of-the-art values) were obtained for creatinine, cholesterol, glucose, urea, uric acid, and cortisol. These values were compared with values obtained with highly accurate reference methods based on isotope dilution-mass spectrometry. Differences were marked in the case of determination of creatinine and cortisol. Concerning the other components, the differences between the state-of-the-art value and the values obtained with the reference methods were negligible. Moreover, the glucose oxidase and the oxime methods for determination of glucose and urea were found to give significantly lower values than the hexokinase and urease methods, respectively. Researchers conclude that methods with a higher degree of accuracy are required for routine determination of creatinine and cortisol.

Bjoerkhem, I.; Bergman, A.; Falk, O.; Kallner, A.; Lantto, O.; Svensson, L.; Akerloef, E.; Blomstrand, R.

1981-05-01

152

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

Microsoft Academic Search

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

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

2006-01-01

153

Achieving traceable chemical measurements: inter-laboratory evaluation of a simplified technique for isotope dilution mass spectrometry (IDMS). Part 1: Methodology for high accuracy analysis of trace metals  

Microsoft Academic Search

A high accuracy measurement procedure developed and validated at the Laboratory of the Government Chemist (LGC) has been transferred to a number of expert United Kingdom laboratories and their experience in applying the technique has been evaluated by inter-laboratory comparisons. It is an “approximate matching” calibration procedure for analysis of trace metals using isotope dilution mass spectrometry (IDMS). Use of

Rita Harte; Gerry Newman; Mike Sargent

2004-01-01

154

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

PubMed

New tools for the determination of characteristic parameters for food authentication are requested to prevent food adulteration from which health concerns, unfair competition could follow. A new coupling in the area of compound-specific carbon 13 isotope ratio (?(13)C) analysis was developed to simultaneously quantify ?(13)C values of sugars and organic acids. The coupling of ion chromatography (IC) together with isotope ratio mass spectrometry (IRMS) can be achieved using a liquid interface allowing a chemical oxidation (co) of organic matter. Synthetic solutions containing 1 polyol (glycerol), 3 carbohydrates (sucrose, glucose and fructose) and 12 organic acids (gluconic, lactic, malic, tartaric, oxalic, fumaric, citric and isocitric) were used to optimize chromatographic conditions (concentration gradient and 3 types of column) and the studied isotopic range (-32.28 to -10.65‰) corresponds to the values found in food products. Optimum chromatographic conditions are found using an IonPac AS15, an elution flow rate of 0.3mLmin(-1) and a linear concentration gradient from 2 to 76mM (rate 21mMmin(-1)). Comparison between ?(13)C value individually obtained for each compound with the coupling IRMS and elemental analyzer, EA-IRMS, and the ones measured on the mixture of compounds by IC-co-IRMS does not reveal any isotope fractionation. Thus, under these experimental conditions, IC-co-IRMS results are accurate and reproducible. This new coupling was tested on two food matrices, an orange juice and a sweet wine. Some optimization is necessary as the concentration range between sugars and organic acids is too large: an increase in the filament intensity of the IRMS is necessary to simultaneously detect the two compound families. These first attempts confirm the good results obtained on synthetic solutions and the strong potential of the coupling IC-co-IRMS in food authentication area. PMID:24267317

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

2013-12-27

155

Gas Chromatography -Mass Spectrometry  

E-print Network

GCMS - 1 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS OF ETHANOL AND BENZENE IN GASOLINE Last updated: June 17, 2014 #12;GCMS - 2 Gas Chromatography - Mass Spectrometry GC-MS ANALYSIS). The goal of this experiment is to separate the components in a sample of gasoline using Gas Chromatography

Nizkorodov, Sergey

156

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

PubMed

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

2014-01-01

157

Isotope Label-Aided Mass Spectrometry Reveals the Influence of Environmental Factors on Metabolism in Single Eggs of Fruit Fly  

PubMed Central

In order to investigate the influence of light/dark cycle on the biosynthesis of metabolites during oogenesis, here we demonstrate a simple experimental protocol which combines in-vivo isotopic labeling of primary metabolites with mass spectrometric analysis of single eggs of fruit fly (Drosophila melanogaster). First, fruit flies were adapted to light/dark cycle using artificial white light. Second, female flies were incubated with an isotopically labeled sugar (13C6-glucose) for 12 h – either during the circadian day or the circadian night, at light or at dark. Third, eggs were obtained from the incubated female flies, and analyzed individually by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS): this yielded information about the extent of labeling with carbon-13. Since the incorporation of carbon-13 to uridine diphosphate glucose (UDP-glucose) in fruit fly eggs is very fast, the labeling of this metabolite was used as an indicator of the biosynthesis of metabolites flies/eggs during 12-h periods, which correspond to circadian day or circadian night. The results reveal that once the flies adapted to the 12-h-light/12-h-dark cycle, the incorporation of carbon-13 to UDP-glucose present in fruit fly eggs was not markedly altered by an acute perturbation to this cycle. This effect may be due to a relationship between biosynthesis of primary metabolites in developing eggs and an alteration to the intake of the labeled substrate – possibly related to the change of the feeding habit. Overall, the study shows the possibility of using MALDI-MS in conjunction with isotopic labeling of small metazoans to unravel the influence of environmental cues on primary metabolism. PMID:23185587

Tseng, Te-Wei; Wu, June-Tai; Chen, Yu-Chie; Urban, Pawel L.

2012-01-01

158

Quantification of nerve agent adducts with albumin in rat plasma using liquid chromatography-isotope dilution tandem mass spectrometry.  

PubMed

A sensitive method for the determination of the organophosphorus nerve agents sarin, soman and VX adducts with tyrosine residue of albumin in rat plasma has been developed and validated using liquid chromatography-isotope dilution tandem mass spectrometry (LC-IDMS/MS). O-(O-Alkyl methylphosphonyl) tyrosine adducts and their deuterated products that were used as the internal standards were synthesised to establish the quantitative isotope-dilution method. Protein purification and solid-phase extraction (SPE) were applied to improve the recovery efficiency, reduce interference and achieve high sensitivity. The method provided a detection limit of 0.01 ng/mL for sarin and soman adducts and 0.05 ng/mL for the VX adduct. The value of the intra-day relative standard deviation over the calibration range was less than 6.16% (n=6), and that of the inter-day was less than 12.7% (n=6). The recovery varied from 86% to 111%. This sensitive method was successfully applied to the analysis of adducts in rat plasma after nerve agent exposure, and the results demonstrated the dose-effect relationships. PMID:22305360

Bao, Yi; Liu, Qin; Chen, Jia; Lin, Ying; Wu, Bidong; Xie, Jianwei

2012-03-16

159

Fast and accurate procedure for the determination of Cr(VI) in solid samples by isotope dilution mass spectrometry.  

PubMed

We present here a new environmental measurement method for the rapid extraction and accurate quantification of Cr(VI) in solid samples. The quantitative extraction of Cr(VI) is achieved in 10 minutes by means of focused microwave assisted extraction using 50 mmol/L Ethylendiamintetraacetic acid (EDTA) at pH 10 as extractant. In addition, it enables the separation of Cr species by anion exchange chromatography using a mobile phase which is a 1:10 dilution of the extracting solution. Thus, neutralization or acidification steps which are prone to cause interconversion of Cr species are not needed. Another benefit of using EDTA is that it allows to measure Cr(III)-EDTA complex and Cr(VI) simultaneously in an alkaline extraction solution. The application of a 10 minutes focused microwave assisted extraction (5 min at 90 °C plus 5 min at 110 °C) has been shown to quantitatively extract all forms of hexavalent chromium from the standard reference materials (SRM) candidate NIST 2700 and NIST 2701. A double spike isotope dilution mass spectrometry (IDMS) procedure was employed to study chromium interconversion reactions. It was observed that the formation of a Cr(III)-EDTA complex avoided Cr(III) oxidation for these two reference materials. Thus, the use of a double spiking strategy for quantification is not required and a single spike IDMS procedure using isotopically enriched Cr(VI) provided accurate results. PMID:23092182

Fabregat-Cabello, Neus; Rodríguez-González, Pablo; Castillo, Ángel; Malherbe, Julien; Roig-Navarro, Antoni F; Long, Stephen E; García Alonso, J Ignacio

2012-11-20

160

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

PubMed

Although substantial technical advances have been achieved during the past decades to extend and facilitate the analysis of growth promoters in cattle, the detection of abuse of synthetic analogs of naturally occurring hormones has remained a challenging issue. When it became clear that the exogenous origin of steroid hormones could be traced based on the (13)C/(12)C isotope ratio of the substances, GC/C/IRMS has been successfully implemented to this aim since the end of the past century. However, due to the costly character of the instrumental setup, the susceptibility of the equipment to errors and the complex and time consuming sample preparation, this method is up until now only applied by a limited number of laboratories. In this review, the general principles as well as the practical application of GC/C/IRMS to differentiate between endogenous steroids and exogenously synthesized homologous compounds in cattle will be discussed in detail, and will be placed next to other existing and to be developed methods based on isotope ratio mass spectrometry. Finally, the link will be made with the field of sports doping, where GC/C/IRMS has been established within the World Anti-Doping Agency (WADA) approved methods as the official technique to differentiate between exogenous and endogenous steroids over the past few years. PMID:23540242

Janssens, Geert; Courtheyn, Dirk; Mangelinckx, Sven; Prévost, Stéphanie; Bichon, Emmanuelle; Monteau, Fabrice; De Poorter, Geert; De Kimpe, Norbert; Le Bizec, Bruno

2013-04-15

161

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

2014-06-01

162

The use of ?13C isotope ratio mass spectrometry for methamphetamine profiling: comparison of ephedrine and pseudoephedrine-based samples to P2P-based samples.  

PubMed

Differentiating methamphetamine samples produced from ephedrine and pseudoephedrine from phenyl-2-propanone precursors is critical for assigning synthetic route information for methamphetamine profiling. The use of isotope ratio mass spectrometry data is now a key component for tracking precursor information. Recent carbon (?(13)C) isotope results from the analysis of numerous methamphetamine samples show clear differentiation for ephedrine and pseudoephedrine-produced samples compared to P2P-produced samples. The carbon isotope differences were confirmed from synthetic route precursor studies. PMID:24378294

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

2014-01-01

163

Determination of cadmium in oyster tissue using isotope dilution inductively coupled plasma mass spectrometry: comparison of results obtained in the standard and He\\/H 2 cell modes  

Microsoft Academic Search

An inductively coupled plasma quadrupole mass spectrometer equipped with an octopole collision\\/reaction cell was used for\\u000a the determination of cadmium in oyster tissue samples using isotope dilution inductively coupled plasma mass spectrometry.\\u000a The oyster samples in question were found to contain Mo and Zr. In our feasibility study on a Cd standard solution (10 ?g\\u000a L?1) containing a matrix of Mo

Yiu-chung Yip; Hei-shing Chu; Kwok-chu Chan; Kam-kit Chan; Ping-yuk Cheung; Wing-cheong Sham

2006-01-01

164

Overcoming matrix effects in electrospray: quantitation of ?-agonists in complex matrices by isotope dilution liquid chromatography-mass spectrometry using singly (13)C-labeled analogues.  

PubMed

In this work, the implementation of isotope dilution mass spectrometry (IDMS) using minimal labeling and isotope pattern deconvolution (IPD) is evaluated as a strategy for the minimization of matrix effects during trace determination of ?2-agonists in complex matrices by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). First, the parameters affecting the measurement of isotopic composition of organic compounds by liquid chromatography electrospray ionization high resolution mass spectrometry with a time-of-flight analyzer were evaluated using as a case of study three different ?2-agonists: clenbuterol, clenproperol and brombuterol. Then, a calibration graph-free IDMS methodology was evaluated in order to overcome matrix effects in LC-ESI-MS in complex samples. In this procedure singly (13)C-labeled analogues of clenbuterol, clenproperol and brombuterol were employed in combination with IPD. Using this approach accurate and precise results were obtained in the simultaneous quantification of ?2-agonists in human urine and bovine liver, even at the sub ngg(-1) and particularly in spite of the previously reported matrix effects. Recovery rates in the range of 97-114% in fortified human urine and from 95% to 111% in fortified bovine liver were obtained with RSD (%) of independent recovery experiments always lower than 6%. These results demonstrate that the proposed methodology based on the use of (13)C1-labeled standards and IPD is a reliable approach for accurate LC-MS quantitation of small molecules and compatible with full-scan high-resolution mass spectrometry. PMID:23523066

González-Antuña, Ana; Domínguez-Romero, Juan C; García-Reyes, Juan F; Rodríguez-González, Pablo; Centineo, Giuseppe; García Alonso, J Ignacio; Molina-Díaz, Antonio

2013-05-01

165

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.

2008-12-01

166

Transition of Iodine Analysis to Accelerator Mass Spectrometry.  

National Technical Information Service (NTIS)

Funding was received from NA-22 to investigate transitioning iodine isotopic analyses to an accelerator mass spectrometry (AMS) system. The present method uses gas-phase chemistry followed by thermal ionization mass spectrometry (TIMS). It was anticipated...

J. E. Delmore

2010-01-01

167

Forensic analysis of explosives using isotope ratio mass spectrometry (IRMS)--part 1: instrument validation of the DELTAplusXP IRMS for bulk nitrogen isotope ratio measurements.  

PubMed

A significant amount of research has been conducted into the use of stable isotopes to assist in determining the origin of various materials. The research conducted in the forensic field shows the potential of isotope ratio mass spectrometry (IRMS) to provide a level of discrimination not achievable utilizing traditional forensic techniques. Despite the research there have been few, if any, publications addressing the validation and measurement uncertainty of the technique for forensic applications. This study, the first in a planned series, presents validation data for the measurement of bulk nitrogen isotope ratios in ammonium nitrate (AN) using the DELTA(plus)XP (Thermo Finnigan) IRMS instrument equipped with a ConFlo III interface and FlashEA 1112 elemental analyzer (EA). Appropriate laboratory standards, analytical methods and correction calculations were developed and evaluated. A validation protocol was developed in line with the guidelines provided by the National Association of Testing Authorities, Australia (NATA). Performance characteristics including: accuracy, precision/repeatability, reproducibility/ruggedness, robustness, linear range, and measurement uncertainty were evaluated for the measurement of nitrogen isotope ratios in AN. AN (99.5%) and ammonium thiocyanate (99.99+%) were determined to be the most suitable laboratory standards and were calibrated against international standards (certified reference materials). All performance characteristics were within an acceptable range when potential uncertainties, including the manufacturer's uncertainty of the technique and standards, were taken into account. The experiments described in this article could be used as a model for validation of other instruments for similar purposes. Later studies in this series will address the more general issue of demonstrating that the IRMS technique is scientifically sound and fit-for-purpose in the forensic explosives analysis field. PMID:20015166

Benson, Sarah J; Lennard, Christopher J; Hill, David M; Maynard, Philip; Roux, Claude

2010-01-01

168

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.

2011-01-01

169

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

PubMed

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

2005-03-01

170

Fourier Transform Mass Spectrometry  

PubMed Central

This article provides an introduction to Fourier transform-based mass spectrometry. The key performance characteristics of Fourier transform-based mass spectrometry, mass accuracy and resolution, are presented in the view of how they impact the interpretation of measurements in proteomic applications. The theory and principles of operation of two types of mass analyzer, Fourier transform ion cyclotron resonance and Orbitrap, are described. Major benefits as well as limitations of Fourier transform-based mass spectrometry technology are discussed in the context of practical sample analysis, and illustrated with examples included as figures in this text and in the accompanying slide set. Comparisons highlighting the performance differences between the two mass analyzers are made where deemed useful in assisting the user with choosing the most appropriate technology for an application. Recent developments of these high-performing mass spectrometers are mentioned to provide a future outlook. PMID:21742802

Scigelova, Michaela; Hornshaw, Martin; Giannakopulos, Anastassios; Makarov, Alexander

2011-01-01

171

The role of isotope ratio mass spectrometry as a tool for the comparison of physical evidence.  

PubMed

This paper considers how likelihood ratios can be derived for a combination of physical, chemical and isotopic measurements. Likelihood ratios were formulated based on the characteristics of a small convenience sample of 20 duct tapes. The propositions considered were: The physical and isotopic characteristics of ten rolls of duct tape were shown to be consistent throughout each roll. The width and thickness of the tapes and the density of the scrim fibres provided equivalent information and the combined physical characteristics provided a basis upon which to discriminate between many of the samples. Scatter-plots and confidence ellipses provided a convenient method to group the isotopic composition of the tape backing material and provided a basis to discriminate between samples which were physically indistinguishable. Considering both the physical and isotopic characteristics it was possible, at best, to ascertain that the evidence provided moderately strong support for the proposition that two samples of tape were derived from the same batch (LR=400). Kernel density estimates were used to model the distribution of isotopic compositions of the backing material. Using this technique it was possible to estimate objectively the probability that a sample with given characteristics could be drawn, at random, from the background population and to calculate a likelihood ratio based on the propositions above. The strength of evidence which could be presented by either model was ultimately limited by the size of the background sample. PMID:25278193

Carter, James F; Doyle, Sean; Phasumane, Bohang-Lintle; NicDaeid, Niamh

2014-09-01

172

Fourier Transform Mass Spectrometry.  

ERIC Educational Resources Information Center

Discusses the nature of Fourier transform mass spectrometry and its unique combination of high mass resolution, high upper mass limit, and multichannel advantage. Examines its operation, capabilities and limitations, applications (ion storage, ion manipulation, ion chemistry), and future applications and developments. (JN)

Gross, Michael L.; Rempel, Don L.

1984-01-01

173

Nicotine, acetanilide and urea multi-level2H-,13C- and15N-abundance reference materials for continuous-flow isotope ratio mass spectrometry  

USGS Publications Warehouse

Accurate determinations of stable isotope ratios require a calibration using at least two reference materials with different isotopic compositions to anchor the isotopic scale and compensate for differences in machine slope. Ideally, the S values of these reference materials should bracket the isotopic range of samples with unknown S values. While the practice of analyzing two isotopically distinct reference materials is common for water (VSMOW-SLAP) and carbonates (NBS 19 and L-SVEC), the lack of widely available organic reference materials with distinct isotopic composition has hindered the practice when analyzing organic materials by elemental analysis/isotope ratio mass spectrometry (EA-IRMS). At present only L-glutamic acids USGS40 and USGS41 satisfy these requirements for ??13C and ??13N, with the limitation that L-glutamic acid is not suitable for analysis by gas chromatography (GC). We describe the development and quality testing of (i) four nicotine laboratory reference materials for on-line (i.e. continuous flow) hydrogen reductive gas chromatography-isotope ratio mass-spectrometry (GC-IRMS), (ii) five nicotines for oxidative C, N gas chromatography-combustion-isotope ratio mass-spectrometry (GC-C-IRMS, or GC-IRMS), and (iii) also three acetanilide and three urea reference materials for on-line oxidative EA-IRMS for C and N. Isotopic off-line calibration against international stable isotope measurement standards at Indiana University adhered to the 'principle of identical treatment'. The new reference materials cover the following isotopic ranges: ??2Hnicotine -162 to -45%o, ??13Cnicotine -30.05 to +7.72%, ?? 15Nnicotine -6.03 to +33.62%; ??15N acetanilide +1-18 to +40.57%; ??13Curea -34.13 to +11.71%, ??15Nurea +0.26 to +40.61% (recommended ?? values refer to calibration with NBS 19, L-SVEC, IAEA-N-1, and IAEA-N-2). Nicotines fill a gap as the first organic nitrogen stable isotope reference materials for GC-IRMS that are available with different ??13N values. Comparative ??13C and ??15N on-line EA-IRMS data from 14 volunteering laboratories document the usefulness and reliability of acetanilides and ureas as EA-IRMS reference materials.

Schimmelmann, A.; Albertino, A.; Sauer, P.E.; Qi, H.; Molinie, R.; Mesnard, F.

2009-01-01

174

Detection of synthetic testosterone use by novel comprehensive two-dimensional gas chromatography combustion-isotope ratio mass spectrometry.  

PubMed

We report the first demonstration of comprehensive two-dimensional gas chromatography combustion-isotope ratio mass spectrometry (GC×GCC-IRMS) for the analysis of urinary steroids to detect illicit synthetic testosterone use, of interest in sport doping. GC coupled to IRMS (GCC-IRMS) is currently used to measure the carbon isotope ratios (CIRs, ?(13)C) of urinary steroids in antidoping efforts; however, extensive cleanup of urine extracts is required prior to analysis to enable baseline separation of target steroids. With its greater separation capabilities, GC×GC has the potential to reduce sample preparation requirements and enable CIR analysis of minimally processed urine extracts. Challenges addressed include online reactors with minimized dimensions to retain narrow peak shapes, baseline separation of peaks in some cases, and reconstruction of isotopic information from sliced steroid chromatographic peaks. Difficulties remaining include long-term robustness of online reactors and urine matrix effects that preclude baseline separation and isotopic analysis of low-concentration and trace components. In this work, steroids were extracted, acetylated, and analyzed using a refined, home-built GC×GCC-IRMS system. 11-Hydroxyandrosterone and 11-ketoetiocolanolone were chosen as endogenous reference compounds because of their satisfactory signal intensity, and their CIR was compared to target compounds androsterone and etiocholanolone. Separately, a GC×GC-quadrupole MS system was used to measure testosterone (T)/epitestosterone (EpiT) concentration ratios. Urinary extracts of urine pooled from professional athletes and urine from one individual that received testosterone gel (T-gel) and one individual that received testosterone injections (T-shots) were analyzed. The average precisions of ?(13)C and ??(13)C measurements were SD(?(13)C) approximately ±1‰ (n = 11). The T-shot sample resulted in a positive for T use with a T/EpiT ratio of >9 and CIR measurements of ??(13)C > 5‰, both fulfilling World Anti-Doping Agency criteria. These data show for the first time that synthetic steroid use is detectable by GC×GCC-IRMS without the need for extensive urine cleanup. PMID:21846122

Tobias, Herbert J; Zhang, Ying; Auchus, Richard J; Brenna, J Thomas

2011-09-15

175

Characterization of candidate reference materials for bone lead via interlaboratory study and double isotope dilution mass spectrometry  

PubMed Central

Summary Four candidate ground bone reference materials (NYS RMs 05-01 through 04), were produced from lead-dosed bovine and caprine sources, and characterized by interlaboratory study. The consensus value ( X ) and expanded standard uncertainty (UX ) were determined from the robust average and standard deviation of the participants’ data for each NYS RM 05-01 through 04. The values were 1.08 ±0.04, 15.3 ±0.5, 12.4 ±0.5, and 29.9 ±1.1 ?g g?1 Pb, respectively. Youden plots of z-scores showed a statistically significant correlation between the results for pairs of NYS RM 05-02 through 04, indicating common sources of between-laboratory variation affecting reproducibility. NYS RM 05-01 exhibited more random variability affecting repeatability at low concentration. Some participants using electrothermal atomic absorption spectrometry (ETAAS) exhibited a negative bias compared to the all-method consensus value. Other methods used included inductively coupled plasma mass spectrometry (ICP-MS), isotope dilution (ID-) ICP-MS, and ICP atomic (optical) emission spectroscopy (-OES). The NYS RMs 05-01 through 04 were subsequently re-analyzed in house using double ID-ICP-MS to assign certified reference values (C ) and expanded uncertainty (UC ) of 1.09 ± 0.03, 16.1 ± 0.3, 13.2 ± 0.3 and 31.5 ± 0.7, respectively, indicating a low bias in the interlaboratory data. SRM 1486 Bone Meal was analyzed for measurement quality assessment obtaining results in agreement with the certified values within the stated uncertainty. Analysis using a primary reference method based on ID-ICP-MS with full quantification of uncertainty calculated according to ISO guidelines provided traceability to SI units. PMID:23087531

Bellis, David J.; Hetter, Katherine M.; Verostek, Mary Frances; Parsons, Patrick J.

2012-01-01

176

An accurate and transferable protocol for reproducible quantification of organic pollutants in human serum using direct isotope dilution mass spectrometry.  

PubMed

A robust method has been developed for easy transfer between analytical laboratories to obtain highly accurate and reproducible quantification of persistent organic pollutants (POPs) in micro-volumes of serum. This method is suited for analysts researching the impact of environmental exposure on human health. When performed by highly trained analysts, existing methods can produce high quality data; however, complex sample preparation steps often cannot be consistently replicated by laboratories, leading to variance in extraction recovery and quantitation. By combining stir-bar sorptive extraction (SBSE) with direct isotope dilution (D-ID) mass spectrometry quantification, a new analytical method was developed. The D-ID quantification significantly improved accuracy, corrected sample-to-sample irreproducibility, and reduced sample preparation time. Independent production of statistically identical data then confirmed transfer of the validated operating protocol to an off-site laboratory with different instrument models. SBSE performance was compared with industry-accepted extraction techniques. D-ID quantification was compared with peer-reviewed relative isotopic response factor (RF) quantification methods. Holding other variables constant, D-ID improved accuracy by 250% and precision by 300% compared with RF; SBSE improved accuracy by 37% compared to industry-accepted extraction methods. Limits of quantification of the analytes ranged from 60 pg g(-1) to 1 ?g g(-1). Protocol transfer exhibited <7% mean between-laboratory error and <2% mean within-laboratory RSD. These results indicate that a transferable method has been developed for academic, government, commercial, and clinical laboratories seeking to maximize throughput and improve quantitative validity. This validated method was applied in a recent clinical study to assess non-communicable disease in children in Pennsylvania, USA. PMID:25302342

Boggess, Andrew J; Rahman, G M Mizanur; Pamukcu, Matt; Faber, Scott; Kingston, H M Skip

2014-10-27

177

A novel methodological approach for ?(18)O analysis of sugars using gas chromatography-pyrolysis-isotope ratio mass spectrometry.  

PubMed

Although the instrumental coupling of gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) for compound-specific ?(18)O analysis has been commercially available for more than a decade, this method has been hardly applied so far. Here we present the first GC-Py-IRMS ?(18)O results for trimethylsilyl-derivatives of plant sap-relevant sugars and a polyalcohol (glucose, fructose, sucrose, raffinose and pinitol). Particularly, we focus on sucrose, which is assimilated in leaves and which is the most important transport sugar in plants and hence of utmost relevance in plant physiology and paleoclimate studies. Replication measurements of sucrose standards and concentration series indicate that the GC-Py-IRMS ?(18)O measurements are not stable over time and that they are amount (area) dependent. We, therefore, suggest running sample batch replication measurements in alternation with standard concentration series of reference material. This allows for carrying out (i) a drift correction, (ii) a calibration against reference material and (iii) an amount (area) correction. Tests with (18)O-enriched water do not provide any evidence for oxygen isotope exchange reactions affecting sucrose and raffinose. We present the first application of GC-Py-IRMS ?(18)O analysis for sucrose from needle extract (soluble carbohydrate) samples. The obtained ?(18)Osucrose/ Vienna Standard Mean Ocean Water (VSMOW) values are more positive and vary in a wider range (32.1-40.1 ‰) than the ?(18)Obulk/ VSMOW values (24.6-27.2 ‰). Furthermore, they are shown to depend on the climate parameters maximum day temperature, relative air humidity and cloud cover. These findings suggest that ?(18)Osucrose of the investigated needles very sensitively reflects the climatically controlled evaporative (18)O enrichment of leaf water and thus highlights the great potential of GC-Py-IRMS ?(18)Osucrose analysis for plant physiology and paleoclimate studies. PMID:24313371

Zech, Michael; Saurer, Matthias; Tuthorn, Mario; Rinne, Katja; Werner, Roland A; Siegwolf, Rolf; Glaser, Bruno; Juchelka, Dieter

2013-01-01

178

Determination of Mercury Content in a Shallow Firn Core from Summit, Greenland by Isotope Dilution Inductively Coupled Plasma Mass Spectrometry  

NASA Technical Reports Server (NTRS)

The total mercury Hg content was determined in 6 cm sections of a near-surface 7 m firn core and in surrounding surface snow from Summit, Greenland (elevation: 3238 m, 72.58 N, 38.53 W) in May 2001 by isotope dilution cold-vapor inductively coupled plasma mass spectrometry (ID-CV-ICP-MS). The focus of this research was to evaluate the capability of the ID-CV-ICPMS technique for measuring trace levels of Hg typical of polar snow and firn. Highly enriched Hg-201 isotopic spike is added to approximately 10 ml melted core and thoroughly mixed. The Hg(+2) in the sample is reduced on line with tin (II) chloride (SnCl2) and the elemental Hg (Hg(0)) vapor pre-concentrated on to gold gauze using a commercial amalgam system. The Hg is then thermally desorbed and introduced into a quadrupole ICP-MS. The blank corrected Hg concentrations determined for all samples ranged from 0.25 ng/L to 1.74 ng/L (ppt) (average 0.59 ng/L plus or minus 0.28 ng/L) and fall within the range of those previously determined by Boutron et al., 1998 (less than or equal to 0.05 ng/L to 2.0 ng/L) for the Summit site. The average blank value was 0.19 ng/L plus or minus 0.045 ng/L (n=6). The Hg values specifically for the firn core range from 0.25 ng/L to 0.87 ng/L (average 0.51 ng/L plus or minus 0.13 ng/L) and show both values declining with time and larger variability in concentration in the top 1.8 m.

Mann, Jacqueline L.; Long, Stephen E.; Shuman, Christopher A.; Kelly, W. Robert

2003-01-01

179

Isolation of bicarbonate from equine urine for isotope ratio mass spectrometry  

Microsoft Academic Search

Sodium bicarbonate administration to horses prior to competition in order to enhance the buffer capacity of the organism is considered as a doping offence. The analysis of the isotopic composition of urinary bicarbonate\\/CO2 (TCO2) may help to identify an exogenous bicarbonate source, as technical sodium bicarbonate exhibits elevated ?C values compared with urinary total carbon. The isolation of TCO2 from

Frank Hülsemann; Ulrich Flenker; Marc Machnik; Wilhelm Schänzer

2007-01-01

180

In situ hafnium isotope ratio analysis of zircon by inductively coupled plasma multiple collector mass spectrometry  

Microsoft Academic Search

Hf isotopic data are reported for ten ?0.01-mm2 subareas of a zircon crystal separated from the ? 318-Ma diatreme of Elie Ness, Fife, Scotland. In situ analysis was achieved by ablation sampling with a Nd:YAG laser into an inductively-coupled plasma, with ions dispersed by a sector magnet and integrated in a 7-Faraday multicollector array. Despite large interferences from Yb (16%

Matthew F. Thirlwall; Andrew J. Walder

1995-01-01

181

Stable isotope imaging of biological samples with high resolution secondary ion mass spectrometry and complementary techniques  

PubMed Central

Stable isotopes are ideal labels for studying biological processes because they have little or no effect on the biochemical properties of target molecules. The NanoSIMS is a tool that can image the distribution of stable isotope labels with up to 50 nm spatial resolution and with good quantitation. This combination of features has enabled several groups to undertake significant experiments on biological problems in the last decade. Combining the NanoSIMS with other imaging techniques also enables us to obtain not only chemical information but also the structural information needed to understand biological processes. This article describes the methodologies that we have developed to correlate atomic force microscopy and backscattered electron imaging with NanoSIMS experiments to illustrate the imaging of stable isotopes at molecular, cellular, and tissue scales. Our studies make it possible to address 3 biological problems: (1) the interaction of antimicrobial peptides with membranes; (2) glutamine metabolism in cancer cells; and (3) lipoprotein interactions in different tissues. PMID:24556558

Jiang, H.; Favaro, E.; Goulbourne, C. N.; Rakowska, P. D.; Hughes, G. M.; Ryadnov, M. G.; Fong, L.G.; Young, S. G.; Ferguson, D. J. P.; Harris, A. L.; Grovenor, C. R. M.

2014-01-01

182

Identification and quantification of human DNA repair protein NEIL1 by liquid chromatography/isotope-dilution tandem mass spectrometry.  

PubMed

Accumulated evidence points to DNA repair capacity as an important factor in cancer and other diseases. DNA repair proteins are promising drug targets and are emerging as prognostic and therapeutic biomarkers. Thus, the knowledge of the overexpression or underexpression levels of DNA repair proteins in tissues will be of fundamental importance. In this work, mass spectrometric assays were developed for the measurement in tissues of the human DNA repair protein NEIL1 (hNEIL1), which is involved in base excision and nucleotide excision repair pathways of oxidatively induced DNA damage. Liquid chromatography/isotope-dilution tandem mass spectrometry (LC-MS/MS), in combination with a purified and fully characterized recombinant (15)N-labeled analogue of hNEIL1 ((15)N-hNEIL1) as an internal standard, was utilized to develop an accurate method for the quantification of hNEIL1. Both hNEIL1 and (15)N-hNEIL1 were hydrolyzed with trypsin, and 18 tryptic peptides from each protein were identified by LC-MS/MS on the basis of their full-scan mass spectra. These peptides matched the theoretical peptides expected from trypsin hydrolysis of hNEIL1 and provided a statistically significant protein score that would unequivocally identify hNEIL1. The product ion spectra of the tryptic peptides from both proteins were recorded, and the characteristic product ions were defined. Selected-reaction monitoring was used to analyze mixtures of hNEIL1 and (15)N-hNEIL1 on the basis of product ions. Additional confirmation of positive identification was demonstrated via separation of the proteins by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and in-gel tryptic digestion followed by LC-MS/MS analysis. These results suggest that the developed assays would be highly suitable for the in vivo positive identification and accurate quantification of hNEIL1 in tissues. PMID:23268652

Reddy, Prasad T; Jaruga, Pawel; Kirkali, Güldal; Tuna, Gamze; Nelson, Bryant C; Dizdaroglu, Miral

2013-02-01

183

Comprehensive quantification of monolignol-pathway enzymes in populus trichocarpa by protein cleavage isotope dilution mass spectrometry.  

PubMed

The economic value of wood/pulp from many tree species is largely dictated by the quantity and chemical properties of lignin, which is directly related to the composition and linkages of monolignols comprising the polymer. Although much is known regarding the monolignol biosynthetic pathway, our understanding is still deficient due to the lack of quantitative information at the proteomic level. We developed an assay based on protein cleavage isotope dilution mass spectrometry (PC-IDMS) for the determination of all potential, primary enzymes involved in the biosynthesis of monolignols and the peroxidases responsible for their polymerization to form lignin in the model tree species, Populus trichocarpa. Described is the identification of quantitative surrogate peptides through shotgun analysis of native and recombinant proteins, optimization of trypsin proteolysis using fractional factorial design of experiments, and development of a liquid chromatography-selected reaction monitoring method for specific detection of all targeted peptides. Of the 25 targeted enzymes, three were undetected in the normal xylem tissues, and all but two of the detectable species showed good day-to-day precision (CV < 10%). This represents the most comprehensive assay for quantification of proteins regulating monolignol biosynthesis and will lead to a better understanding of lignin formation at a systems level. PMID:22524869

Shuford, Christopher M; Li, Quanzi; Sun, Ying-Hsuan; Chen, Hsi-Chuan; Wang, Jack; Shi, Rui; Sederoff, Ronald R; Chiang, Vincent L; Muddiman, David C

2012-06-01

184

Determining mycotoxins in baby foods and animal feeds using stable isotope dilution and liquid chromatography tandem mass spectrometry.  

PubMed

We developed a stable isotope dilution assay with liquid chromatography tandem mass spectrometry (LC-MS/MS) to determine multiple mycotoxins in baby foods and animal feeds. Samples were fortified with [(13)C]-uniformly labeled mycotoxins as internal standards ([(13)C]-IS) and prepared by solvent extraction (50% acetonitrile in water) and filtration, followed by LC-MS/MS analysis. Mycotoxins in each sample were quantitated with the corresponding [(13)C]-IS. In general, recoveries of aflatoxins (2-100 ng/g), deoxynivalenol, fumonisins (50-2000 ng/g), ochratoxin A (20-1000 ng/kg), T-2 toxin, and zearalenone (40-2000 ng/g) in tested matrices (grain/rice/oatmeal-based formula, animal feed, dry cat/dog food) ranged from 70 to 120% with relative standard deviations (RSDs) <20%. The method provides sufficient selectivity, sensitivity, accuracy, and reproducibility to screen for aflatoxins at ng/g concentrations and deoxynivalenol and fumonisins at low ?g/g concentrations in baby foods and animal feeds, without using conventional standard addition or matrix-matched calibration standards to correct for matrix effects. PMID:25153173

Zhang, Kai; Wong, Jon W; Krynitsky, Alexander J; Trucksess, Mary W

2014-09-10

185

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.

1982-05-01

186

Isotope dilution high-performance liquid chromatography-tandem mass spectrometry method for quantifying urinary metabolites of synthetic pyrethroid insecticides.  

PubMed

This paper describes a method for measuring cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acids (cis-DCCA and trans-DCCA), cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (DBCA), 3-phenoxybenzoic acid (3PBA), and 4-fluoro-3-phenoxybenzoic acid (4F3PBA) in human urine. These compounds are considered to be reliable biomarkers of exposure for many pyrethroid insecticides used in the United States. In this method, stable isotopically labeled analogues of trans-DCCA and 3PBA were spiked into urine as internal standards. After solid-phase extraction, the extracts were analyzed by high-performance liquid chromatography coupled with tandem mass spectrometry using turbo ion-spray atmospheric pressure ionization. The limits of detection (LODs) ranged from 0.1 to 0.5 microg/L. Within-day relative standard deviations ranged from 1.8 to 13% and between-day relative standard deviations ranged from 0.5 to 18%. Absolute analyte recoveries ranged from 72 to 93%. Chromatographic retention times were less than 8 min. This method was used to measure urinary concentrations of these metabolites in persons with no known exposure to pyrethroids and some with suspected residential exposure. Metabolites of synthetic pyrethroids were detected in 74% of the samples analyzed. cis-DCCA, trans-DCCA, DBCA, 4F3PBA, and 3PBA were detected in 36, 50, 3, 9, and 64% of the samples analyzed, respectively. PMID:15195798

Baker, Samuel E; Olsson, Anders O; Barr, Dana B

2004-04-01

187

Detection of allantoin in clinical samples using hydrophilic liquid chromatography with stable isotope dilution negative ion tandem mass spectrometry.  

PubMed

Allantoin is the major oxidation product of urate in humans and is a potential biomarker of oxidative stress. Several methods are used to measure allantoin in biological samples but they have inherent issues that can include lack of specificity and sensitivity, difficulty in sample preparation, or artefactual generation of allantoin. We have developed a method for measuring allantoin using hydrophilic liquid chromatography with stable isotope dilution tandem mass spectrometry (HILIC-MS/MS). It was validated for measuring allantoin in plasma, synovial fluid and urine from human subjects. The limit of quantification was determined to be 10 fmol and the assay displayed excellent linearity for the wide range of concentrations found in clinical samples. Relative standard deviations were <5% for between-day and <7% for within-day variation. Accuracy was between 100% and 104%. Concentrations of allantoin in plasma of healthy controls (2.0 ?M; interquartile range 1.4-3.6 ?M, n=35) was significantly lower (p<0.001) than that in plasma from patients with rheumatoid arthritis (3.7 ?M; IQR 3.0-5.6 ?M, n=43) and in synovial fluid of patients with gout (3.3 ?M; IQR 2.8-5.8 ?M, n=10). This newer HILIC-MS/MS method is a simple and highly sensitive assay for detection of allantoin. It can be used to assess the level of oxidative stress in human pathologies. PMID:22398212

Turner, Rufus; Stamp, Lisa K; Kettle, Anthony J

2012-04-01

188

Four frequently used test systems for serum cholesterol evaluated by isotope dilution gas chromatography-mass spectrometry candidate reference method.  

PubMed

We evaluated the performance of four frequently used cholesterol test systems, using split-sample measurements with a panel of 79 patients' specimens and isotope dilution gas chromatography-mass spectrometry (ID GS-MS) as a comparison method. The test systems were from Beckman, a Boehringer Mannheim, Merck, and Johnson & Johnson Clinical Diagnostics, performed on the Synchron CX7, Hitachi 717, Mega, and Ektachem 250 analyzers, respectively. The liner regression data for the method comparison [ID GS-MS as independent variable (x)] were for Beckman: slope = 1.012, intercept = 0.0243 mmol/L, dispersion (S(y/x)) = 0.1303 mmol/l, and correlation coefficient (r) = 0.9867; for Boehringer Mannheim: slope = 1.002, intercept = 0.114 mmol/L, Sy/x = 0.0759 mmol/L, r = 0.9954; for Merck: slope = 1.034, intercept = -0.0613 mmol/L, Sy/x = 0.0886 mmol/L, r = 0.9941; and for Johnson & Johnson Clinical Diagnostics: slope = 1.007, intercept = 0.01 mmol/L, Sy/x = 0.15 mmol/L, and r = 0.9811. These data demonstrate excellent state-of-the-art cholesterol measurement for some of the most widely used test systems. PMID:8605669

Thienpont, L M; Van Landuyt, K G; Stöckl, D; De Leenheer, A P

1996-04-01

189

Advanced Identification of Proteins in Uncharacterized Proteomes by Pulsed in Vivo Stable Isotope Labeling-based Mass Spectrometry*  

PubMed Central

Despite progress in the characterization of their genomes, proteomes of several model organisms are often only poorly characterized. This problem is aggravated by the presence of large numbers of expressed sequence tag clones that lack homologues in other species, which makes it difficult to identify new proteins irrespective of whether such molecules are involved in species-specific biological processes. We have used a pulsed stable isotope labeling with amino acids in cell culture (SILAC)-based mass spectrometry method, which is based on the detection of paired peptides after [13C6]lysine incorporation into proteins in vivo, to greatly increase the confidence of protein identification in cross-species database searches. The method was applied to identify nearly 3000 proteins in regenerating tails of the urodele amphibian Notophthalmus viridescens, which possesses outstanding capabilities in the regeneration of complex tissues. We reason that pulsed in vivo SILAC represents a versatile tool to identify new proteins in species for which only limited sequence information exists. PMID:20139370

Looso, Mario; Borchardt, Thilo; Kruger, Marcus; Braun, Thomas

2010-01-01

190

Mass Spectrometry for the Masses  

ERIC Educational Resources Information Center

A simple, qualitative experiment is developed for implementation, where the gas chromatography-mass spectrometry (GC-MS) plays an important role, into the laboratory curriculum of a chemistry course designed for nonscience majors. This laboratory experiment is well suited for the students as it helps them to determine the validity of their…

Persinger, Jared D.; Hoops, Geoffrey, C.; Samide, Michael J.

2004-01-01

191

Nevan Krogan: Mass Spectrometry  

NSDL National Science Digital Library

This lecture from the iBioSeminars project, presented by Nevan Krogan of the Department of Cellular and Molecular Pharmacology at UC-San Francisco, covers mass spectrometry and its application to molecular biology. Mass spectrometry is a powerful tool for elucidating the elemental composition of a sample or molecule. More recently, it has been used to characterize biological material, in particular proteins and protein complexes, in a variety of organisms. This lecture will review the underlying principles of how a mass spectrometer works, discuss up to date instrumentation that is presently being used in the biological research setting and provide specific examples of how mass spectrometry is being used to reveal functional insight into different biological systems. The video runs 27:36 and can be downloaded in a number of formats: QuickTime, MP4, M4V, and PPT. The video can also be streamed through YouTube or iTunes U.

Krogan, Nevan

2013-07-12

192

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

NASA Astrophysics Data System (ADS)

As metagenomics increases our insight into microbial community diversity and metabolic potential, new approaches are required to determine the biogeochemical expression of this potential within ecosystems. Because stable isotopic analysis of the major bioactive elements (C, N) has been used historically to map flows of substrates and energy among macroscopic food webs, similar principles may apply to microbes. To address this challenge, we have developed a new analytical approach called Protein Stable Isotope Fingerprinting (P-SIF). P-SIF generates natural stable isotopic fingerprints of microbial individual or community proteomes. The main advantage of P-SIF is the potential to bridge the gap between diversity and function, thereby providing a window into the "black box" of environmental microbiology and helping to decipher the roles of uncultivated species. Our method implements a three-way, orthogonal scheme to separate mixtures of whole proteins into subfractions dominated by single or closely-related proteins. Protein extracts first are isoelectrically focused in a gel-free technique that yields 12 fractions separated over a gradient of pH 3-10. Each fraction then is separated by size-exclusion chromatography into 20 pools, ranging from >100kD to ~10kD. Finally, each of these pools is subjected to HPLC and collected in 40 time-slices based on protein hydrophobicity. Theoretical calculation reveals that the true chromatographic resolution of the total scheme is 5000, somewhat less than the 9600 resulting fractions. High-yielding fractions are subjected to ?13C analysis by spooling-wire microcombustion irMS (SWiM-irMS) optimized for samples containing 1-5 nmol carbon. Here we will present the method, results for a variety of pure cultures, and preliminary data for a sample of mixed environmental proteins. The data show the promise of this method for unraveling the metabolic complexity hidden within microbial communities.

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

2012-12-01

193

Mass Spectrometry Primer  

NSDL National Science Digital Library

This website developed by Waters Corporation provides a brief primer on mass spectrometry which includes information on instrumentation, a discussion of mass accuracy, resolution, and LC-MS. As such the site should be a valuable resource for both students and faculty.

2011-06-13

194

Simultaneous detection and quantification of 3-nitrotyrosine and 3-bromotyrosine in human urine by stable isotope dilution liquid chromatography tandem mass spectrometry  

Microsoft Academic Search

Nitration and bromination of proteins, giving rise to the respective 3-nitrotyrosine (3NT) and 3-bromotyrosine (3BT), are implicated in asthma, allergic inflammatory disorders, and cancer. We have developed an isotope dilution liquid chromatography electrospray ionization tandem mass spectrometry (LC\\/MS\\/MS) assay for simultaneous analysis of protein-bound 3NT and 3BT in human urine. The detection limits (S\\/N=3) were 10pg (44fmol) for 3NT and

Hauh-Jyun Candy Chen; Wei-Loong Chiu

2008-01-01

195

Simultaneous determination of reduced glutathione, glutathione disulphide and glutathione sulphonamide in cells and physiological fluids by isotope dilution liquid chromatography–tandem mass spectrometry  

Microsoft Academic Search

A stable isotope dilution liquid chromatography tandem mass spectrometry (LC–MS\\/MS) method was developed and validated for simultaneously quantifying glutathione (GSH), glutathione disulphide (GSSG) and glutathione sulphonamide (GSA) from biological samples. GSA is a selective product of the reaction of GSH with hypochlorous acid and a potential biomarker of myeloperoxidase activity. GSH was detected as the N-ethylmaleimide alkylated adduct, as formation

D. Tim Harwood; Anthony J. Kettle; Siobhain Brennan; Christine C. Winterbourn

2009-01-01

196

Application of stable isotope dilution assays based on liquid chromatography-tandem mass spectrometry for the assessment of folate bioavailability.  

PubMed

A pilot study was performed to prove the suitability of stable isotope dilution assays for assessing the bioavailability of endogenous folates in foods. By using [2H(4)]folic acid, [2H(4)]tetrahydrofolate, [2H(4)]5-methyltetrahydrofolate, [2H(4)]5-formyltetrahydrofolate and [2H(4)]10-formylfolic acid as internal standards, folates in spinach, apple juice and blood plasma were quantified by liquid chromatography coupled to tandem mass spectrometry. To liberate the pteroyl monoglutamates, sample extracts of foods were treated by rat plasma. Sample clean-up was achieved by solid-phase extraction on anion-exchange cartridges, which proved to be sufficient to obtain mass chromatograms devoid of matrix interferences. The bioavailability study was designed as a short-time protocol with three meals, the first consisting of 600 g spinach (meal A), the second consisting of 600 g apple sauce with additionally 400 microg synthetic folic acid (meal B) and the third consisting solely of 600 g apple sauce (meal C). Prior to the meals, the participating volunteer's tissue was saturated with folates to achieve a significant response of plasma folate to the meals. After consumption of meals A and B a significant rise in folate plasma level compared to meal C (mean level at 28 microg/ml) was observed. The relative bioavailability of folate following meal A exceeded significantly the suggested value of 50% for food folates by taking the dose-normalized area under the curve (AUC) following ingestion of meal B as reference. PMID:12860024

Rychlik, Michael; Netzel, Michael; Pfannebecker, Inga; Frank, Thomas; Bitsch, Irmgard

2003-07-25

197

[Determination of the percentage of grain whisky in commercial whiskies by isotopic mass spectrometry].  

PubMed

Commercial whisky is generally a blend between malt whisky and grain whisky. Corn is one of the main sources of grain and it is now well known that in corn the carbon dioxide assimilation proceeds through carboxylation of phosphoenolpyruvate but in many other plants like barley atmospheric carbon dioxide is fixed on ribulose 1,5 diphosphate. Each pathway of carbon dioxide assimilation is characterized by a fractionation factor of carbon isotopes. Consequently, the organic matter and also the fermentation alcohol of corn or barley show different 13C/12C ratio. The determination of the 13C/12C ratio in the alcohol of blended whisky allows the determination of the percentage of corn whisky. PMID:754596

Koziet, J; Bricout, J; Azoulay, N

1978-01-01

198

Measurement uncertainty in single, double and triple isotope dilution mass spectrometry.  

PubMed

Triple IDMS has been applied for the first time to the quantification of element concentrations. It has been compared with single and double IDMS obtained on the same sample set in order to evaluate the advantages and disadvantages of triple IDMS over single and double IDMS as an analytical reference procedure. The measurement results of single, double and triple IDMS are indistinguishable, considering rounding due to the individual measurement uncertainties. As expected, the relative expanded uncertainties (k?=?2) achieved with double IDMS (0.08%) are dramatically smaller than those obtained with single IDMS (1.4%). Triple IDMS yields the smallest relative expanded uncertainties (k?=?2, 0.077%) unfortunately at the expense of a much higher workload. Nevertheless triple IDMS has the huge advantage that the isotope ratio of the spike does not need to be determined. Elements with high memory effects, highly enriched spikes or highest metrological requirements may be typical applications for triple IDMS. PMID:22223313

Vogl, Jochen

2012-02-15

199

Development of a simple, fast, and accurate method for the direct quantification of selective estrogen receptor modulators using stable isotope dilution mass spectrometry.  

PubMed

A rapid analytical procedure was developed to quantify major selective estrogen receptor modulators (SERMs) simultaneously using stable isotope dilution mass spectrometry (SID-LCMS). Two novel isotopically labeled (SIL) analogues of natural SERMs, genistein and daidzein, were synthesized using a H/D exchange reaction mechanism. Computational chemistry coupled with MS and NMR data confirmed the site and mechanism of deuteration. The SIL analogues, which were mono- and dideutero substituted at the ortho positions, exhibited minimal deuterium isotope effects and were stable under the employed sample preparation protocol and MS analysis. An isotopic overlap correction was successfully employed to improve the accuracy and precision of the analytical method. The developed method, which was found to be sensitive, selective, precise and accurate, could be a valuable tool for research focused on determining the bioavailability of individual SERMs. PMID:23805827

Yerramsetty, Vamsidhar; Roe, Mikel; Cohen, Jerry; Hegeman, Adrian; Ismail, Baraem

2013-07-24

200

Mass fractionation processes of transition metal isotopes  

Microsoft Academic Search

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper

X. K. Zhu; Y. Guo; R. J. P. Williams; R. K. O’Nions; A. Matthews; N. S. Belshaw; G. W. Canters; E. C. de Waal; U. Weser; B. K. Burgess; B. Salvato

2002-01-01

201

Development and validation of a new analytical method for the determination of 1,4-dichlorobenzene in honey by gas chromatography–isotope dilution mass spectrometry after steam-distillation  

Microsoft Academic Search

A simple, fast, sensitive and robust analytical method using gas chromatography (GC)–isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography–mass spectrometry (GC–MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled

E. V. Botitsi; P. N. Kormali; S. N. Kontou; A. Economou; D. F. Tsipi

2006-01-01

202

Quantification of the H7N7 Influenza Hemagglutinin and Neuraminidase by Isotope-Dilution Mass Spectrometry  

PubMed Central

Influenza vaccination is the primary method for preventing influenza and its severe complications. Government agencies dedicate much time and resources to surveillance of circulating influenza strains and try to predict which strains would be most likely to be transmitted among humans in order to develop a safe and effective influenza vaccine each year. Influenza viral strains undergo rapid mutations and may experience an abrupt change in the surface proteins hemagglutinin (HA) and neuraminidase (NA), which can result in a virus that is radically different from those previously circulating in human populations. This is the reason that seasonal vaccines must be annually updated. The mutations and their effects on the virus and its subsequent transmissibility to or between humans cannot be adequately foreseen. Thus, the strategy of predicting which strain of influenza may cause the next worldwide pandemic so that vaccines can be manufactured and stockpiled prior to the emergence of an influenza pandemic may not be successful. It is instead, imperative that the process of producing a vaccine that will protect the public in the face of an unpredicted virus strain be streamlined and as swift as possible. We have developed an isotope dilution mass spectrometry method to quantify HA and NA in H7N7 influenza samples. The IDMS method involves enzymatic digestion of viral proteins and the specific detection of target peptides. Four HA peptides and two NA peptides of the H7N7 influenza strain were used in the analysis to ensure complete digestion of the protein, verify accuracy of the measurement, and provide flexibility in the case of amino acid changes among H7N7 strains. The IDMS method is an accurate, precise, sensitive, and selective method to quantify the amount of HA and NA antigens in crude allantoic fluid, purified virus samples, and final vaccine presentations.

Williams, T.; Pirkle, J.; Barr, J.; Santana, Wanda

2013-01-01

203

Isotope Ratio Measurement of Uranium in Safeguards Environmental Samples by Inductively-Coupled Plasma Mass Spectrometry (ICP-MS)  

Microsoft Academic Search

In order to measure isotope ratio of uranium in safeguards environmental samples with ICP-MS precisely, production of polyatomic ions of IrAr, PtAr and AuAr was measured and mass bias of ICP-MS is investigated by using isotopic standards of uranium and lead. The intensities of IrAr, PtAr and AuAr relative to the atomic ions were found to be 1.8×10?6 ,1 .6×10?5

Masaaki MAGARA; Takaaki SAKAKIBARA; Setsumi KUROSAWA; Masato TAKAHASHI; Satoshi SAKURAI; Yukiko HANZAWA; Fumitaka ESAKA; Kazuo WATANABE; Shigekazu USUDA

2002-01-01

204

Isotope Ratio Measurement of Uranium in Safeguards Environmental Samples by Inductively-Coupled Plasma Mass Spectrometry (ICP-MS)  

Microsoft Academic Search

In order to measure isotope ratio of uranium in safeguards environmental samples with ICP-MS precisely, production of polyatomic ions of IrAr, PtAr and AuAr was measured and mass bias of ICP-MS is investigated by using isotopic standards of uranium and lead. The intensities of IrAr, PtAr and AuAr relative to the atomic ions were found to be 1.8×10, 1.6×10 and

Masaaki MAGARA; Takaaki SAKAKIBARA; Setsumi KUROSAWA; Masato TAKAHASHI; Satoshi SAKURAI; Yukiko HANZAWA; Fumitaka ESAKA; Kazuo WATANABE; Shigekazu USUDA

2002-01-01

205

Elemental analyses of soil and sediment fused with lithium borate using isotope dilution laser ablation-inductively coupled plasma-mass spectrometry.  

PubMed

Quantitative analysis using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remains challenging primarily due to the lack of appropriate reference materials available for the wide variety of samples of interest and to elemental fractionation effects. Isotopic dilution mass spectrometry (IDMS) is becoming the methodology of choice to address these issues because the different isotopes of an element represent near-perfect internal standards. In this work, we investigated the lithium borate fusion of powdered solid samples, including soils, sediments, rock mine waste and a meteorite, as a strategy to homogenously distribute, i.e. equilibrate the elements and the added isotopically enriched standards. A comparison of this methodology using two pulsed laser ablation systems (ArF* excimer and Nd:YAG) with different wavelengths as well as two ICP-MS instruments (quadrupole and double-focusing sector field) was performed. Emphasis was put on using standard equipment to show the potential of the proposed strategy for its application in routine laboratories. Cr, Zn, Ba, Sr and Pb were successfully determined by LA-ICP-IDMS in six Standard Reference Materials (SRMs) representing different matrices of environmental interest. Experimental results showed the SRM fused glasses exhibited a low level of heterogeneity (intra- and inter-sample) for both natural abundance and isotopically enriched samples (RSD <3%, n=3, 1?). A good agreement between experimental results and the certified values was also observed. PMID:23953208

Malherbe, Julien; Claverie, Fanny; Alvarez, Aitor; Fernandez, Beatriz; Pereiro, Rosario; Molloy, John L

2013-09-01

206

Conceptual Study on New Isotope Analysis Technique with Resonance Ionization Mass Spectrometry Using Inductively Coupled Plasma as an Atomic Source (ICP-RIMS)  

SciTech Connect

We have proposed the novel isotope analysis technique with Resonance Ionization Mass Spectrometry using Inductively Coupled Plasma as an atomic source (ICP-RIMS). Each component of ICP-RIMS is conceptually designed. We conclude that the orthogonal acceleration time-of-flight mass spectrometer (oa-TOF-MS) driven by a high-repetition-rate pulsed laser would be suitable system for ICP-RIMS. We, additionally, suggest that the first vacuum stage of the vacuum interface, which is between the sampling and skimmer cones, is desired to maintain as low pressure as possible in order to suppress the Doppler broadening and to skim the supersonic jet effectively.

Watanabe, K.; Uritani, A. [Department of Materials, Physics and Energy Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 (Japan); Higuchi, Y.; Tomita, H.; Kawarabayashi, J.; Iguchi, T. [Department of Quantum Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, 464-8603 (Japan)

2009-03-17

207

Accuracy in the isotope dilution mass spectrometry of uranium in rubidium uranium sulphate Rb[sub 2]U(SO[sub 4])[sub 3  

SciTech Connect

Problems encountered in the determination of uranium in rubidium uranium sulphate (Rb[sub 2]U(SO[sub 4])[sub 3]) employing isotope dilution thermal ionization mass spectrometry (ID-TIMS) are discussed. The positive bias of 0.2 to 0.3% in the determination of uranium in Rb[sub 2]U(SO[sub 4])[sub 3] by ID-TIMS with respect to the stoichiometric composition has been resolved by modifying the chemical exchange procedures. The concentration of uranium in Rb[sub 2]U(SO[sub 4])[sub 3] could be determined with an accuracy better than 0.1% employing the HClO[sub 4] treatment for proper isotopic exchange between the spike and sample isotopes. 12 refs., 1 fig., 5 tabs.

Ramakumar, K.L.; Jeyakumar, S.; Raman, V.A.; Gnanayyan, L.; Rao, R.; Saxena, M.K.; Kavimandan, V.D.; Jain, H.C. (Bhabha Atomic Research Centre, Bombay (India))

1993-05-01

208

Development of a stable isotope approach for the inductively coupled plasma-mass spectrometry determination of oxidized metallothionein in biological materials.  

PubMed

The use of isotope dilution analysis (IDA) with inductively coupled plasma-mass spectrometry (ICP-MS) for the determination of oxidized metallothionein (MT) by a Cd-saturation method is investigated. The method developed here is a modification of an earlier methodology which used a radioactive Cd isotope ((109)Cd). While retaining the many advantages of this previous approach, the procedure presented here uses stable isotope ratio measurements ((114)Cd/(111)Cd) for the determination of MT. Experimental parameters governing the instrumental precision and accuracy for isotope ratio measurements of Cd by ICP-MS were characterized. Systematic errors, including mass bias, detector dead time, and spectroscopic interferences, could be easily corrected. The isotope dilution ICP-MS method was validated by the determination of very low levels of cadmium in biological certified reference materials (NIST SRM 2670 freeze-dried urine, IAEA H-8 horse kidney, and BCR TP-25 lichens). Finally, the IDA procedure was evaluated for the determination of oxidized MT by a Cd-saturation method previously developed using radioactive (109)Cd. The final procedure was applied to the quantification of MT in Long-Evans Cinnamon rat liver cytosol samples and the results were compared with data obtained for the same samples using the reference (109)Cd methodology. A good agreement between the analytical values obtained by both methods was observed. PMID:10873273

Valles Mota, J P; Linde Arias, A R; Fernández de la Campa, M R; García Alonso, J I; Sanz-Medel, A

2000-07-01

209

MASS SPECTROMETRY IN ENVIRONMENTAL SCIENCES  

EPA Science Inventory

This review covers applications of mass spectrometry to the environmental sciences. From the early applications of mass spectrometry to environmental research in the 1960s and 1970s, mass spectrometry has played an important role in aiding our understanding of environmental poll...

210

A robust methodology for high precision isotopic analysis of boron by thermal ionization mass spectrometry using Na2BO2+ ion  

NASA Astrophysics Data System (ADS)

A detailed study to develop a robust methodology for determining 11B/10B isotope ratio using sodium metaborate (Na2BO2+) in positive thermal ionisation mass spectrometry (P-TIMS) was performed. Different parameters of sample preparation and sample loading procedure, using single tantalum filament assembly, were optimized and their effects on ion intensity and precision in isotope ratio were evaluated. A comparative evaluation of precision achievable using Na2CO3 and NaCl to adjust the B/Na mole ratio in the sample was also carried out. This was done to confirm the robustness of the approach for analysing different kinds of sample matrices e.g., solids and solutions which require chemical purification and pre-concentration prior to TIMS analysis. NIST isotopic reference material SRM-951 with 11B/10B isotope ratio of 4.044 +/- 0.003 was used for various experiments. Loading of boron in the form of boromannitol complex along with sodium carbonate (for solid samples) and with NaCl (for solutions) on the graphite coated single tantalum filament assembly was found to give high precision (better than 1[per mille sign]) in the isotope ratios using 500 ng to 1 [mu]g of boron. The results were not influenced by variations in the B/Na mole ratio, which is an important aspect of using this methodology for analyzing unknown samples. Robustness of the developed methodology is demonstrated by analyzing solid samples as well as solutions for boron isotopic composition.

Rao, Radhika M.; Parab, Ankush R.; Sasibhushan, K.; Aggarwal, Suresh K.

2009-08-01

211

Biological Cluster Mass Spectrometry  

PubMed Central

This article reviews the new physics and new applications of secondary ion mass spectrometry using cluster ion probes. These probes, particularly C60, exhibit enhanced molecular desorption with improved sensitivity owing to the unique nature of the energy-deposition process. In addition, these projectiles are capable of eroding molecular solids while retaining the molecular specificity of mass spectrometry. When the beams are microfocused to a spot on the sample, bioimaging experiments in two and three dimensions are feasible. We describe emerging theoretical models that allow the energy-deposition process to be understood on an atomic and molecular basis. Moreover, experiments on model systems are described that allow protocols for imaging on biological materials to be implemented. Finally, we present recent applications of imaging to biological tissue and single cells to illustrate the future directions of this methodology. PMID:20055679

Winograd, Nicholas; Garrison, Barbara J.

2010-01-01

212

Development of isotope dilution-liquid chromatography/mass spectrometry combined with standard addition techniques for the accurate determination of tocopherols in infant formula.  

PubMed

During the development of isotope dilution-liquid chromatography/mass spectrometry (ID-LC/MS) for tocopherol analysis in infant formula, biased measurement results were observed when deuterium-labeled tocopherols were used as internal standards. It turned out that the biases came from intermolecular H/D exchange and intramolecular H/D scrambling of internal standards in sample preparation processes. Degrees of H/D exchange and scrambling showed considerable dependence on sample matrix. Standard addition-isotope dilution mass spectrometry (SA-IDMS) based on LC/MS was developed in this study to overcome the shortcomings of using deuterium-labeled internal standards while the inherent advantage of isotope dilution techniques is utilized for the accurate recovery correction in sample preparation processes. Details of experimental scheme, calculation equation, and uncertainty evaluation scheme are described in this article. The proposed SA-IDMS method was applied to several infant formula samples to test its validity. The method was proven to have a higher-order metrological quality with providing very accurate and precise measurement results. PMID:23830431

Lee, Joonhee; Jang, Eun-Sil; Kim, Byungjoo

2013-07-17

213

Determination of the 87Sr/86Sr isotope ratio in USGS silicate reference materials by multi-collector ICP-mass spectrometry  

NASA Astrophysics Data System (ADS)

Multi-collector ICP-mass spectrometry (MC-ICP-MS) was used for 87Sr/86Sr isotope ratio determination in newly introduced silicate reference materials from the US Geological Survey (USGS): granite G-3, andesite AGV-2, and basalt BCR-2. Next to the SrCO3 isotopic standard NIST SRM 987, also analogous USGS reference materials from the previous generation, and for which reference 87Sr/86Sr data obtained by TIMS are available, were analysed for validation purposes. Sample preparation consisted of acid digestion and subsequent isolation of Sr by means of a dedicated and commercially available crown ether-based resin. The Sr fractions thus obtained were analysed via MC-ICP-MS whereby mass discrimination was corrected for internally, while the isobaric interference at a mass-to-charge ratio of 86 caused by Kr impurities in the Ar gas was mathematically corrected for by using the signal for a Kr isotope free from spectral overlap. Finally, also the effect of the small amount of Rb that may still be present in the Sr fraction was corrected for mathematically on the basis of the signal intensity for 85Rb. The MC-ICP-MS results for G-2, AGV-1 and BCR-1 showed an excellent agreement with the corresponding TIMS values (<0.003% bias in all cases), such that it can be assumed that also the 87Sr/86Sr isotope ratio results obtained for the new reference materials are reliable.

Balcaen, Lieve; Schrijver, Isabel De; Moens, Luc; Vanhaecke, Frank

2005-04-01

214

Evaluation of the n(235U)/n(238U) isotope ratio measurements in a set of uranium samples by thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

The measurement of n(235U)/n(238U) isotope amount ratio in a set of representative uranium samples with enrichment levels ranging from 0.5 to 20.0 wt.% of 235U was carried out by thermal ionization mass spectrometry using the traditional and the total evaporation methods. The uncertainties of the measurement results were evaluated according to the recommendations of the ISO guide to the expression of uncertainty in measurement. They were then compared to the requirements of the IAEA international target values for measurement uncertainties in safeguarding nuclear materials.

de Oliveira, O. Pereira; Bolle, W. De; Richter, S.; Alonso, A.; Kühn, H.; Sarkis, J. E. S.; Wellum, R.

2005-11-01

215

Further development of IDGS: Isotope dilution gamma-ray spectrometry  

NASA Astrophysics Data System (ADS)

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 percent for Pu-239 and Pu-240 isotopic analyses and approximately 1 percent for the plutonium concentration analysis.

Li, T. K.; Parker, J. L.; Kuno, Y.; Sato, S.; Kamata, M.; Akiyama, T.

216

Practical and theoretical considerations in the gas chromatography/combustion/isotope ratio mass spectrometry delta(13)C analysis of small polyfunctional compounds.  

PubMed

Carbohydrates and proteins are among the most abundant naturally occurring biomolecules and so suitable methods for their reliable stable isotope analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) are required. Due to the non-volatile nature of these compounds they require hydrolytic cleavage to their lower molecular weight subunits and derivatisation prior to GC/C/IRMS analysis. The addition of carbon to the molecules and any kinetic isotopic fractionation associated with derivatisation must be accounted for in order to provide meaningful stable isotope values and estimates of propagated errors. To illustrate these points amino acid trifluoroacetate/isopropyl esters and alditol acetates were prepared from authentic amino acids and monosaccharides, respectively. As predicted from the derivatisation reaction mechanisms, a kinetic isotope effect was observed which precludes direct calculation of delta(13)C values of the amino acids and monosaccharides by simple mass balance equations. This study shows that the kinetic isotope effect associated with derivatisation is both reproducible and robust, thereby allowing the use of correction factors. We show how correction factors can be determined and accurately account for the addition of derivative carbon. As a consequence of the addition of a molar excess of carbon and the existence of a kinetic isotope effect during derivatisation, errors associated with determined delta(13)C values must be assessed. We illustrate how such errors can be quantified (for monosaccharides +/-1.3 per thousand and for amino acids between +/-0.8 per thousand and +/-1.4 per thousand). With the magnitude of the errors for a given delta(13)C value of a monosaccharide or amino acid quantified, it is possible to make reliable interpretations of delta(13)C values, thereby validating the determination of delta(13)C values of amino acids as TFA/IP esters and monosaccharides as alditol acetates. PMID:11319796

Docherty, G; Jones, V; Evershed, R P

2001-01-01

217

Determination of uranium isotopic ratios in biological samples using laser ablation inductively coupled plasma double focusing sector field mass spectrometry with cooled ablation chamber  

NASA Astrophysics Data System (ADS)

An analytical procedure has been proposed for the determination of precise uranium isotope ratios in a thin uranium layer on a biological surface by laser ablation inductively coupled plasma sector field mass spectrometry (LA-ICP-MS). A cooled laser ablation chamber using a Peltier element was developed in order to analyze element distribution in thin cross-sections of frozen tissues with a lateral resolution in the [mu]m range. In order to study the figures of merit of LA-ICP-MS with the cooled laser ablation chamber, one drop (20 [mu]L, U concentration 200 ng mL-1), each of the certified isotope reference materials NIST U350 and NIST U930, the uranium isotopic standard CCLU-500 and also a drop of uranium with a natural isotopic pattern was deposited and analyzed on the biological surface (flower leaf). The precision and accuracy of isotope ratio measurements are significantly improved using cooled laser ablation chamber in comparison to non-cooled chamber. The precision of the measurements of isotope ratios in the range of 2.0-1.6% for 234U/238U, 1.3-0.4% for 235U/238U and 2.1-1.0% for 236U/238U in selected uranium isotopic standards reference material were determined by microlocal analysis (diameter of laser ablation crater: 15, 25 and 50 [mu]m) using LA-ICP-MS with a cooled laser ablation chamber. The accuracy of 234U/238U, 235U/238U and 236U/238U isotope ratio measurements varied in the range of 4.2-1.1%, 2.4-0.5% and 4.8-1.1%, respectively, and were dependent on the diameter of the laser beam used.

Zoriy, M. V.; Kayser, M.; Izmer, A.; Pickhardt, C.; Becker, J. S.

2005-04-01

218

Mass Spectrometry Video  

NSDL National Science Digital Library

This video, distributed on YouTube by the Royal Society of Chemistry is on the basic principles of mass spectrometry, using a magnetic sector instrument to demonstrate how specific m/z ratios can be selected. The theory and operation of MS, including the chemistry of ionization and fragmentation is described at an introductory level. There is also an excellent example of the use of high resolution MS to differentiate between nominal mass and actual mass. The video does a very good job of explaining the concept such that only a little background knowledge is required. The video is short enough (6 mins), that it would be very useful in a class setting or for students outside of class. The ultimate strength of this video is the general nature of the content that makes it appealing to a wide audience. The video may be most appropriate in a lower-level general education science course (i.e forensic science) or as a quick orientation video for instrumental analysis students prior to introducing mathematical or operational concepts. This video would also be helpful for a lay science person who wishes to learn more about mass spectrometry from a general interest perspective.

2011-06-08

219

Neuroscience and Accelerator Mass Spectrometry  

SciTech Connect

Accelerator mass spectrometry (AMS) is a mass spectrometric method for quantifying rare isotopes. It has had great impact in geochronology and archaeology and is now being applied in biomedicine. AMS measures radioisotopes such as {sup 3}H, {sup 14}C, {sup 26}Al, {sup 36}Cl and {sup 41}Ca, with zepto- or attomole sensitivity and high precision and throughput, enabling safe human pharmacokinetic studies involving: microgram doses, agents having low bioavailability, or toxicology studies where administered doses must be kept low (<1 {micro}g/kg). It is used to study long-term pharmacokinetics, to identify biomolecular interactions, to determine chronic and low-dose effects or molecular targets of neurotoxic substances, to quantify transport across the blood-brain barrier and to resolve molecular turnover rates in the human brain on the timescale of decades. We will here review how AMS is applied in neurotoxicology and neuroscience.

Palmblad, M N; Buchholz, B A; Hillegonds, D J; Vogel, J S

2004-08-02

220

Resonance ionization mass spectrometry of ion beam sputtered neutrals for element- and isotope-selective analysis of plutonium in micro-particles.  

PubMed

Micro-particles containing actinides are of interest for risk assessments of contaminated areas, nuclear forensic analyses, and IAEA as well as Euratom safeguards programs. For their analysis, secondary ion mass spectrometry (SIMS) has been established as the state-of-the-art standard technique. In the case of actinide mixtures within the particles, however, SIMS suffers from isobaric interferences (e.g., (238)U/(238)Pu, (241)Am/(241)Pu). This can be eliminated by applying resonance ionization mass spectrometry which is based on stepwise resonant excitation and ionization of atoms with laser light, followed by mass spectrometric detection of the produced ions, combining high elemental selectivity with the analysis of isotopic compositions. This paper describes the instrumental modifications for coupling a commercial time-of-flight (TOF)-SIMS apparatus with three-step resonant post-ionization of the sputtered neutrals using a high-repetition-rate (kHz) Nd:YAG laser pumped tunable titanium:sapphire laser system. Spatially resolved ion images obtained from actinide-containing particles in TOF-SIMS mode demonstrate the capability for isotopic and spatial resolution. Results from three-step resonant post-ionization of bulk Gd and Pu samples successfully demonstrate the high elemental selectivity of this process. PMID:19557397

Erdmann, N; Kratz, J-V; Trautmann, N; Passler, G

2009-11-01

221

An inexpensive, fast, and reliable method for vacuum extraction of soil and plant water for stable isotope analyses by mass spectrometry.  

PubMed

The stable isotopes of water (hydrogen and oxygen isotopes) are of utmost interest in ecology and the geosciences. In many cases water has to be extracted directly from a matrix such as soil or plant tissue before isotopes can be analyzed by mass spectrometry. Currently, the most widely used technique for water is cryogenic vacuum extraction. We present a simple and inexpensive modification of this method and document tests conducted with soils of various grain size and tree core replicates taken on four occasions during 2010. The accuracies for sandy soils are between 0.4‰ and 3‰ over a range of 21‰ and 165‰ for ?(18)O and ?(2)H, respectively. Spiking tests with water of known isotope composition were conducted with soil and tree core samples; they indicate reliable precision after an extraction time of 15?min for sandy soils. For clayey soils and tree cores, the deviations were up to 0.63‰ and 4.7‰ for ?(18)O and ?(2)H, respectively. This indicates either that the extraction time should be extended or that mechanisms different from Rayleigh fractionation play a role. The modified protocol allows a fast and reliable extraction of large numbers of water samples from soil and plant material in preparation for stable isotope analyses. PMID:21953958

Koeniger, Paul; Marshall, John D; Link, Timothy; Mulch, Andreas

2011-10-30

222

Rapid Communications in Mass Spectrometry Revised version. May 4nd  

E-print Network

Water trap - 100°C CO2 m/z = 44, 45, 46 Gas Chromatography Combustion Isotope Ratio Mass Spectrometry and intramolecular levels, this paper reviews selected applications of compound-specific isotope analysis in various, the development of gas chromatography coupled to a combustion furnace then to an isotope ratio mass spectrometer3

Paris-Sud XI, Université de

223

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.  

PubMed

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

2014-08-01

224

Multidimensional enantio gas chromtography/mass spectrometry and gas chromatography-combustion-isotopic ratio mass spectrometry for the authenticity assessment of lime essential oils (C. aurantifolia Swingle and C. latifolia Tanaka).  

PubMed

This article focuses on the genuineness assessment of Lime oils (Citrus aurantifolia Swingle and C. latifolia Tanaka), by Multi Dimensional Gas Chromatography (MDGC) to determine the enantiomeric distribution of ?-thujene, camphene, ?-pinene, sabinene, ?-phellandrene, ?-phellandrene, limonene, linalool, terpinen-4-ol, ?-terpineol and by gas chromatography-combustion isotope ratio mass spectrometry (GC-C-IRMS) to determine the isotopic ratios of ?-pinene, ?-pinene, limonene, ?-terpineol, neral, geranial, ?-caryophyllene, trans-?-bergamotene, germacrene B. To the author's knowledge this is the first attempt to assess the authenticity and differentiate Persian Lime from Key lime oils by GC-C-IRMS. The results of the two analytical approaches were compared. The simultaneous use of the two techniques provides more reliable capability to detect adulteration in Citrus essential oils. In fact, in some circumstance only one of the two techniques allows to discriminate adulterated or contaminated oils. In cases where only small anomalies are detected by the two techniques due to subtle adulterations, their synergic use allows to express judgments. The advantage of both techniques is the low number of components the analyst must evaluate, reducing the complexity of the data necessary to deal with. Moreover, the conventional analytical approach based on the evaluation of the whole volatile fraction can fail to reveal the quality of the oils, if the adulteration is extremely subtle. PMID:22088669

Bonaccorsi, Ivana; Sciarrone, Danilo; Schipilliti, Luisa; Dugo, Paola; Mondello, Luigi; Dugo, Giovanni

2012-02-24

225

Accelerator mass spectrometry  

SciTech Connect

Accelerator mass spectroscopy (AMS) can be used for efficient detection of long-lived isotopes at part-per-quadrillion sensitivities with good precision. In this article we present an overview of AMS and its recent use in archaeology, geochemistry and biomolecular tracing. All AMS systems use cesium sputter ion sources to produce negative ions from a small button of a solid sample containing the element of interest, such as graphite, metal halide, or metal oxide, often mixed with a metal powder as binder and thermal conductor. Experience shows that both natural and biomedical samples are compatible in a single AMS system, but few other AMS sites make routine {sup 14}C measurements for both dating and tracing. AMS is, in one sense, just `a very sensitive decay counter`, but if AMS sensitivity is creatively coupled to analytical chemistry of certain isotopes, whole new areas of geosciences, archaeology, and life sciences can be explored. 29 refs., 2 figs., 1 tab.

Vogel, J.S.; Turteltaub, K.W.; Finkel, R. [Lawrence Livermore National Lab., CA (United States); Nelson, D.E.

1995-06-01

226

Mass Spectrometry of Glycans  

PubMed Central

Powerful new strategies based on mass spectrometry are revolutionizing the structural analysis and profiling of glycans and glycoconjugates. We survey here the major biosynthetic pathways that underlie the biological diversity in glycobiology, with emphasis on glycoproteins, and the approaches that can be used to address the resulting heterogeneity. Included among these are derivatizations, on- and off-line chromatography, electrospray and matrix-assisted laser desorption/ionization, and a variety of dissociation methods, the recently introduced electron-based techniques being of particular interest. PMID:24010834

Han, Liang; Costello, Catherine E.

2014-01-01

227

Method development for the redox speciation analysis of iron by ion chromatography-inductively coupled plasma mass spectrometry and carryover assessment using isotopically labeled analyte analogues.  

PubMed

An ion chromatography-inductively coupled plasma mass spectrometry (IC-ICP-MS) method was developed for the redox speciation analysis of iron (Fe) based on in-column complexation of Fe(2+) and Fe(3+) by dipicolinic acid (DPA). The effects of column type, mobile phase composition and molecular ion interference were studied in the method optimization. The carryover of the target species in the IC-ICP-MS method was uniquely and effectively evaluated using isotopically enriched analogues of the analytes ((54)Fe(2+) and (57)Fe(3+)). Standard solutions of the enriched standards were injected into the system following analysis of a sample, and the ratios of the isotopes of iron in the enriched standards were calculated based on the chromatographic peak areas. The concentrations of the analytes carried over from the sample to the enriched standards were determined using the quantitative relationship in isotope dilution mass spectrometry (IDMS). In contrast to the routine way of evaluating carryover effect by injecting a blank solution after sample analysis, the use of isotopically enriched standards identified significant analyte carryover in the present method. Extensive experiments were carried out to systematically identify the source of the carryover and to eliminate the problem; the separation column was found to be the exclusive source. More than 95% of the analyte carryover was eliminated by reducing the length of the column. The detection limit of the IC-ICP-MS method (MDL) for the iron species was 2ngg(-1). The method was used to determine Fe(2+) and Fe(3+) in synthetic aqueous standard solutions and a beverage sample. PMID:24819017

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

2014-06-20

228

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

SciTech Connect

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

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

2012-01-15

229

Inorganic trace analysis by mass spectrometry  

NASA Astrophysics Data System (ADS)

Mass spectrometric methods for the trace analysis of inorganic materials with their ability to provide a very sensitive multielemental analysis have been established for the determination of trace and ultratrace elements in high-purity materials (metals, semiconductors and insulators), in different technical samples (e.g. alloys, pure chemicals, ceramics, thin films, ion-implanted semiconductors), in environmental samples (waters, soils, biological and medical materials) and geological samples. Whereas such techniques as spark source mass spectrometry (SSMS), laser ionization mass spectrometry (LIMS), laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), glow discharge mass spectrometry (GDMS), secondary ion mass spectrometry (SIMS) and inductively coupled plasma mass spectrometry (ICP-MS) have multielemental capability, other methods such as thermal ionization mass spectrometry (TIMS), accelerator mass spectrometry (AMS) and resonance ionization mass spectrometry (RIMS) have been used for sensitive mono- or oligoelemental ultratrace analysis (and precise determination of isotopic ratios) in solid samples. The limits of detection for chemical elements using these mass spectrometric techniques are in the low ng g -1 concentration range. The quantification of the analytical results of mass spectrometric methods is sometimes difficult due to a lack of matrix-fitted multielement standard reference materials (SRMs) for many solid samples. Therefore, owing to the simple quantification procedure of the aqueous solution, inductively coupled plasma mass spectrometry (ICP-MS) is being increasingly used for the characterization of solid samples after sample dissolution. ICP-MS is often combined with special sample introduction equipment (e.g. flow injection, hydride generation, high performance liquid chromatography (HPLC) or electrothermal vaporization) or an off-line matrix separation and enrichment of trace impurities (especially for characterization of high-purity materials and environmental samples) is used in order to improve the detection limits of trace elements. Furthermore, the determination of chemical elements in the trace and ultratrace concentration range is often difficult and can be disturbed through mass interferences of analyte ions by molecular ions at the same nominal mass. By applying double-focusing sector field mass spectrometry at the required mass resolution—by the mass spectrometric separation of molecular ions from the analyte ions—it is often possible to overcome these interference problems. Commercial instrumental equipment, the capability (detection limits, accuracy, precision) and the analytical application fields of mass spectrometric methods for the determination of trace and ultratrace elements and for surface analysis are discussed.

Becker, Johanna Sabine; Dietze, Hans-Joachim

1998-10-01

230

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.

1984-05-01

231

High precision uranium, thorium and radium isotope ratio measurements by high dynamic range thermal ionisation mass spectrometry  

NASA Astrophysics Data System (ADS)

Mass spectrometric methods are presented for the precise determination of the isotopic compositions of uranium, thorium and radium. M+ ions were produced by thermal ionisation. Analysis involved either a dynamic routine using the Daly detector or a static routine employing both the Daly detector and off-axis Faraday detectors. Instrument performance was assessed using a set of uranium standards, CBNM IRM 072. The response of the Daly detector was linear up to ratios of at least 5 × 104 and when operated dynamically it is ideally suited to the measurement of ion beams in the range 5-1 × 105 cps. The static mode of analysis was employed successfully for the measurement of isotope ratios up to 5 × 105.

Cohen, Anthony S.; Belshaw, Nicholas S.; O'Nions, R. Keith

1992-07-01

232

Isotopic tracer studies of oxygen transport through SiO2 films at 1000 °C using secondary ion mass spectrometry  

NASA Astrophysics Data System (ADS)

Dry oxides (?8 ppm H2O) grown on Si(100) at 1000 °C at 1 atm using purified 16O2 and purified 18O2 were analyzed using secondary ion mass spectrometry. 18O is observed at the interface, in the bulk of the 16O oxide, and at the surface in agreement with other recent reports. Our results show little lattice diffusion in agreement with Mikkelsen's work [Appl. Phys. Lett. 45, 1187 (1984)]. A previous report [J. Electrochem. Soc. 131, 1944 (1984)] of appreciable lattice diffusion is due to higher water content.

Han, C. J.; Helms, C. R.

1986-03-01

233

Correction for the 17O interference in ?(13C) measurements when analyzing CO2 with stable isotope mass spectrometry  

USGS Publications Warehouse

Measurements of ?(13C) determined on CO2 with an isotope-ratio mass spectrometer (IRMS) must be corrected for the amount of 17O in the CO2. For data consistency, this must be done using identical methods by different laboratories. This report aims at unifying data treatment for CO2 IRMS by proposing (i) a unified set of numerical values, and (ii) a unified correction algorithm, based on a simple, linear approximation formula. Because the oxygen of natural CO2 is derived mostly from the global water pool, it is recommended that a value of 0.528 be employed for the factor ?, which relates differences in 17O and 18O abundances. With the currently accepted N(13C)/N(12C) of 0.011 180(28) in VPDB (Vienna Peedee belemnite) reevaluation of data yields a value of 0.000 393(1) for the oxygen isotope ratio N(17O)/N(16O) of the evolved CO2. The ratio of these quantities, a ratio of isotope ratios, is essential for the 17O abundance correction: [N(17O)/N(16O)]/[N(13C)/N(12C)] = 0.035 16(8). The equation [?(13C) ? 45?VPDB-CO2 + 2 17R/13R (45?VPDB-CO2 – ?46?VPDB-CO2)] closely approximates ?(13C) values with less than 0.010 ‰ deviation for normal oxygen-bearing materials and no more than 0.026 ‰ in extreme cases. Other materials containing oxygen of non-mass-dependent isotope composition require a more specific data treatment. A similar linear approximation is also suggested for ?(18O). The linear approximations are easy to implement in a data spreadsheet, and also help in generating a simplified uncertainty budget.

Coplen, Tyler B.; Brand, Willi A.; Assonov, Sergey S.

2010-01-01

234

Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin.  

PubMed

Copper is an essential trace metal that shows a vertical recycled-scavenged profile in the ocean. To help elucidate the biogeochemical cycling of Cu in the present and past oceans, it is important to determine the distribution of Cu isotopes in seawater. However, precise isotopic analysis of Cu has been impaired by the low concentrations of Cu as well as co-existing elements that interfere with measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The objective of this study is to develop a simple Cu pre-concentration method using Nobias-chelate PA1 resin (Hitachi High Technologies). This extraction followed by anion exchange, allows precise analysis of the Cu isotopic composition in seawater. Using this method, Cu was quantitatively concentrated from seawater and >99.9999% of the alkali and alkaline earth metals were removed. The technique has a low procedural blank of 0.70 ng for Cu for a 2L sample and the precision of the Cu isotopic analysis was ±0.07‰ (±2SD, n=6). We applied this method to seawater reference materials (i.e., CASS-5 and NASS-6) and seawater samples obtained from the northwestern Pacific Ocean. The range of dissolved ?(65)Cu was 0.40-0.68‰. PMID:23746405

Takano, Shotaro; Tanimizu, Masaharu; Hirata, Takafumi; Sohrin, Yoshiki

2013-06-19

235

Optimisation of derivatisation procedures for the determination of delta13C values of amino acids by gas chromatography/combustion/isotope ratio mass spectrometry.  

PubMed

Compound-specific stable carbon isotope analysis of amino acids by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) is a highly selective and sensitive method for probing the biosynthetic/diagenetic pathways, pool size and turnover rates of proteins, previously intractable to bulk isotope analyses. However, amino acids are polyfunctional, non-volatile compounds which require derivatisation prior to GC analysis. While a wide range of derivatives exist for the GC analysis of amino acids only a handful have been utilised for their GC/C/IRMS analysis. Significantly, none of those derivatives currently employed appear completely satisfactory and a thorough assessment of their relative utility is lacking. Seven derivatives (three previously reported and four novel) for obtaining delta(13)C values of amino acids via GC/C/IRMS analysis were compared. More specifically, standard mixtures of 15 protein amino acids were converted into N-acetylmethyl (NACME) esters, N-acetyl n-propyl (NANP) esters, N-acetyl i-propyl (NAIP) esters, N-trifluoroacetyl-i-propyl (TFA-IP) esters, N-pivaloyl methyl (NPME) esters, N-pivaloyl n-propyl (NPNP) esters and N-pivaloyl i-propyl (NPIP) esters. Each derivative was assessed with respect to its applicability to carbon isotope determinations of all the common alpha-amino acids, reaction yield, chromatographic resolution, stability, analyte-to-derivative carbon ratio, kinetic isotope effects and errors associated with their carbon isotope determinations. The NACME derivative was concluded to be the preferred derivative mainly due to the highest analyte-to-derivative carbon ratio being achieved, resulting in the lowest analytical errors for amino acid delta(13)C value determinations, ranging from +/-0.6 per thousand for phenylalanine, leucine and isoleucine to +/-1.1 per thousand for serine and glycine. PMID:17990247

Corr, Lorna T; Berstan, Robert; Evershed, Richard P

2007-01-01

236

Amino acid precursors from a simulated lower atmosphere of Titan, Experiments of cosmic ray energy source with 13C- and 18O-stable isotope probing mass spectrometry  

E-print Network

The organic haze of aerosols that shrouds the Saturnian moon Titan has previously been studied by both observations and laboratory simulation experiments. Here we report the abiotic formation of amino acid precursors in complex organic molecules during experimental simulation of the environment near Titan's surface with proton irradiation. Pyrolysis of the organic molecules formed in the simulated Titan atmosphere by proton irradiation at 600 degree-C yielded compounds that contained HCN and NH3. These experimental results are consistent with the molecular information obtained by pyrolysis gas chromatography-mass spectrometry (pyrolysis GC-MS) of samples collected by the Huygens probe to Titan. Scanning electron microscopy (SEM) and three-dimensional atomic force microscopy (AFM) images of the irradiation products reveal nanometer-scale filaments and globules in complex amorphous structures (approximately 1000 Da). Isotope probing experiments by matrix-assisted laser desorption ionization time-of-flight mass ...

Taniuchi, Toshinori; Kobayashi, Kensei

2013-01-01

237

Analysis of triclosan and triclocarban in human nails using isotopic dilution liquid chromatography-tandem mass spectrometry.  

PubMed

In this study, we were able to develop a simple analytical procedure to assay the presence of two antimicrobial agents, triclosan (TCS) and triclocarban (TCC), in human nails. Samples were digested using sodium hydroxide (NaOH), extracted using dichloromethane, and analyzed using ultra performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry operating in the negative ion mode. Mean recoveries were performed at three fortification levels ranging from 98.1% to 106.3% with relative standard deviations between 1.8% and 18.1% (n=6). The limits of quantification (LOQ) for the method were 2.0 and 0.2?g/kg for TCS and TCC, respectively. Both compounds were ubiquitously found in all real samples (n=20) with concentrations ranging from ?g/kg to several mg/kg. PMID:23911541

Shi, Ying; Liu, Xiangjun; Zhang, Jing; Shao, Bing

2013-09-01

238

Isotope ratio analysis of actinides, fission products, and geolocators by high-efficiency multi-collector thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

A ThermoFisher "Triton" multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotope ratio analysis of actinides (uranium, plutonium, and americium), fission products and geolocators (strontium, cesium, and neodymium). Total efficiencies (atoms loaded to ions detected) of up to 0.5-2% for U, Pu, and Am, and 1-30% for Sr, Cs, and Nd can be reported employing resin bead load techniques onto flat ribbon Re filaments or resin beads loaded into a millimeter-sized cavity drilled into a Re rod. This results in detection limits of <0.1 fg (104 atoms to 105 atoms) for 239-242+244Pu, 233+236U, 241-243Am, 89,90Sr, and 134,135,137Cs, and <=1 pg for natural Nd isotopes (limited by the chemical processing blank) using a secondary electron multiplier (SEM) or multiple-ion counters (MICs). Relative standard deviations (RSD) as small as 0.1% and abundance sensitivities of 1 × 106 or better using a SEM are reported here. Precisions of RSD [approximate]0.01-0.001% using a multi-collector Faraday cup array can be achieved at sub-nanogram concentrations for strontium and neodymium and are suitable to gain crucial geolocation information. The analytical protocols reported herein are of particular value for nuclear forensic and nuclear safeguard applications.

Bürger, S.; Riciputi, L. R.; Bostick, D. A.; Turgeon, S.; McBay, E. H.; Lavelle, M.

2009-09-01

239

Determination of carbon isotope ratios in amino acids, proteins, and oligosaccharides by inductively coupled plasma-mass spectrometry.  

PubMed

Carbon isotope ratios ((12)C/(13)C) are measured for aqueous solutions of tryptophan, myoglobin, and beta-cyclodextrin using C(+) ions from an inductively coupled plasma (ICP) and a prototype twin quadrupole mass spectrometer (MS). (13)C/(12)C ratios can be determined with a relative standard deviation (RSD) of approximately 1%. This precision is close to the limiting value predicted by counting statistics (1.16%). Spectral interference on (13)C(+), presumably from (12)C(1)H(+), comes from the incomplete dissociation of myoglobin and/or beta-cyclodextrin, but not tryptophan. Decreasing the aerosol gas flow rate slightly from that which yields maximum signal eliminates this (12)C(1)H(+) interference. The count rate of the minor isotope ((13)C(+)) can be artificially enhanced by increasing the voltage of the (13)C(+) detector, and/or by shifting the ion beam splitter offset from the central axis. Instrumental modifications to the MS that improve the sensitivity are also described. PMID:12686476

Luong, Elise T; Houk, R S

2003-04-01

240

Amino acid delta13C analysis of hair proteins and bone collagen using liquid chromatography/isotope ratio mass spectrometry: paleodietary implications from intra-individual comparisons.  

PubMed

We report a novel method for the chromatographic separation and measurement of stable carbon isotope ratios (delta(13)C) of individual amino acids in hair proteins and bone collagen using the LC-IsoLink system, which interfaces liquid chromatography (LC) with isotope ratio mass spectrometry (IRMS). This paper provides baseline separation of 15 and 13 of the 18 amino acids in bone collagen and hair proteins, respectively. We also describe an approach to analysing small hair samples for compound-specific analysis of segmental hair sections. The LC/IRMS method is applied in a historical context by the delta(13)C analysis of hair proteins and bone collagen recovered from six individuals from Uummannaq in Greenland. The analysis of hair and bone amino acids from the same individual, compared for the first time in this study, is of importance in palaeodietary reconstruction. If hair proteins can be used as a proxy for bone collagen at the amino acid level, this validates compound-specific isotope studies using hair as a model for palaeodietary reconstruction. Our results suggest that a small offset observed in the bulk delta(13)C values of the hair and bone samples may be attributed to two factors: (i) amino acid compositional differences between hair and bone proteins, and (ii) differential turnover rates of the tissues and the amino acid pools contributing to their synthesis. This application proposes that hair may be a useful complementary or alternative source of compound-specific paleodietary information. PMID:20131322

Raghavan, Maanasa; McCullagh, James S O; Lynnerup, Niels; Hedges, Robert E M

2010-03-15

241

Combining Capillary Electrophoresis Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry and Stable Isotopic Labeling Techniques for Comparative Crustacean Peptidomics  

PubMed Central

Herein we describe a sensitive and straightforward off-line capillary electrophoresis (CE) matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) interface in conjunction with stable isotopic labeling (SIL) technique for comparative neuropeptidomic analysis in crustacean model organisms. Two SIL schemes, including a binary H/D formaldehyde labeling technique and novel, laboratory-developed multiplexed dimethylated leucine-based isobaric tagging reagents, have been evaluated in these proof-of-concept experiments. We employ these isotopic labeling techniques in conjunction with CE-MALDI MS for quantitative peptidomic analyses of the pericardial organs isolated from two crustacean species, the European green crab Carcinus maenas and the blue crab Callinectes sapidus. Isotopically labeled peptide pairs are found to co-migrate in CE fractions and quantitative changes in relative abundances of peptide pairs are obtained by comparing peak intensities of respective peptide pairs. Several neuropeptide families exhibit changes in response to salinity stress, suggesting potential physiological functions of these signaling peptides. PMID:20334868

Wang, Junhua; Zhang, Yuzhuo; Xiang, Feng; Zhang, Zichuan; Li, Lingjun

2010-01-01

242

Combining capillary electrophoresis matrix-assisted laser desorption/ionization mass spectrometry and stable isotopic labeling techniques for comparative crustacean peptidomics.  

PubMed

Herein we describe a sensitive and straightforward off-line capillary electrophoresis (CE) matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) interface in conjunction with stable isotopic labeling (SIL) technique for comparative neuropeptidomic analysis in crustacean model organisms. Two SIL schemes, including a binary H/D formaldehyde labeling technique and novel, laboratory-developed multiplexed dimethylated leucine-based isobaric tagging reagents, have been evaluated in these proof-of-concept experiments. We employ these isotopic labeling techniques in conjunction with CE-MALDI-MS for quantitative peptidomic analyses of the pericardial organs isolated from two crustacean species, the European green crab Carcinus maenas and the blue crab Callinectes sapidus. Isotopically labeled peptide pairs are found to co-migrate in CE fractions and quantitative changes in relative abundances of peptide pairs are obtained by comparing peak intensities of respective peptide pairs. Several neuropeptide families exhibit changes in response to salinity stress, suggesting potential physiological functions of these signaling peptides. PMID:20334868

Wang, Junhua; Zhang, Yuzhuo; Xiang, Feng; Zhang, Zichuan; Li, Lingjun

2010-06-25

243

A high precision isotope ratio mass spectrometry method for measuring the O{sub 2}/N{sub 2} ratio of air  

SciTech Connect

Studies of the distribution of O{sub 2} in air will inform us about critical problems in the global carbon cycle which are not readily accessed by other measurements, including the rate of seasonal net production in the oceans on a hemispheric scale, the rate at which the oceans are taking up anthropogenic CO{sub 2}, and the net of change of the continental biomass. In this paper, we outline a method for measuring the O{sub 2}/N{sub 2} ratio of air to a standard error of {+-}6 per meg ({+-}0.006{per_thousand}) for a sample analyzed in quadruplicate, corresponding to {+-}1.2 ppmV O{sub 2} in air out of 210,000. The method involves measuring the ratio of {sup 16}O{sub 2} to {sup 15}N{sup 14}N by isotope ratio mass spectrometry. Potential and actual problems with this method include fractionation as sample and reference gases are introduced to the mass spectrometer, mass spectrometric nonlinearity, effects of imbalance of sample and reference ion currents on the measured isotopic ratio, isobaric interferences at masses 28 and 29 due to the formation of CO{sup +} from CO{sub 2} in the source, and zero enrichments. We discuss the magnitude of errors introduced by these factors and outline the relevant corrections. The ultimate mass spectrometric uncertainty is about {+-}2 per meg ({+-}0.4 ppmV) for a 1 h instrumental analysis. Overall precision is currently limited by fractionation as sample and reference gases are introduced into the mass spectrometer. A considerable improvement in precision may be possible.

Bender, M.L.; Ellis, J.T.; Orchardo, J. [Univ. of Rhode Island, Kingston, RI (United States)] [Univ. of Rhode Island, Kingston, RI (United States); Tans, P.P. [National Oceanic and Atmospheric Administration, Boulder, CO (United States)] [National Oceanic and Atmospheric Administration, Boulder, CO (United States); Habfast, K. [Finnigan MAT GmbH, Bremen (Germany)] [Finnigan MAT GmbH, Bremen (Germany)

1994-11-01

244

Development of SI-traceable C-peptide certified reference material NMIJ CRM 6901-a using isotope-dilution mass spectrometry-based amino acid analyses.  

PubMed

A certified reference material (CRM) is a higher-order calibration material used to enable a traceable analysis. This paper describes the development of a C-peptide CRM (NMIJ CRM 6901-a) by the National Metrology Institute of Japan using two independent methods for amino acid analysis based on isotope-dilution mass spectrometry. C-peptide is a 31-mer peptide that is utilized for the evaluation of ?-cell function in the pancreas in clinical testing. This CRM is a lyophilized synthetic peptide having the human C-peptide sequence, and contains deamidated and pyroglutamylated forms of C-peptide. By adding water (1.00 ± 0.01) g into the vial containing the CRM, the C-peptide solution in 10 mM phosphate buffer saline (pH 6.6) is reconstituted. We assigned two certified values that represent the concentrations of total C-peptide (mixture of C-peptide, deamidated C-peptide, and pyroglutamylated C-peptide) and C-peptide. The certified concentration of total C-peptide was determined by two amino acid analyses using pre-column derivatization liquid chromatography-mass spectrometry and hydrophilic chromatography-mass spectrometry following acid hydrolysis. The certified concentration of C-peptide was determined by multiplying the concentration of total C-peptide by the ratio of the relative area of C-peptide to that of the total C-peptide measured by liquid chromatography. The certified value of C-peptide (80.7 ± 5.0) mg/L represents the concentration of the specific entity of C-peptide; on the other hand, the certified value of total C-peptide, (81.7 ± 5.1) mg/L can be used for analyses that does not differentiate deamidated and pyroglutamylated C-peptide from C-peptide itself, such as amino acid analyses and immunochemical assays. PMID:22610603

Kinumi, Tomoya; Goto, Mari; Eyama, Sakae; Kato, Megumi; Kasama, Takeshi; Takatsu, Akiko

2012-07-01

245

?D and ?13C analyses of atmospheric volatile organic compounds by thermal desorption gas chromatography isotope ratio mass spectrometry.  

PubMed

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

2011-09-16

246

Amino acid precursors from a simulated lower atmosphere of titan: experiments of cosmic ray energy source with ¹³C- and ¹?O-stable isotope probing mass spectrometry.  

PubMed

The organic haze of aerosols that shrouds the Saturnian moon Titan has previously been studied by both observations and laboratory simulation experiments. Here we report the abiotic formation of amino acid precursors in complex organic molecules during experimental simulation of the environment near Titan's surface with proton irradiation. Pyrolysis of the organic molecules formed in the simulated Titan atmosphere by proton irradiation at 600°C yielded compounds that contained HCN and NH? (m/z = 27 and 17). These experimental results are consistent with the molecular information obtained by pyrolysis gas chromatography/mass spectrometry (pyrolysis GC/MS) of samples collected by the Huygens probe to Titan. Scanning electron microscopy (SEM) and three-dimensional atomic force microscopy (AFM) images of the irradiation products reveal nanometer-scale filaments and globules in complex amorphous structures (approximately 1000 Da). Isotope probing experiments by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) show that oxygen atoms were incorporated into the racemic amino acids by hydrolysis of ¹?O-labeled water. We suggest that the amino acid precursors possibly formed after water hydrolysis, as suggested in a previous observational study (C. A. Griffith, T. Owen, T. R. Geballe, J. Rayner, and P. Rannou, Science, 2003, 300, 628). We propose that cosmic rays are a significant and effective energy source for producing complex organics and amino acid precursors in Titan's atmospheric haze. PMID:23934557

Taniuchi, Toshinori; Takano, Yoshinori; Kobayashi, Kensei

2013-01-01

247

Electronic nose and isotope ratio mass spectrometry in combination with chemometrics for the characterization of the geographical origin of Italian sweet cherries.  

PubMed

Sweet cherries from two Italian regions, Apulia and Emilia Romagna, were analysed using electronic nose (EN) and isotope ratio mass spectrometry (IRMS), with the aim of distinguishing them according to their geographic origin. The data were elaborated by statistical techniques, examining the EN and IRMS datasets both separately and in combination. Preliminary exploratory overviews were performed and then linear discriminant analyses (LDA) were used for classification. Regarding EN, different approaches for variable selection were tested, and the most suitable strategies were highlighted. The LDA classification results were expressed in terms of recognition and prediction abilities and it was found that both EN and IRMS performed well, with IRMS showing better cross-validated prediction ability (91.0%); the EN-IRMS combination gave slightly better results (92.3%). In order to validate the final results, the models were tested using an external set of samples with excellent results. PMID:25306321

Longobardi, F; Casiello, G; Ventrella, A; Mazzilli, V; Nardelli, A; Sacco, D; Catucci, L; Agostiano, A

2015-03-01

248

The measurement of theophylline in human serum or plasma using gas chromatography and isotope dilution-mass spectrometry (GC-IDMS) taking other substituted xanthines into consideration.  

PubMed

A method is described which uses a combination of gas chromatography and isotope dilution-mass spectrometry (GC-IDMS) to determine the concentration of theophylline (1,3-dimethyl xanthine) in human plasma or serum samples. The effects of similar substituted xanthines - namely theobromine (3,7-dimethyl xanthine), paraxanthine (1,7-dimethyl xanthine) 1,3-dimethyl-7-(2-hydroxyethyl) xanthine (internal standard HPLC) and caffeine (1,3,7-trimethyl xanthine) were tested to confirm the specificity of the method. The derivatisation of all xanthines was performed with N-methyl-N-trimethylsilyl trifluroacetamide (MSTFA). The internal standard used was 2-(13)C ,1,3-(15)N2-theophylline. The extraction and derivatisation procedures were examined in detail and optimised stepwise during the development of the method. High-performance liquid chromatography (HPLC) was used for comparison. PMID:12389715

Kress, Michael; Meissner, Dieane; Kaiser, Patricia; Hanke, Rainer; Wood, William Graham

2002-01-01

249

Determination of picomolar levels of platinum in estuarine waters: a comparison of cathodic stripping voltammetry and isotope dilution-inductively coupled plasma mass spectrometry.  

PubMed

A comparative study to determine picomolar concentrations of platinum in natural waters was performed using two different analytical techniques. Results obtained by cathodic stripping voltammetry (CSV) were compared with those obtained by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICPMS) combined with anion exchange resin column extraction method. Using successive UV irradiations with low-pressure mercury (L-Hg) lamp for 4h prior to CSV analysis, the results of both methods were comparable. Without adequate photolytic decomposition, the results obtained using CSV were generally lower than those obtained using ID-ICPMS in the estuarine waters around Tokyo Bay. This difference implies the presence of organically complexed Pt species in the estuarine waters. The Pt enrichment in the middle of the Tokyo Bay estuaries probably reflects the anthropogenic release of Pt from highly populated areas in Tokyo. PMID:17723753

Obata, Hajime; Yoshida, Tetsuaki; Ogawa, Hiroshi

2006-10-27

250

Measurement of U and Pu isotope ratios in hair and nail samples using extraction chromatography and multi-collector inductively coupled plasma mass spectrometry.  

PubMed

A bioassay capable of monitoring occupational or environmental exposure to special nuclear materials would be a useful tool for nuclear nonproliferation programs. Hair and nail are potential biomonitors of exposure to U and Pu. A method is described to measure isotope ratios of ultra-trace concentrations of U and Pu in hair and nail samples. The method uses multiple extraction chromatography resins to separate U and Pu fractions from the sample matrix. The U recovery was quantitative while the Pu recovery ranged from 81% to 109%, with a U decontamination factor of 5×10(4). Following the separation (234)U/(238)U, (235)U/(238)U and (240)Pu/(239)Pu were measured in human hair and hair and nail samples using multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS). The human hair and nail samples had elevated ratios of (234)U/(238)U which could reflect exposure to naturally fractionated U. PMID:25127622

Brown, J N W; Robertson, J D; Brockman, J D

2014-11-01

251

A Method Revealing Bacterial Cell-wall Architecture by Time-dependent Isotope Labeling and Quantitative Liquid Chromatography/Mass Spectrometry  

PubMed Central

The molecular details of the biosynthesis and resulting architecture of the bacterial cell wall remain unclear but are essential to understanding the activity of glycopeptide antibiotics, the recognition of pathogens by hosts, and the processes of bacterial growth and division. Here we report a new strategy to elucidate bacterial cell-wall architecture based on time-dependent isotope labeling of bacterial cells quantified by liquid chromatography/accurate mass measurement mass spectrometry. The results allow us to track the fate of cell-wall precursors (which contain the vancomycin-binding site) in Enterococcus faecium, a leading antibiotic-resistant pathogen. By comparing isotopic enrichments of post-insertionally modified cell-wall precursors, we find that tripeptides and species without Asx bridges are specific to mature cell wall. Additionally, we find that the sequence of cell-wall maturation varies throughout a cell cycle. We suggest that actively dividing E. faecium cells have three zones of unique peptidoglycan processing. Our results reveal new organizational characteristics of the bacterial cell wall that are important to understanding tertiary structure and designing novel drugs for antibiotic-resistant pathogens. PMID:19281243

Patti, Gary J.; Chen, Jiawei; Gross, Michael L.

2009-01-01

252

Binding of ?4?5 by Adenosine A1 and A2A Receptors Determined by Stable Isotope Labeling with Amino Acids in Cell Culture and Mass Spectrometry†  

PubMed Central

Characterization of G protein ?? dimer isoform expression in different cellular contexts has been impeded by low levels of protein expression, broad isoform heterogeneity, and antibodies of limited specificity, sensitivity or availability. As a new approach, we used quantitative mass spectrometry to characterize native ?? dimers associated with adenosine A1:?i1 and adenosine A2A:?S receptor fusion proteins expressed in HEK-293 cells. Cells expressing A1:?i1 were cultured in media containing [13C6] Arg and [13C6] Lys, and ?? labeled with heavy isotopes purified. Heavy ?? was combined with either recombinant ?? purified from Sf9 cells, ?? purified from the A2A:?S expressed in HEK-293 cells cultured in standard media, or an enriched ?? fraction from HEK-293 cells. Samples were separated by SDS-PAGE, and protein bands containing ? and ? were excised, digested with trypsin, separated by HPLC and isotope ratios analyzed by mass spectrometry. Three ? isoforms, ?1, ?2 and ?4, and seven ? isoforms, ?2, ?4, ?5, ?7, ?10, ?11 and ?12 were identified in the analysis. ?1 and ?5 were most abundant in the enriched ?? fraction, and this ?? profile was generally mirrored in the fusion proteins. However, both A2A:?S and A1:?i1 bound more ?4 and ?5 compared to the enriched ?? fraction; also, more ?4 was associated with A2A:?S than A1:?i1. Both fusion proteins also contained less ?2, ?10 and ?12 than the enriched ?? fraction. These results suggest that preferences for particular ?? isoforms may be driven in part by structural motifs common to adenosine receptor family members. PMID:21128647

Wang, Dora Bigler; Sherman, Nicholas E.; Shannon, John D.; Leonhardt, Susan A.; Mayeenuddin, Linnia H.; Yeager, Mark; McIntire, William E.

2011-01-01

253

Capillary isotachophoresis mass spectrometry  

SciTech Connect

The on-line combination of capillary isotachophoresis (CITP) with mass spectrometry is demonstrated for the first time. The CITP/MS interface is based upon electrospray ionization and is identical with that developed previously for capillary zone electrophoresis (CZE)/MS. Separations were conducted in untreated 100 ..mu..m i.d. fused silica capillaries having lengths of 0.6-2.5 m, at voltages up to 35 kV. The method involves elution of the leading electrolyte to the electrospray source followed by a sequence of separated analyte bands (if sufficient time is provided for development) and, finally, the trailing electrolyte. The CITP/MS was demonstrated to allow very high resolution separations of quaternary phosphonium ions and other ionic substances having very small differences in electrophoretic mobilities. Nearly ideal band shapes are obtained in most separations despite the presence of electroosmotic flow. The potential for application to very dilute sample solutions is demonstrated by detection of analytes having 10/sup /minus/9/ M concentrations, with signal to noise ratios of approximately 10/sup 2/ for some components, which as at least 2 orders of magnitude better than CZE/MS. CITP/MS appears to be an attractive complement to CZE/MS for dilute (low ionic strength) solutions since much greater sample sizes can be addressed without loss of efficiency.

Udseth, H.R.; Loo, J.A.; Smith, R.D.

1989-02-01

254

Collision-induced dissociation of the A + 2 isotope ion facilitates glucosinolates structure elucidation by electrospray ionization-tandem mass spectrometry with a linear quadrupole ion trap.  

PubMed

An approach is presented that can be of general applicability for structural elucidation of naturally occurring glucosinolates (GLSs) in crude plant extracts based on the fragmentation of isotopic A and A + 2 peaks. The most important fragmentation pathways were studied by tandem mass spectrometry (MS(n), n = 2, 3) using a linear quadrupole ion trap (LTQ) upon GLSs separation by optimized reversed-phase liquid chromatography (RPLC) and electrospray ionization (ESI) in negative ion mode. As the LTQ MS analyzer ensures high sensitivity and linearity, the fragmentation behavior under collision induced dissociation (CID) of the isotopic peaks A and A + 2 as precursor ions was carefully examined. All GLSs (R-C(7)H(11)O(9)NS(2)(-)) share a common structure with at least two sulfur atoms and significant isotopic abundance of (34)S. Thus, dissociation of the +2 Da isotopomeric ions results in several fragment ion doublets containing a combination of (32)S and (34)S. Accordingly, their relative abundances allow one to speed up the structural recognition of GLSs with great confidence, as it produces more structurally informative ions than conventional tandem MS performed on A ions. This approach has been validated on known GLSs bearing two, three, four, and six sulfur atoms by comparing expected and measured isotopic peak abundance ratios (I(A)/I(A)(+2)). Both group- and compound-specific fragments were observed; the predominant pathway of fragmentation of GLSs gives rise to species having the following m/z values, [M - SO(3) - H](-), [M - 196 - H](-), [M - 178 - H](-), and [M - 162 - H](-) after H rearrangement from the R- side chain. The present strategy was successfully applied to extracts of rocket salad leaves (Eruca sativa L.), which was sufficient for the chemical identification of a not already known 6-methylsulfonyl-3-oxohexyl-GLS, a long-chain-length aliphatic glucosinolate, which contains three sulfurs and exhibits a deprotonated molecular ion at m/z 494.1. PMID:20521824

Cataldi, Tommaso R I; Lelario, Filomena; Orlando, Donatella; Bufo, Sabino A

2010-07-01

255

Establishing ion ratio thresholds based on absolute peak area for absolute protein quantification using protein cleavage isotope dilution mass spectrometry.  

PubMed

Quantitative mass spectrometry has become central to the field of proteomics and metabolomics. Selected reaction monitoring is a widely used method for the absolute quantification of proteins and metabolites. This method renders high specificity using several product ions measured simultaneously. With growing interest in quantification of molecular species in complex biological samples, confident identification and quantitation has been of particular concern. A method to confirm purity or contamination of product ion spectra has become necessary for achieving accurate and precise quantification. Ion abundance ratio assessments were introduced to alleviate some of these issues. Ion abundance ratios are based on the consistent relative abundance (RA) of specific product ions with respect to the total abundance of all product ions. To date, no standardized method of implementing ion abundance ratios has been established. Thresholds by which product ion contamination is confirmed vary widely and are often arbitrary. This study sought to establish criteria by which the relative abundance of product ions can be evaluated in an absolute quantification experiment. These findings suggest that evaluation of the absolute ion abundance for any given transition is necessary in order to effectively implement RA thresholds. Overall, the variation of the RA value was observed to be relatively constant beyond an absolute threshold ion abundance. Finally, these RA values were observed to fluctuate significantly over a 3 year period, suggesting that these values should be assessed as close as possible to the time at which data is collected for quantification. PMID:25154770

Loziuk, Philip L; Sederoff, Ronald R; Chiang, Vincent L; Muddiman, David C

2014-09-29

256

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. PMID:24339906

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

2013-01-01

257

Use of stable isotopically enriched proteins and directly coupled high-performance liquid chromatography inductively coupled plasma mass spectrometry for quantitatively monitoring the transfer of metals between proteins.  

PubMed

Studies have shown that metallothionein (MT) may play an important role in modulating the activity of certain Zn-regulated enzymes under various oxidoreductive conditions by either donating or removing Zn. To better determine the role of MT in interprotein metal transfer, we describe a procedure that uses stable isotopically enriched (67)Zn(7) metallothionein 2 ((67)Zn(7)-MT-2) to quantitatively determine the stoichiometry of transfer of Zn from the protein to a recipient apo-metalloenzyme, apo-carbonic anhydrase (apo-CA) by directly coupled ion exchange high-performance liquid chromatography inductively coupled plasma mass spectrometry. Quantitatively, the transfer of (67)Zn was consistent with the enzymatic activation of the apo-enzyme as judged by its esterase activity and ability to cleave p-nitrophenyl acetate. Maximum enzyme activation occurred at an MT-2:apo-CA molar ratio of 1, implying the release of a single atom of Zn from MT-2. Preincubation of (67)Zn(7)-MT-2 with an excess of oxidized glutathione (GSSG) increased metal donation fourfold, whereas reduced glutathione (GSH) inhibited donation by approximately 50%. By using multiple recipient and donor proteins having different stable isotopic signatures, the technique has the potential for quantitatively studying the kinetic and thermodynamic aspects of Zn transfer between numerous competing ligands in vitro, an important first step toward understanding the regulatory role of this metal in protein functioning and cellular metabolism in vivo. PMID:17673155

Mason, Andrew Z; Moeller, Rhonda; Thrippleton, Kelly A; Lloyd, Douglas

2007-10-01

258

[Determination of urinary cotinine of children exposed to passive smoking by stable isotope dilution gas chromatography-triple quadrupole mass spectrometry].  

PubMed

An analytical method for the determination of urinary cotinine of children exposed to passive smoking was established based on stable isotope dilution by gas chromatography-triple quadrupole mass spectrometry (GC-MS/MS). The samples were extracted and purified with chloroform. The extracts were determined by GC-MS/MS in multiple reaction monitoring (MRM) mode. The cotinine-d3 as an isotope internal standard was applied to quantify and confirm the urinary cotinine of children exposed to passive smoking. The method had a good linearity from 0.1 microg/L to 10 microg/L with the correlation coefficient (r) > 0.998. The recoveries of the cotinine in blank urine were from 79.2% to 112.8% at spiked levels of 0.1, 1.0 and 10 microg/ L, with relative standard deviations (RSDs) from 2.1% to 5. 8%. The limit of quantification ( LOQ) of the method was 0.1 microg/L. The developed method is accurate, sensitive, rapid and can be applied to detect urinary cotinine of children exposed to passive smoking at home. PMID:25269267

Wang, Yun; Huang, Zhiqiang; Ye, Ying; Zhang, Ying; Xiao, Shuiyuan

2014-06-01

259

Quantification of Cry1Ab in genetically modified maize leaves by liquid chromatography multiple reaction monitoring tandem mass spectrometry using 18O stable isotope dilution.  

PubMed

Cry1Ab is one of the most common Bacillus thuringiensis (Bt) proteins in genetically modified crops, which exhibits strong resistance against insect pests. In the present study, a sensitive and precise liquid chromatography stable isotope dilution multiple reaction monitoring tandem mass spectrometry (LC-SID-MRM-MS) assay was developed and validated to quantify the amount of Cry1Ab expression in transgenic maize leaves. The measurement of protein was converted to measurement of unique peptides to Cry1Ab protein. Two peptides unique to Cry1Ab were synthesized and labeled in H(2)(18)O to generate (18)O stable isotope peptides as internal standards. The validated method obtained superior specificity and good linearity. And the inter- and intra-day precision and accuracy for all samples were satisfactory. The results demonstrated Cry1Ab protein was 31.7 ± 4.1 ?g g(-1) dry weight in Bt-176 transgenic maize leaves. It proved that the novel LC-SID-MRM-MS method was sensitive and selective to quantify Cry1Ab in the crude extract without time-consuming pre-separation or purification procedures. PMID:22543512

Zhang, Yongqian; Lai, Chengjun; Su, Rui; Zhang, Mei; Xiong, Yan; Qing, Hong; Deng, Yulin

2012-06-01

260

Determination of the natural abundance delta15N of nortropane alkaloids by gas chromatography-isotope ratio mass spectrometry of their ethylcarbamate esters.  

PubMed

An important route for the detoxification of tropane alkaloids involves N-demethylation to the nor-compounds followed by further degradation. In order to study the mechanisms of the pertinent reactions, a suitable means to determine the isotope ratios of the substrates and products is required. However, the polarity and functionality of the nortropane compounds makes their analysis as free bases difficult. A method is described which allows both the quantification of nortropane alkaloids and the determination of their natural abundance delta(15)N values. The protocol exploits the derivatisation of the alkaloids by reaction with ethyl chloroformate in aqueous medium and the quantitative extraction of the ensuing ethylcarbamate esters. The improved chromatographic properties of these derivatives gives ample separation of the isomeric nortropine and norpseudotropine for measurement of their delta(15)N (per thousand) values by isotope ratio mass spectrometry interfaced to gas chromatography. Adequate separation could not be achieved with the underivatised compounds. Repeatability and precision are sufficient to allow differences in the delta(15)N values (Deltadelta(15)N) > 0.8 per thousand to be measured, with a standard deviation routinely approximately 0.3 per thousand. The methodology has been tested by determining the changes in the delta(15)N values of nortropine and norpseudotropine during degradation by cell suspension cultures of a Pseudomonas strain expressing a specific capacity for tropine catabolism. The precision and reproducibility are shown sufficient to allow the evolution of the delta(15)N values to be followed during the fermentation. PMID:20024532

Kosieradzka, Katarzyna; Tea, Illa; Gentil, Emmanuel; Robins, Richard J

2010-02-01

261

Accurate quantification of polycyclic aromatic hydrocarbons in dust samples using microwave-assisted solvent extraction combined with isotope-dilution mass spectrometry.  

PubMed

For accurate quantification of polycyclic aromatic hydrocarbons (PAHs) in dust samples, we investigated the use of microwave-assisted solvent extraction (MAE) combined with isotope-dilution mass spectrometry (IDMS) using deuterium-labelled PAHs (D-PAHs). Although MAE with a methanol/toluene mixture (1:3 by volume) at 160°C for 40 min was best for extracting PAHs from tunnel dust among examined, the recovery yields of D-PAHs decreased with increasing molecular weight (<40% for MW?264; that of deuterium-labelled indeno[123-cd]pyrene (D-IcdP) was only 7.1%). Although the residues were extracted a second time, the observed concentrations did not change dramatically (<5%), and the recovery yields of heavier D-PAHs (i.e., MW?264) were approximately half of those of the first extract, including D-IcdP (3.4%). These results suggest that both partitioning and isotopic equilibria of PAHs and D-PAHs between sample and solvent were achieved for extractable heavier PAHs under the condition. Thus, the observed concentrations of PAHs obtained by MAE-IDMS were reasonable, even though recovery yields of D-PAHs were <50%. From the results of carbon analyses and extractable contents, lower recovery yields of D-PAHs from the tunnel dust were due to a large content of char with low extractable contents. PMID:21704757

Itoh, Nobuyasu; Fushimi, Akihiro; Yarita, Takashi; Aoyagi, Yoshie; Numata, Masahiko

2011-08-01

262

Compact hydrogen\\/helium isotope mass spectrometer  

Microsoft Academic Search

The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently,

Herbert O. Funsten; David J. McComas; Earl E. Scime

1996-01-01

263

Linear electric field mass spectrometry  

DOEpatents

A mass spectrometer and methods for mass spectrometry. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field.

McComas, David J. (Los Alamos, NM); Nordholt, Jane E. (Los Alamos, NM)

1992-01-01

264

Linear electric field mass spectrometry  

DOEpatents

A mass spectrometer and methods for mass spectrometry are described. The apparatus is compact and of low weight and has a low power requirement, making it suitable for use on a space satellite and as a portable detector for the presence of substances. High mass resolution measurements are made by timing ions moving through a gridless cylindrically symmetric linear electric field. 8 figs.

McComas, D.J.; Nordholt, J.E.

1992-12-01

265

Reversed-phase liquid chromatography/electrospray ionization/mass spectrometry with isotope dilution for the analysis of nitrate and nitrite in water.  

PubMed

A new method was developed for the analysis of nitrate and nitrite in a variety of water matrices by using reversed-phase liquid chromatography/electrospray ionization/mass spectrometry in the negative ion mode. For this direct analysis method, nitrate and nitrite anions were well separated under the optimized LC conditions, detected by monitoring m/z 62 and m/z 46 ions, and quantitated by using an isotope dilution technique that utilized the isotopically labeled analogs. The method sensitivity, accuracy, and precision were investigated, along with matrix effects resulting from common inorganic matrix anions. The isotope dilution technique, along with sample pretreatment using barium, silver, and hydrogen cartridges, effectively compensated for the ionization suppression caused by the major water matrix anions, including chloride, sulfate, phosphate, and carbonate. The method detection limits, based on seven reagent water replicates fortified at 0.01 mg N/L nitrate and 0.1 mg N/L nitrite, were 0.001 mg N/L for nitrate and 0.012-0.014 mg N/L for nitrite. The mean recoveries from the replicate fortified reagent water and lab water samples containing the major water matrix anions, were 92-103% for nitrate with an imprecision (relative standard deviation, RSD) of 0.4-2.1% and 92-110% for nitrite with an RSD of 1.1-4.4%. For the analysis of nitrate and nitrite in drinking water, surface water, and groundwater samples, the obtained results were generally consistent with those obtained from the reference methods. The mean recoveries from the replicate matrix spikes were 92-123% for nitrate with an RSD of 0.6-7.7% and 105-113% for nitrite with an RSD of 0.3-1.8%. PMID:21168849

Li, Yongtao; Whitaker, Joshua S; McCarty, Christina L

2011-01-21

266

Mass spectrometry. [in organic chemistry  

NASA Technical Reports Server (NTRS)

A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

1978-01-01

267

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

PubMed

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

2004-08-25

268

Measurements of natural uranium concentration and isotopic composition with permil-level precision by inductively coupled plasma-quadrupole mass spectrometry  

NASA Astrophysics Data System (ADS)

A new analytical technique using inductively coupled plasma-quadrupole mass spectrometry (ICP-QMS) has been developed that produces permil-level precision in the measurement of uranium concentration ([U]) and isotopic composition (?234U) in natural materials. A 233U-236U double spike method was used to correct for mass fractionation during analysis. To correct for ratio drifting, samples were bracketed by uranium standard measurements. A sensitivity of 6-7 × 108 cps/ppm was generated with a sample solution uptake rate of 30 ?L/min. With a measurement time of 15-20 min, standards of 30-ng uranium produced a within-run precision better than 3‰ (±2 R.S.D.) for ?234U and better than 2‰ for [U]. Replicate measurements made on standards show that a between-run reproducibility of 3.5‰ for ?234U and 2‰ for [U] can be achieved. ICP-QMS data of ?234U and [U] in seawater, coral, and speleothem materials are consistent with the data measured by other ICP-MS and TIMS techniques. Advantages of the ICP-QMS method include low cost, easy maintenance, simple instrumental operation, and few sample preparation steps. Sample size requirements are small, such as 10-14 mg of coral material. The results demonstrate that this technique can be applied to natural samples with various matrices.

Shen, Chuan-Chou; Lin, Huei-Ting; Chu, Mei-Fei; Yu, Ein-Fen; Wang, Xianfeng; Dorale, Jeffrey A.

2006-09-01

269

The determination of carbon dioxide concentration using atmospheric pressure ionization mass spectrometry/isotopic dilution and errors in concentration measurements caused by dryers.  

PubMed

An atmospheric pressure ionization mass spectrometry/isotopically labeled standard (APIMS/ILS) method has been developed for the determination of carbon dioxide (CO(2)) concentration. Descriptions of the instrumental components, the ionization chemistry, and the statistics associated with the analytical method are provided. This method represents an alternative to the nondispersive infrared (NDIR) technique, which is currently used in the atmospheric community to determine atmospheric CO(2) concentrations. The APIMS/ILS and NDIR methods exhibit a decreased sensitivity for CO(2) in the presence of water vapor. Therefore, dryers such as a nafion dryer are used to remove water before detection. The APIMS/ILS method measures mixing ratios and demonstrates linearity and range in the presence or absence of a dryer. The NDIR technique, on the other hand, measures molar concentrations. The second half of this paper describes errors in molar concentration measurements that are caused by drying. An equation describing the errors was derived from the ideal gas law, the conservation of mass, and Dalton's Law. The purpose of this derivation was to quantify errors in the NDIR technique that are caused by drying. Laboratory experiments were conducted to verify the errors created solely by the dryer in CO(2) concentration measurements post-dryer. The laboratory experiments verified the theoretically predicted errors in the derived equations. There are numerous references in the literature that describe the use of a dryer in conjunction with the NDIR technique. However, these references do not address the errors that are caused by drying. PMID:18574165

DeLacy, Brendan G; Bandy, Alan R

2008-01-01

270

Mass Spectrometry in the Postgenomic Era  

E-print Network

Mass Spectrometry in the Postgenomic Era Brian T. Chait Laboratory for Mass Spectrometry reserved 0066-4154/11/0707-0239$20.00 Keywords cellular systems, proteomics, protein complexes, native mass spectrometry, lipidomics Abstract Mass spectrometry (MS) is rapidly becoming an essential tool for bi- ologists

Chait, Brian T.

271

Instrumentation for mass spectrometry: 1997  

SciTech Connect

All mass spectrometry experiments involve the manipulation of material, an interface with the mass spectrometer, ionization, ion manipulation/analysis, detection and data collection/reduction. Each of these elements involve instrumentation. The wide range of species now amenable to mass spectrometry and the diverse areas of physical science in which it plays a role have led to a seemingly unlimited array of instrumental combinations. However, only a limited number of mass analyzers, and their combinations, dominate. The dominant analyzers include time-of-flight, Fourier transform ion cyclotron resonance, the Paul trap, the mass filter, and the sector mass spectrometer. Why there are so few (or so many, depending upon one`s point of view) can be understood upon consideration of a set of mass analyzer figures of merit. These include mass resolution, mass accuracy, mass range, dynamic range, abundance sensitivity, precision, efficiency, speed, MS{sup n} capability, compatibility with the ionizer, cost, and size. The most appropriate form of mass spectrometry is determined by the priorities of the particular measurement placed on the various mass analyzer characteristics and the relative strengths of the analyzers in meeting the requirements. Each of the analyzer types has a unique set of figures of merit that makes it optimally suited for particular applications. This paper discusses these figures of merit, provides data illustrating recent developments for each analyzer type, and gives the figures of merit of each type of analyzer as they stand in 1997. 101 refs., 24 figs.

McLuckey, S.A.

1997-08-01

272

Multiplexed Analysis of Cage and Cage Free Chicken Egg Fatty Acids Using Stable Isotope Labeling and Mass Spectrometry  

PubMed Central

Binary stable isotope labeling couple with LC-ESI-MS has been used as a powerful non-targeted approach for the relative quantification of lipids, amino acids, and many other important metabolite classes. A multiplexed approach using three or more isotopic labeling reagents greatly reduces analytical run-time while maintaining excellent sensitivity and reproducibility. Three isotopic cholamine labeling reagents have been developed to take advantage of the pre-ionized character of cholamine, for ESI, and the ease by which stable isotopes can be incorporated into the cholamine structure. These three cholamine labeling reagents have been used to relatively quantify three fatty acid samples simultaneously. The quantification resulted in the observation of 12 fatty acids that had an average absolute error of 0.9% and an average coefficient of variation of 6.1%. Caged versus cage-free isotope labeling experiments showed that cage-free eggs have an increased level of omega-3 fatty acids as compared to caged eggs. This multiplexed fatty acid analysis provides an inexpensive and expedited tool for broad-based lipid profiling that will further aid discoveries in the mechanisms of fatty acid action in cells. PMID:24317525

Torde, Richard G.; Therrien, Andrew J.; Shortreed, Michael R.; Smith, Lloyd M.; Lamos, Shane M.

2014-01-01

273

Multiplexed analysis of cage and cage free chicken egg fatty acids using stable isotope labeling and mass spectrometry.  

PubMed

Binary stable isotope labeling couple with LC-ESI-MS has been used as a powerful non-targeted approach for the relative quantification of lipids, amino acids, and many other important metabolite classes. A multiplexed approach using three or more isotopic labeling reagents greatly reduces analytical run-time while maintaining excellent sensitivity and reproducibility. Three isotopic cholamine labeling reagents have been developed to take advantage of the pre-ionized character of cholamine, for ESI, and the ease by which stable isotopes can be incorporated into the cholamine structure. These three cholamine labeling reagents have been used to relatively quantify three fatty acid samples simultaneously. The quantification resulted in the observation of 12 fatty acids that had an average absolute error of 0.9% and an average coefficient of variation of 6.1%. Caged versus cage-free isotope labeling experiments showed that cage-free eggs have an increased level of omega-3 fatty acids as compared to caged eggs. This multiplexed fatty acid analysis provides an inexpensive and expedited tool for broad-based lipid profiling that will further aid discoveries in the mechanisms of fatty acid action in cells. PMID:24317525

Torde, Richard G; Therrien, Andrew J; Shortreed, Michael R; Smith, Lloyd M; Lamos, Shane M

2013-01-01

274

A Glossary for Mass Spectrometry  

NSDL National Science Digital Library

This useful article from the journal Mass Spectrometry features a compilation of some of the more widely used terms that non-mass spectrometrists may encounter, and for which a simple definition would be helpful. The link will lead users to a PDF file which may be downloaded or viewed online.

Busch, Kenneth L.

2011-05-25

275

Quantitative profiling of differentiation-induced microsomal proteins using isotope-coded affinity tags and mass spectrometry  

Microsoft Academic Search

An approach to the systematic identification and quantification of the proteins contained in the microsomal fraction of cells is described. It consists of three steps: (1) preparation of microsomal fractions from cells or tissues representing different states; (2) covalent tagging of the proteins with isotope-coded affinity tag (ICAT) reagents followed by proteolysis of the combined labeled protein samples; and (3)

David K. Han; Jimmy Eng; Huilin Zhou; Ruedi Aebersold

2001-01-01

276

Measurement of ?18O, ?17O, and 17O-excess in water by off-axis integrated cavity output spectroscopy and isotope ratio mass spectrometry.  

PubMed

Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant (17)O isotope in addition to (2)H and (18)O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements ?(18)O, ?(17)O, and (17)O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard Greenland Ice Sheet Precipitation (GISP) demonstrate the precision and accuracy of OA-ICOS: ?(18)OVSMOW-SLAP = -24.74 ± 0.07‰ (1?) and ?(17)OVSMOW-SLAP = -13.12 ± 0.05‰ (1?). For comparison, the International Atomic Energy Agency (IAEA) value for ?(18)OVSMOW-SLAP is -24.76 ± 0.09‰ (1?) and an average of previously reported values for ?(17)OVSMOW-SLAP is -13.12 ± 0.06‰ (1?). Multiple (26) high-precision measurements of GISP provide a (17)O-excessVSMOW-SLAP of 23 ± 10 per meg (1?); an average of previously reported values for (17)O-excessVSMOW-SLAP is 22 ± 11 per meg (1?). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in ?(18)O, ?(17)O, and (17)O-excess. The ability to measure accurately ?(18)O, ?(17)O, and (17)O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of ?(17)O and (17)O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

Berman, Elena S F; Levin, Naomi E; Landais, Amaelle; Li, Shuning; Owano, Thomas

2013-11-01

277

Comparison of isotope dilution mass spectrometry and graphite furnace atomic absorption spectrometry with Zeeman background correction for determination of plasma selenium  

Microsoft Academic Search

There has been increasing interest in the measurement of selenium in plasma because of the toxicological and nutritional importance of selenium. More recently selenium has been implicated as an anticarcinogen and a carcino-preventive agent. Several techniques are used to measure plasma selenium concentrations. One of the most popular, at present, is the use of graphite furnace atomic absorption spectrometry with

S. A. Lewis; N. W. Hardison; Claude. Veillon

1986-01-01

278

Ion Trap Mass Spectrometry  

SciTech Connect

This chapter describes research conducted in a few research groups in the 1990s in which RF quadrupole ion trap mass spectrometers were coupled to a powerful atomic ion source, the inductively coupled plasma used in conventional ICP-MS instruments. Major section titles for this chapter are: RF Quadrupole Ion Traps Features of RF Quadrupole Ion Trap Mass Spectrometers Selective Ion Trapping methods Inductively Coupled Plasma Source Ion Trap Mass Spectrometers

Eiden, Greg C.

2005-09-01

279

Imaging mass spectrometry in microbiology  

PubMed Central

Mass spectrometry tools which allow for the 2-D visualization of the distribution of trace metals, metabolites, surface lipids, peptides and proteins directly from biological samples without the need for chemical tagging or antibodies are becoming increasingly useful for microbiology applications. These tools, comprised of different imaging mass spectrometry techniques, are ushering in an exciting new era of discovery by allowing for the generation of chemical hypotheses based on of the spatial mapping of atoms and molecules that can correlate to or transcend observed phenotypes. In this review, we explore the wide range of imaging mass spectrometry techniques available to microbiologists and describe their unique applications to microbiology with respect to the types of microbiology samples to be investigated. PMID:21822293

Watrous, Jeramie D.; Dorrestein, Pieter C.

2013-01-01

280

Symposium on accelerator mass spectrometry  

SciTech Connect

The area of accelerator mass spectrometry has expanded considerably over the past few years and established itself as an independent and interdisciplinary research field. Three years have passed since the first meeting was held at Rochester. A Symposium on Accelerator Mass Spectrometry was held at Argonne on May 11-13, 1981. In attendance were 96 scientists of whom 26 were from outside the United States. The present proceedings document the program and excitement of the field. Papers are arranged according to the original program. A few papers not presented at the meeting have been added to complete the information on the status of accelerator mass spectrometry. Individual papers were prepared separately for the data base.

None

1981-01-01

281

Online gas chromatography combustion/pyrolysis-isotope ratio mass spectrometry (HRGC-C/P-IRMS) of (+/-)-Dihydroactinidiolide from tea ( Camellia sinensis ) and rooibos tea ( Aspalathus linearis ).  

PubMed

Online capillary gas chromatography-isotope ratio mass spectrometry in both the combustion and the pyrolysis modes (HRGC-C/P-IRMS) was employed to perform authentication studies of the flavoring agent (+/-)-dihydroactinidiolide. Thus, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values of synthetic (ex synthetic beta-ionone and natural beta-carotene) as well as enzymatically (ex synthetic and natural beta-carotene) produced references were studied in comparison with those of the natural substance isolated from black (n = 17) and green teas (n = 6) ( Camellia sinensis ) as well as Rooibos tea ( Aspalathus linearis ) (n = 7). The isotope values determined for both the synthetic and enzymatically produced samples of (+/-)-dihydroactinidiolide reflected the influence of the origin of their educts. Hence, in cases when synthetic educts were used, the delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranged from -27.0 to -28.4 per thousand and from -28 to -169 per thousand, respectively, whereas the use of natural educts led to ranges from -30.3 to -31.6 per thousand and from -154 to -228 per thousand, respectively. As to the tea samples, delta(13)C(V-PDB) and delta(2)H(V-SMOW) values ranging from -29.0 to -34.1 per thousand and from -153 to -274 per thousand, respectively, were recorded for (+/-)-dihydroactinidiolide from black and green teas, whereas that from Rooibos tea showed (2)H/(1)H ratios ranging from -189 to -210 per thousand as well as slightly enriched values in the (13)C/(12)C ratios ranging from -24.4 to -27.1 per thousand. PMID:19514730

del Mar Caja, María; Preston, Christina; Menzel, Michael; Kempf, Michael; Schreier, Peter

2009-07-01

282

Determination of the 13C/12C ratio of ethanol derived from fruit juices and maple syrup by isotope ratio mass spectrometry: collaborative study.  

PubMed

A collaborative study of the carbon-13 isotope ratio mass spectrometry (13C-IRMS) method based on fermentation ethanol for detecting some sugar additions in fruit juices and maple syrup is reported. This method is complementary to the site-specific natural isotope fractionation by nuclear magnetic resonance (SNIF-NMR) method for detecting added beet sugar in the same products (AOAC Official Methods 995.17 and 2000.19), and uses the same initial steps to recover pure ethanol. The fruit juices or maple syrups are completely fermented with yeast, and the alcohol is distilled with a quantitative yield (>96%). The carbon-13 deviation (delta13C) of ethanol is then determined by IRMS. This parameter becomes less negative when exogenous sugar derived from plants exhibiting a C4 metabolism (e.g., corn or cane) is added to a juice obtained from plants exhibiting a C3 metabolism (most common fruits except pineapple) or to maple syrup. Conversely, the delta13C of ethanol becomes more negative when exogenous sugar derived from C3 plants (e.g., beet, wheat, rice) is added to pineapple products. Twelve laboratories analyzed 2 materials (orange juice and pure cane sugar) in blind duplicate and 4 sugar-adulterated materials (orange juice, maple syrup, pineapple juice, and apple juice) as Youden pairs. The precision of that method for measuring delta13C was similar to that of other methods applied to wine ethanol or extracted sugars in juices. The within-laboratory (Sr) values ranged from 0.06 to 0.16%o (r = 0.17 to 0.46 percent per thousand), and the among-laboratories (SR) values ranged from 0.17 to 0.26 percent per thousand (R = 0.49 to 0.73 percent per thousand). The Study Directors recommend that the method be adopted as First Action by AOAC INTERNATIONAL. PMID:15287660

Jamin, Eric; Martin, Frédérique; Martin, Gilles G

2004-01-01

283

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

PubMed

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

2014-08-01

284

Isotope dilution mass spectrometry of 10B and 6LiF reference deposits used for the determination of the neutron lifetime  

NASA Astrophysics Data System (ADS)

The accurate characterization of 10B and 6LiF reference deposits is of the highest importance in absolute neutron counting e.g. for the determination of the lifetime of the free neutron [J. Byrne , Phys. Rev. Lett., 65 (1990) 289]. A series of 10B and 6LiF deposits, with different surface densities, were prepared on silicon substrates by vacuum deposition and analyzed by isotope dilution mass spectrometry (IDMS), subsequent to their relative characterization by neutron induced charged particle counting and determination of their surface area. The IDMS results were performed to calibrate the (n,[alpha]) measurements. They carry a total uncertainty (ls equivalent) on the number of 10B atoms in the deposit of 0.48% on Series I (without chemical purification) and 0.58% on Series II (with chemical purification). The corresponding uncertainty on the number of 6Li atoms in the deposit is 0.25%. The systematic components of these uncertainties are 0.12% on the 10B content and 0.21% on the 6Li content. An intercomparison on the basis of the count rates of the (n,[alpha]) measurements, the surface areas and the IDMS results shows an excellent agreement between the results for 10B and 6Li.

Lamberty, A.; de Bièvre, P.

1991-10-01

285

Rapid determination of trace dicyandiamide in mussels from Zhejiang coast by ultra-fast liquid chromatography-tandem mass spectrometry with isotope internal standard dilution technique.  

PubMed

In this study, a rapid and accurate ultra-fast liquid chromatography-tandem quadrupole mass spectrometry (UFLC-MS/MS) method coupled with the isotope internal standard dilution technique was established and validated to determine trace dicyandiamide (DCD) in mussels. The sample was extracted by acetonitrile, and chromatographic separations were performed on an Acquity UPLC BEH Amide column by using water-acetonitrile (9:91, v/v) as the mobile phase within 3 min. DCD was determined by using DCD-(15)N4 as an internal standard. The results showed that the recoveries were between 96.2 and 103 % with relative standard deviations (RSDs) in the range of 0.6-6.0 %. The limit of quantification (LOQ) was 0.05 ?g/kg. This method can be applied to the routine analysis for the rapid and sensitive determination of trace DCD in mussels. Overall, the data reiterate the importance of investigating the presence of DCD in marine biological samples, which can act as food quality controls for human health. PMID:25035051

Zhang, Yun; Gong, Wen-Jie; Zhao, Yong-Gang; Zhou, Hua

2014-12-01

286

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). PMID:24808927

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

2014-01-01

287

Ultratrace and precise isotope analysis by double- focusing sector field inductively coupled plasma mass spectrometry† Invited Lecture  

Microsoft Academic Search

of isobaric singly charged atomic ions, mass spectrometers sensitive multi-element analysis has been established for the with significantly higher mass resolution (e.g., Fourier trans- determination of trace and ultratrace elements in high-purity form or ion trap mass spectrometers)7-9 are required. The materials, environmental samples and radioactive waste interference problems with atomic ions of analyte and molecu- materials. Some applications of

Johanna Sabine Becker; Hans-Joachim Dietze

288

Isotope Dilution High-Performance Liquid Chromatography–Tandem Mass Spectrometry Method for Quantifying Urinary Metabolites of Synthetic Pyrethroid Insecticides  

Microsoft Academic Search

This paper describes a method for measuring cis- and trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-1-carboxylic acids (cis-DCCA and trans-DCCA), cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylic acid (DBCA), 3-phenoxybenzoic acid (3PBA), and 4-fluoro-3-phenoxybenzoic acid (4F3PBA) in human urine. These compounds are considered to be reliable biomarkers of exposure for many pyrethroid insecticides used in the United States. In this method, stable isotopically labeled analogues of trans-DCCA and 3PBA were spiked into

Samuel E. Baker; Anders O. Olsson; Dana B. Barr

2004-01-01

289

Recent advances in biomedical applications of accelerator mass spectrometry  

Microsoft Academic Search

The use of radioisotopes has a long history in biomedical science, and the technique of accelerator mass spectrometry (AMS), an extremely sensitive nuclear physics technique for detection of very low-abundant, stable and long-lived isotopes, has now revolutionized high-sensitivity isotope detection in biomedical research, because it allows the direct determination of the amount of isotope in a sample rather than measuring

Sang Soo Hah

2009-01-01

290

Counting individual sulfur atoms in a protein by ultrahighresolution Fourier transform ion cyclotron resonance mass spectrometry: Experimental resolution of isotopic fine structure in proteins  

PubMed Central

A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of ?1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at ?2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/?m50% ?8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 ± 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak. PMID:9751700

Shi, Stone D.-H.; Hendrickson, Christopher L.; Marshall, Alan G.

1998-01-01

291

Applications of resonance ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

We describe here several types of mass spectrometry in which the mass selectivity is combined with a highly selective laser ionization method to achieve both high sensitivity and very high selectivity. These methods combine the most sensitive and highly selective laser ionization methods with mass selectivity in order to improve on both the sensitivity and the Z and A selectivity previously achievable in detecting atomic species. Applications of these methods include the dating of geophysical specimens, the on line analysis of rare short-lived isotopes produced in high-energy collisions, the detection of low levels of heavy metals or radioactive isotopes in biological samples, the detection of impurities in ultrapure materials, and a host of other applications. Because some versions of this method offer sensitivity to a hundred atoms of a particular isotope of an element in a macroscopic sample, there are new possibilities for fundamental studies of rare events. Several types of facilities for elemental and isotopic analysis will be described.

Payne, M. G.; Deng, Lu; Thonnard, N.

1994-08-01

292

Measurement of ?18O, ?17O, and 17O-excess by Off-Axis Integrated Cavity Output Spectroscopy and Isotope Ratio Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Water stable isotopes have for many years been used to study the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been mounting interest in measurement and use of the less-abundant 17O isotope in addition to 2H and 18O. Off-axis integrated cavity output spectroscopy (OA-ICOS) measures ?18O, ?17O, and 17O-excess in liquid water without sample preparation or highly-trained operators. OA-ICOS allows measurements to be made on a relatively compact and affordable instrument by researchers collecting the samples. Numerous (514) high-throughput measurements of the international water standard GISP are used to demonstrate the precision and accuracy of OA-ICOS: ?18O =-24.74 × 0.06 ‰ (HWHM) and ?17O = -13.12 × 0.04 ‰ (HWHM). For comparison, the IAEA value for ?18O of GISP is 24.76 × 0.09 ‰ (1?) and an average of previously reported values for ?17O of GISP is -13.12 × 0.06 ‰ (1?). Repeated (26) high-precision measurements of GISP provide a 17O-excess of 23 × 9 per meg (HWHM); an average of previously reported values for 17O-excess is 22 × 11 per meg (1?). The precision of OA-ICOS measurements of ?18O, ?17O, and 17O-excess can be further enhanced by additional averaging. Comparison with two independent isotope ratio mass spectrometry (IRMS) laboratories shows that OA-ICOS has equivalent accuracy and precision as the current fluorination-IRMS techniques in ?18O, ?17O, and 17O-excess. The capability to accurately measure ?18O, ?17O, and 17O-excess in liquid water inexpensively and without sample preparation is expected to enhance both the number and breadth of applications of ?17O and 17O-excess for understanding of the water cycle, atmospheric convection, and climate modeling among others. 17O-excess measurement accuracy demonstrated by measurements of GISP and four commercially-available USGS standards by OA-ICOS and two independent IRMS labs. Error bars represent one standard error of the mean. The line behind the GISP columns shows the collected average of 3 previously reported IRMS measurements.

Berman, E. S.; Levin, N.; Landais, A.; Li, S.; Owano, T. G.

2013-12-01

293

Isotope-coded carbamidomethylation for quantification of N-glycoproteins with online microbore hollow fiber enzyme reactor-nanoflow liquid chromatography-tandem mass spectrometry.  

PubMed

This paper introduces a simple, inexpensive, and robust quantitative proteomic method for quantifying N-linked glycoproteins based on isotope-coded carbamidomethylation (iCCM) incorporated into an online microbore hollow fiber enzyme reactor and nanoflow liquid chromatography-tandem mass spectrometry (mHFER-nLC-MS/MS). The iCCM quantitation uses carbamidomethylation (CM; a routine protection of thiol groups before proteolysis) of the Cys residue of proteins with iodoacetamide (IAA) or its isotope (IAA-(13)C2,D2: 4 Da difference). CM-/iCCM-labeled proteome samples are mixed for proteolysis; then, online enrichment of N-glycopeptides using lectin affinity is carried out in an mHFER before nLC-MS/MS for quantification using multiple reaction monitoring (MRM). Initial evaluation of the iCCM method varying the mixing ratio of CM-/iCCM-labeled bovine serum albumin (BSA) standards yielded successful quantification of 18 peptides with less than 2% variation in the calculated ratio of light/heavy-labeled peptides. The iCCM quantitation with mHFER-nLC-MS/MS was evaluated with three standard glycoproteins (?-1-acid glycoproteins, fetuin and transferrin) and then applied to serum glycoproteins from liver cancer patients and controls, resulting in successful quantification of 73 N-glycopeptides (from 49 N-glycoproteins), among which 19 N-glycopeptides from 14 N-glycoproteins showed more than a 2.5-fold aberrant change in liver cancer patients' sera compared with the pooled control. Although iCCM quantitation with mHFER-nLC-MS/MS applies only to glycopeptides with Cys residue, the method can offer several advantages over other labeling methods when applied to targeted glycoproteins: The iCCM method does not require an additional labeling reaction under special conditions nor complicated procedures to purify labeled products using additional columns. Isotope labeling at the protein level can minimize potential uncertainty originating from unequal efficiencies in protein digestion in separate vials and retrieval of each labeled peptide when labeling takes place at the peptide level. In addition, the labeling reagents for the iCCM method are readily obtained at a reasonable cost, which can make protein quantification easily accessible. PMID:24960276

Kim, Jin Yong; Oh, Donggeun; Kim, Sook-Kyung; Kang, Dukjin; Moon, Myeong Hee

2014-08-01

294

Open Mass Spectrometry Search Algorithm  

Microsoft Academic Search

Large numbers of MS\\/MS peptide spectra generated in proteomics experiments require efficient, sensitive and specific algorithms for peptide identification. In the Open Mass Spectrometry Search Algorithm [OMSSA], specificity is calculated by a classic probability score using an explicit model for matching experimental spectra to sequences. At default thresholds, OMSSA matches more spectra from a standard protein cocktail than a comparable

Lewis Y. Geer; Sanford P. Markey; Jeffrey A. Kowalak; Lukas Wagner; Ming Xu; Dawn M. Maynard; Xiaoyu Yang; Wenyao Shi; Stephen H. Bryant

2004-01-01

295

Tandem Mass Spectrometry in Physiology  

NSDL National Science Digital Library

Tandem mass spectrometry coupled to liquid chromatography (LC-MS/MS) allows identification of proteins in a complex mixture without need for protein purification ("shotgun" proteomics). Recent progress in LC-MS/MS-based quantification, phosphoproteomic analysis, and targeted LC-MS/MS using multiple reaction monitoring (MRM) has made LC-MS/MS a powerful tool for the study of cell physiology.

2007-12-01

296

Association between cigarette smoking and urinary excretion of 1,N2-ethenoguanine measured by isotope dilution liquid chromatography-electrospray ionization/tandem mass spectrometry.  

PubMed

Levels of the promutagenic 1,N2-ethenoguanine (1,N2-epsilonGua), an etheno DNA adduct derived mainly from lipid peroxidation, in experimental animals are associated with risk of cancer formation. Since 1,N2-epsilonGua can be repaired by human glycosylases, it is possible to use it as a biomarker for cancer risk assessment in humans. In the present study, a highly sensitive and specific stable isotope dilution liquid chromatography-electrospray ionization/tandem mass spectrometry (LC-ESI/MS/MS) was developed for accurate quantification of 1,N2-epsilonGua in human urine. The sample pretreatment involved a consecutive strong cation exchange solid-phase extraction (SPE) and reversed phase SPE chromatography. The pretreated sample was analyzed by LC-ESI/MS/MS under multiple reaction monitoring mode (MRM) using a triple quadrupole mass spectrometer. The detection limit of 1,N2-epsilonGua using this LC-ESI/MS/MS assay was 1.0 pg (5.8 fmol) injected on-column. Levels of urine samples collected from healthy volunteers were found to range from 0 to 199 pg/mL, and levels as low as 5.0 pg/mL (29 pM) could be accurately quantified. After adjusting for creatinine levels and body weight, an statistically significant association was observed between urinary levels of 1,N2-epsilonGua and cigarette smoking (p = 0.0006). This highly specific and sensitive assay should be valuable in measuring urinary 1,N2-epsilonGua as a potential noninvasive biomarker for oxidative DNA damage. PMID:16533024

Chen, Hauh-Jyun Candy; Chiu, Wei-Loong

2005-10-01

297

Identification and quantification of DNA repair proteins by liquid chromatography/isotope-dilution tandem mass spectrometry using their fully 15N-labeled analogues as internal standards.  

PubMed

Oxidatively induced DNA damage is implicated in disease, unless it is repaired by DNA repair. Defects in DNA repair capacity may be a risk factor for various disease processes. Thus, DNA repair proteins may be used as early detection and therapeutic biomarkers in cancer and other diseases. For this purpose, the measurement of the expression level of these proteins in vivo will be necessary. We applied liquid chromatography/isotope-dilution tandem mass spectrometry (LC-MS/MS) for the identification and quantification of DNA repair proteins human 8-hydroxyguanine-DNA glycosylase (hOGG1) and Escherichia coli formamidopyrimidine DNA glycosylase (Fpg), which are involved in base-excision repair of oxidatively induced DNA damage. We overproduced and purified (15)N-labeled analogues of these proteins to be used as suitable internal standards to ensure the accuracy of quantification. Unlabeled and (15)N-labeled proteins were digested with trypsin and analyzed by LC-MS/MS. Numerous tryptic peptides of both proteins were identified on the basis of their full-scan mass spectra. These peptides matched the theoretical peptide fragments expected from trypsin digestion and provided statistically significant protein scores that would unequivocally identify these proteins. We also recorded the product ion spectra of the tryptic peptides and defined the characteristic product ions. Mixtures of the analyte proteins and their (15)N-labeled analogues were analyzed by selected-reaction monitoring on the basis of product ions. The results obtained suggest that the methodology developed would be highly suitable for the positive identification and accurate quantification of DNA repair proteins in vivo as potential biomarkers for cancer and other diseases. PMID:21619077

Dizdaroglu, Miral; Reddy, Prasad T; Jaruga, Pawel

2011-08-01

298

Characterization of Diesel Fuel by Chemical Separation Combined with Capillary Gas Chromatography (GC) Isotope Ratio Mass Spectrometry (IRMS)  

SciTech Connect

The purpose of this study was to perform a preliminary investigation of compound-specific isotope analysis (CSIA) of diesel fuels to evaluate whether the technique could distinguish between the diesel samples from different sources/locations. The ability to differentiate or correlate diesel samples could be valuable for detecting fuel tax evasion schemes. Two fractionation techniques were used to isolate the n-alkanes from the fuel. Both ?13C and ?D values for the n-alkanes were then determined by CSIA in each sample. Plots of ?D versus ?13C with sample n-alkane points connected in order of increasing carbon number gave well separated clusters with characteristic shapes for each sample. Principal components analysis (PCA) with ?13C, ?D, or combined ?13C and ?D data on the yielded scores plots that could clearly differentiate the samples, thereby demonstrating the potential of this approach for fingerprinting fuel samples using the ?13C and ?D values.

Harvey, Scott D.; Jarman, Kristin H.; Moran, James J.; Sorensen, Christina M.; Wright, Bob W.

2011-09-15

299

MASS SPECTROMETRY-BASED METABOLOMICS  

PubMed Central

This review presents an overview of the dynamically developing field of mass spectrometry-based metabolomics. Metabolomics aims at the comprehensive and quantitative analysis of wide arrays of metabolites in biological samples. These numerous analytes have very diverse physico-chemical properties and occur at different abundance levels. Consequently, comprehensive metabolomics investigations are primarily a challenge for analytical chemistry and specifically mass spectrometry has vast potential as a tool for this type of investigation. Metabolomics require special approaches for sample preparation, separation, and mass spectrometric analysis. Current examples of those approaches are described in this review. It primarily focuses on metabolic fingerprinting, a technique that analyzes all detectable analytes in a given sample with subsequent classification of samples and identification of differentially expressed metabolites, which define the sample classes. To perform this complex task, data analysis tools, metabolite libraries, and databases are required. Therefore, recent advances in metabolomics bioinformatics are also discussed. PMID:16921475

Dettmer, Katja; Aronov, Pavel A.; Hammock, Bruce D.

2007-01-01

300

UPb isotope geochronology of zircon: evaluation of the laser probe-inductively coupled plasma mass spectrometry technique  

Microsoft Academic Search

Using a laser ablation microprobe-inductively coupled plasma mass spectrometer (LP-ICPMS) we have determined 238U, 207Pb, 206Pb, and 204Pb abundances of several zircon populations whose ages have previously been measured by other techniques (principally ion microprobe). Ages of the samples range from 360–2800 Ma. A frequency quadrupled Nd-YAG UV laser (266 nm) which produces pit sizes of 10–15 ?m was used

Takafumi Hirata; Robert W. Nesbitt

1995-01-01

301

THERMOSPRAY MASS SPECTROMETRY AND THERMOSPRAY MASS SPECTROMETRY/MASS SPECTROMETRY OF TWO DEOXYGUANOSINE CARCINOGEN ADDUCTS  

EPA Science Inventory

Analysis of N-(deoxyguanosin-8-yl)-2-acetylaminofluorene (dG-C8-AAF) and N-(deoxyguanosin-8-yl)-2-aminofluorene (dG-C8-AF) by thermospray mass spectrometry (TSP/MS) provided (MH)+ ions. TSP/MS/MS of the (MH)+ ions produced (BH2)+ ions....

302

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

PubMed

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

2014-07-01

303

Mass spectrometry and renal calculi  

PubMed Central

The present review represents a concise and complete survey of the literature covering 2004–2009, concerning the mass spectrometric techniques involved in the structural investigation of renal calculi. After a short presentation of the fundamental mass spectrometric techniques (MALDI–TOF, QTOF, MS–MS) as well as hyphenated methods (GC–MS, LC–MS, CE–MS), an extensive study of the urinary proteome analysis as well as the detection and quantification by mass spectrometry of toxins, drugs and metabolites from renal calculi is presented. PMID:20968197

Purcarea, VL; Sisu, I; Sisu, E

2010-01-01

304

Mass spectrometry of aerospace materials  

NASA Technical Reports Server (NTRS)

Mass spectrometry is used for chemical analysis of aerospace materials and contaminants. Years of analytical aerospace experience have resulted in the development of specialized techniques of sampling and analysis which are required in order to optimize results. This work has resulted in the evolution of a hybrid method of indexing mass spectra which include both the largest peaks and the structurally significant peaks in a concise format. With this system, a library of mass spectra of aerospace materials was assembled, including the materials responsible for 80 to 90 percent of the contamination problems at Goddard Space Flight Center during the past several years.

Colony, J. A.

1976-01-01

305

Effect of the detector dead-time uncertainty on the analytical result of minor elements in low-alloy steel by isotope dilution/ICP sector field mass spectrometry.  

PubMed

In the present study the effects of the detector dead-time and its uncertainties on the accuracy and uncertainty of isotope dilution mass spectrometry (IDMS) were considered through an interlaboratory study on the analysis of low-alloy steel by using an ICP-sector field mass spectrometer. Also, an optimized mixing ratio of the sample and the spike to obtain highly precise results was theoretically and experimentally investigated. The detector dead-time used in the interlaboratory study showed a negative value. However, it less affected the trueness of the analytical result if the dead-time correction for the measured isotope ratio was done properly. As many researchers have pointed out, the detector dead-time showed a clear mass dependence. Therefore, it is desirable to check the dead-time in every target element by using assay standards or isotopic standards, which would lead to an accurate result even if the detector dead-time is a negative value. On the other hand, the effect of the uncertainty of the detector dead-time can be minimized when both isotope ratios and ICP-MS signals of the [sample + spike] blend in IDMS are equal to those of [spike + assay standard] in reverse IDMS. From standpoints of error magnification theory and the precision of the isotope ratio measurement, an optimized isotope ratio of the sample-spike blend would be 1.0 for an element with a large difference in ten times and more between the atomic fractions of two isotopes used for IDMS. In the case of an element with no significant difference between the atomic fractions of two isotopes, an optimized isotope ratio can be calculated by a formula expressed as a function of the atomic fractions of the sample and the spike as well as the signal of ICP-MS. PMID:25213815

Nonose, Naoko; Hioki, Akiharu; Chiba, Koichi

2014-01-01

306

Mass-independent isotope effects.  

PubMed

Three fundamental properties of atomic nuclei-mass, spin (and related magnetic moment), and volume-are the source of isotope effects. The mostly deserved and popular, with almost hundred-year history, is the mass-dependent isotope effect. The first mass-independent isotope effect which chemically discriminates isotopes by their nuclear spins and nuclear magnetic moments rather than by their masses was detected in 1976. It was named as the magnetic isotope effect because it is controlled by magnetic interaction, i.e., electron-nuclear hyperfine coupling in the paramagnetic species, the reaction intermediates. The effect follows from the universal physical property of chemical reactions to conserve angular momentum (spin) of electrons and nuclei. It is now detected for oxygen, silicon, sulfur, germanium, tin, mercury, magnesium, calcium, zinc, and uranium in a great variety of chemical and biochemical reactions including those of medical and ecological importance. Another mass-independent isotope effect was detected in 1983 as a deviation of isotopic distribution in reaction products from that which would be expected from the mass-dependent isotope effect. On the physical basis, it is in fact a mass-dependent effect, but it surprisingly results in isotope fractionation which is incompatible with that predicted by traditional mass-dependent effects. It is supposed to be a function of dynamic parameters of reaction and energy relaxation in excited states of products. The third, nuclear volume mass-independent isotope effect is detected in the high-resolution atomic and molecular spectra and in the extraction processes, but there are no unambiguous indications of its importance as an isotope fractionation factor in chemical reactions. PMID:23301791

Buchachenko, Anatoly L

2013-02-28

307

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: rhalden@jhsph.edu

2007-01-15

308

Determination of the H isotopic composition of individual components in fine-scale mixtures of organic matter and phyllosilicates with the nanoscale secondary ion mass spectrometry.  

PubMed

When organic matter is mixed on a nanometer scale with clay minerals, the individual D/H ratios of the two H-bearing phases cannot be directly measured even with the nominal spatial resolution of nanoscale secondary ion mass spectrometry (NanoSIMS, 50-100 nm). To overcome this limitation, a new analytical protocol is proposed based on the deconvolution of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios measured by NanoSIMS. Indeed, since the yields of H(-) and (16)OH(-) are different for organics and clays, it should be theoretically possible to determine the mixing ratio of these two components in the area analyzed by the ion probe. Using organics with different D/H ratios, the interdependence of the D(-)/H(-) and (16)OD(-)/(16)OH(-) ionic ratios was determined in pure samples. Then using the H(-) and (16)OH(-) yields and the isotopic ratios measured on pure organic matter and clays, the expected D(-)/H(-) and (16)OD(-)/(16)OH(-) variations as a function of the mixing proportions were determined. These numerical predictions are consistent with measurements on laboratory prepared mixtures of D-rich organic matter and D-poor phyllosilicates, validating both the proposed experimental protocol and its use for meteorites. With an improvement of the precision of the ionic ratios by a factor of 10, it should possible to expend this protocol to samples having natural terrestrial D/H variations. Such an improvement could be attainable with the development of synthetic deuterated reference samples. PMID:23121456

Piani, Laurette; Remusat, Laurent; Robert, François

2012-12-01

309

Adaptation of continuous-flow cavity ring-down spectroscopy for batch analysis of ?13C of CO2 and comparison with isotope ratio mass spectrometry.  

PubMed

Measurements of ?(13)C in CO(2) have traditionally relied on samples stored in sealed vessels and subsequently analyzed using magnetic sector isotope ratio mass spectrometry (IRMS), an accurate but expensive and high-maintenance analytical method. Recent developments in optical spectroscopy have yielded instruments that can measure ?(13)CO(2) in continuous streams of air with precision and accuracy approaching those of IRMS, but at a fraction of the cost. However, continuous sampling is unsuited for certain applications, creating a need for conversion of these instruments for batch operation. Here, we present a flask (syringe) adaptor that allows the collection and storage of small aliquots (20-30 mL air) for injection into the cavity ring-down spectroscopy (CRDS) instrument. We demonstrate that the adaptor's precision is similar to that of traditional IRMS (standard deviation of 0.3‰ for 385 ppm CO(2) standard gas). In addition, the concentration precision (±0.3% of sample concentration) was higher for CRDS than for IRMS (±7% of sample concentration). Using the adaptor in conjunction with CRDS, we sampled soil chambers and found that soil-respired ?(13)C varied between two different locations in a piñon-juniper woodland. In a second experiment, we found no significant discrimination between the respiration of a small beetle (~5 mm) and its diet. Our work shows that the CRDS system is flexible enough to be used for the analysis of batch samples as well as for continuous sampling. This flexibility broadens the range of applications for which CRDS has the potential to replace magnetic sector IRMS. PMID:21766378

Berryman, E M; Marshall, J D; Rahn, T; Cook, S P; Litvak, M

2011-08-30

310

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

PubMed

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

2014-06-15

311

Fast and sample cleanup-free measurement of nicotine and cotinine by stable isotope dilution ultra-performance liquid chromatography-tandem mass spectrometry.  

PubMed

We developed a stable isotope dilution ultra-performance liquid chromatography-electrospray ionization tandem mass spectrometry assay to measure nicotine and cotinine, the major oxidative and pharmacologically less active metabolite of nicotine, in human urine. A simple dilution step was used as sample preparation and the measurement of nicotine and cotinine was performed during a 1.5-min run-time using nicotine-D? and cotinine-D? as internal standards. Multiple calibration curves for the analysis of both nicotine and cotinine exhibited a consistent excellent linearity and reproducibility in the range of 5-35,000 ?g/L (r>0.999). Limits of Detection were 0.7 ?g/L for nicotine and 0.4 ?g/L for cotinine, and Lower Limits of Quantification were 1.7 ?g/L for nicotine and 1.1 ?g/L for cotinine. The intraassay coefficients of variation (CVs) for nicotine and cotinine were <4% and <2%, respectively, the interassay CVs were <6% for nicotine and <4% for cotinine. The inaccuracy was <6% for both substances. The mean recovery was 103.2% (range 96.8-105.1%) for nicotine and 97.4% (range 94.3-99.2%) for cotinine. A method comparison showed that the values of nicotine metabolites in human urine samples (n=98) measured by a commercially available chemiluminescent immunoassay tested on analyzer IMMULITE 2000 were much higher than the cotinine concentration in the same urine samples measured by our UPLC-MS/MS assay. The Passing-Bablok regression line was: immunoassay=4.62 (UPLC-MS/MS)+3.64 [?g/L]; r=0.75. This robust, sensitive and interference-free UPLC-MS/MS assay permits rapid and accurate determination of nicotine and cotinine in human urine. PMID:22608097

Kuhn, Joachim; Vollmer, Tanja; Martin, Claudia; Hendig, Doris; Knabbe, Cornelius

2012-01-01

312

Simultaneous measurement of amiodarone and desethylamiodarone in human plasma and serum by stable isotope dilution liquid chromatography-tandem mass spectrometry assay.  

PubMed

A stable isotope dilution liquid chromatography-electrospray ionization tandem mass spectrometry (LC-MS/MS) assay to measure amiodarone, the most frequently used agent for maintaining sinus rhythm in patients with atrial fibrillation, and its major metabolite desethylamiodarone in human plasma and serum was developed. Measurement of amiodarone and desethylamiodarone was performed during a 4.0-min run-time using amiodarone-D(4) and desethylamiodarone-D(4) as internal standards. Calibration curves covering 12 calibrators measured in four replicates each for the analysis of both amiodarone and desethylamiodarone were linear and reproducible in the range of 0.01-40.0 mg/L (r>0.999). Limits of detection in plasma matrix were 2.7 microg/L for amiodarone and 1.9 microg/L for desethylamiodarone, and lower limits of quantification in plasma matrix were 7.5 microg/L for amiodarone and 2.5 microg/L for desethylamiodarone. Interassay imprecision and inaccuracy were <8% and <9% for both substances. Mean extraction yield was 99.6% (range 92.6-107.7%) for amiodarone and 90.2% (range 80.0-94.7%) for desethylamiodarone. Agreement was moderate for amiodarone (n=162) and desethylamiodarone (n=117), respectively, between the present method and a HPLC method with UV detection using a commercially available reagent set for the HPLC analysis of these drugs. The Passing-Bablok regression line was HPLC=0.98 (LC-MS/MS)+0.10 [mg/L]; r=0.94 for amiodarone and HPLC=1.05 (LC-MS/MS)+0.02 [mg/L]; r=0.90 for desethylamiodarone. This sensitive and interference-free LC-MS/MS assay permits rapid and accurate determination of amiodarone and desethylamiodarone in human plasma and other body fluids. PMID:19720490

Kuhn, Joachim; Götting, Christian; Kleesiek, Knut

2010-01-01

313

Computational mass spectrometry for small molecules  

PubMed Central

The identification of small molecules from mass spectrometry (MS) data remains a major challenge in the interpretation of MS data. This review covers the computational aspects of identifying small molecules, from the identification of a compound searching a reference spectral library, to the structural elucidation of unknowns. In detail, we describe the basic principles and pitfalls of searching mass spectral reference libraries. Determining the molecular formula of the compound can serve as a basis for subsequent structural elucidation; consequently, we cover different methods for molecular formula identification, focussing on isotope pattern analysis. We then discuss automated methods to deal with mass spectra of compounds that are not present in spectral libraries, and provide an insight into de novo analysis of fragmentation spectra using fragmentation trees. In addition, this review shortly covers the reconstruction of metabolic networks using MS data. Finally, we list available software for different steps of the analysis pipeline. PMID:23453222

2013-01-01

314

Computational mass spectrometry for small molecules.  

PubMed

: The identification of small molecules from mass spectrometry (MS) data remains a major challenge in the interpretation of MS data. This review covers the computational aspects of identifying small molecules, from the identification of a compound searching a reference spectral library, to the structural elucidation of unknowns. In detail, we describe the basic principles and pitfalls of searching mass spectral reference libraries. Determining the molecular formula of the compound can serve as a basis for subsequent structural elucidation; consequently, we cover different methods for molecular formula identification, focussing on isotope pattern analysis. We then discuss automated methods to deal with mass spectra of compounds that are not present in spectral libraries, and provide an insight into de novo analysis of fragmentation spectra using fragmentation trees. In addition, this review shortly covers the reconstruction of metabolic networks using MS data. Finally, we list available software for different steps of the analysis pipeline. PMID:23453222

Scheubert, Kerstin; Hufsky, Franziska; Böcker, Sebastian

2013-01-01

315

Development of isotope labeling liquid chromatography mass spectrometry for mouse urine metabolomics: quantitative metabolomic study of transgenic mice related to Alzheimer's disease.  

PubMed

Because of a limited volume of urine that can be collected from a mouse, it is very difficult to apply the common strategy of using multiple analytical techniques to analyze the metabolites to increase the metabolome coverage for mouse urine metabolomics. We report an enabling method based on differential isotope labeling liquid chromatography mass spectrometry (LC-MS) for relative quantification of over 950 putative metabolites using 20 ?L of urine as the starting material. The workflow involves aliquoting 10 ?L of an individual urine sample for (12)C-dansylation labeling that target amines and phenols. Another 10 ?L of aliquot was taken from each sample to generate a pooled sample that was subjected to (13)C-dansylation labeling. The (12)C-labeled individual sample was mixed with an equal volume of the (13)C-labeled pooled sample. The mixture was then analyzed by LC-MS to generate information on metabolite concentration differences among different individual samples. The interday repeatability for the LC-MS runs was assessed, and the median relative standard deviation over 4 days was 5.0%. This workflow was then applied to a metabolomic biomarker discovery study using urine samples obtained from the TgCRND8 mouse model of early onset familial Alzheimer's disease (FAD) throughout the course of their pathological deposition of beta amyloid (A?). It was showed that there was a distinct metabolomic separation between the AD prone mice and the wild type (control) group. As early as 15-17 weeks of age (presymptomatic), metabolomic differences were observed between the two groups, and after the age of 25 weeks the metabolomic alterations became more pronounced. The metabolomic changes at different ages corroborated well with the phenotype changes in this transgenic mice model. Several useful candidate biomarkers including methionine, desaminotyrosine, taurine, N1-acetylspermidine, and 5-hydroxyindoleacetic acid were identified. Some of them were found in previous metabolomics studies in human cerebrospinal fluid or blood samples. This work illustrates the utility of this isotope labeling LC-MS method for biomarker discovery using mouse urine metabolomics. PMID:25164377

Peng, Jun; Guo, Kevin; Xia, Jianguo; Zhou, Jianjun; Yang, Jing; Westaway, David; Wishart, David S; Li, Liang

2014-10-01

316

Mass Spectrometry and Computational Proteomics Vineet Bafna  

E-print Network

Mass Spectrometry and Computational Proteomics Vineet Bafna Computer Science & Engineering, Univ Abstract Mass Spectrometry is the tool of choice for Proteomics, with applications to peptide sequencing of algorithms for interpreting mass spectrometry (MS) data is provided. This overview is not intended

Bafna, Vineet

317

Application of Mass Spectrometry in Proteomics  

Microsoft Academic Search

Mass spectrometry has arguably become the core technology in proteomics. The application of mass spectrometry based techniques for the qualitative and quantitative analysis of global proteome samples derived from complex mixtures has had a big impact in the understanding of cellular function. Here, we give a brief introduction to principles of mass spectrometry and instrumentation currently used in proteomics experiments.

Ida Chiara Guerrera; Oliver Kleiner

2005-01-01

318

Sulfur isotope analysis of cinnabar from Roman wall paintings by elemental analysis/isotope ratio mass spectrometry--tracking the origin of archaeological red pigments and their authenticity.  

PubMed

The most valuable pigment of the Roman wall paintings was the red color obtained from powdered cinnabar (Minium Cinnabaris pigment), the red mercury sulfide (HgS), which was brought from mercury (Hg) deposits in the Roman Empire. To address the question of whether sulfur isotope signatures can serve as a rapid method to establish the provenance of the red pigment in Roman frescoes, we have measured the sulfur isotope composition (?(34)S value in ‰ VCDT) in samples of wall painting from the Roman city Aventicum (Avenches, Vaud, Switzerland) and compared them with values from cinnabar from European mercury deposits (Almadén in Spain, Idria in Slovenia, Monte Amiata in Italy, Moschellandsberg in Germany, and Genepy in France). Our study shows that the ?(34)S values of cinnabar from the studied Roman wall paintings fall within or near to the composition of Almadén cinnabar; thus, the provenance of the raw material may be deduced. This approach may provide information on provenance and authenticity in archaeological, restoration and forensic studies of Roman and Greek frescoes. PMID:20857439

Spangenberg, Jorge E; Lavric, Jost V; Meisser, Nicolas; Serneels, Vincent

2010-10-15

319

Direct mass measurements on francium isotopes and deduced masses for odd- z neighbouring elements  

NASA Astrophysics Data System (ADS)

The masses of 204-210, 212Fr and 224-228Fr have been determined with direct on-line mass spectrometry. From previously known Qa values, the masses of 28 isotopes of Pa, Ac, At, Bi and Tl are deduced. All these experimental masses are compared with the current mass predictions.

Epherre, M.; Audi, G.; Thibault, C.; Klapisch, R.; Huber, G.; Touchard, F.; Wollnik, H.

1980-05-01

320

Mass spectrometry. [review of techniques  

NASA Technical Reports Server (NTRS)

Advances in mass spectrometry (MS) and its applications over the past decade are reviewed in depth, with annotated literature references. New instrumentation and techniques surveyed include: modulated-beam MS, chromatographic MS on-line computer techniques, digital computer-compatible quadrupole MS, selected ion monitoring (mass fragmentography), and computer-aided management of MS data and interpretation. Areas of application surveyed include: organic MS and electron impact MS, field ionization kinetics, appearance potentials, translational energy release, studies of metastable species, photoionization, calculations of molecular orbitals, chemical kinetics, field desorption MS, high pressure MS, ion cyclotron resonance, biochemistry, medical/clinical chemistry, pharmacology, and environmental chemistry and pollution studies.

Burlingame, A. L.; Kimble, B. J.; Derrick, P. J.

1976-01-01

321

A mass spectrometry primer for mass spectrometry imaging  

PubMed Central

Mass spectrometry imaging (MSI), a rapidly growing subfield of chemical imaging, employs mass spectrometry (MS) technologies to create single- and multi-dimensional localization maps for a variety of atoms and molecules. Complimentary to other imaging approaches, MSI provides high chemical specificity and broad analyte coverage. This powerful analytical toolset is capable of measuring the distribution of many classes of inorganics, metabolites, proteins and pharmaceuticals in chemically and structurally complex biological specimens in vivo, in vitro, and in situ. The MSI approaches highlighted in this Methods in Molecular Biology volume provide flexibility of detection, characterization, and identification of multiple known and unknown analytes. The goal of this chapter is to introduce investigators who may be unfamiliar with MS to the basic principles of the mass spectrometric approaches as used in MSI. In addition to guidelines for choosing the most suitable MSI method for specific investigations, cross-references are provided to the chapters in this volume that describe the appropriate experimental protocols. PMID:20680583

Rubakhin, Stanislav S.; Sweedler, Jonathan V.

2011-01-01

322

On the capabilities of isotope dilution alpha spectrometry in the determination of plutonium concentration  

NASA Astrophysics Data System (ADS)

The determination of plutonium in spent fuel solution by isotope dilution alpha spectrometry (IDAS) is described. Two aliquots of spent fuel solution were separately spiked with well characterized solutions of 238Pu and 239Pu. The pure spiked and unspiked plutonium solutions were obtained using a partition chromatographic technique. The alpha activity ratios of {238Pu}/{(239Pu+240Pu)} have been measured by alpha spectrometry and the concentration of plutonium calculated using isotopic composition data from mass spectrometry measurements. In parallel, the plutonium concentration was also determined by isotope dilution mass spectrometry (IDMS). The main aim of this experiment was to show the capability of IDAS compared to IDMS. Therefore the factors affecting the precision and accuracy of the IDAS method are discussed in detail. Also the outline of IDAS based exclusively on radiometric measurements (isotopic composition of plutonium by gamma spectrometry) is presented and its capabilities discussed.

Parus, J.; Raab, W.; Swietly, H.; Cappis, J.; Deron, S.

1992-02-01

323

Standard test method for analysis of total and isotopic uranium and total thorium in soils by inductively coupled plasma-mass spectrometry  

E-print Network

1.1 This test method covers the measurement of total uranium (U) and thorium (Th) concentrations in soils, as well as the determination of the isotopic weight percentages of 234U, 235U, 236U, and 238U, thereby allowing for the calculation of individual isotopic uranium activity or total uranium activity. This inductively coupled plasma-mass spectroscopy (ICP-MS) method is intended as an alternative analysis to methods such as alpha spectroscopy or thermal ionization mass spectroscopy (TIMS). Also, while this test method covers only those isotopes listed above, the instrumental technique may be expanded to cover other long-lived radioisotopes since the preparation technique includes the preconcentration of the actinide series of elements. The resultant sample volume can be further reduced for introduction into the ICP-MS via an electrothermal vaporization (ETV) unit or other sample introduction device, even though the standard peristaltic pump introduction is applied for this test method. The sample preparatio...

American Society for Testing and Materials. Philadelphia

2008-01-01

324

Evaluation of Resonance Ionization Mass Spectrometry for the Determination of 135Cs / 137Cs Isotope Ratios in Low-Level Samples  

SciTech Connect

Determination of the ratio of 135Cs / 137Cs radioisotopes using resonance ionization mass spectrometry (RIMS) has been evaluated for measurements requiring extreme background suppression characteristics. Single-resonance excitation of Cs 6s 2S1/2 (F = 4) ® 6p 2P3/2 (F¢ = 5) with an extended cavity diode laser was followed by photoionization with the 488 nm line of an argon ion laser. While the principal objective was to avoid isobaric interferences, an optical selectivity of ~ 3 orders of magnitude against stable 133Cs was attained for both 135Cs and 137Cs. The overall RIMS efficiency was found to be ~ 2´10-6 with a combined (mass spectrometer and laser) selectivity of ~ 1010. The performance with respect to efficiency, selectivity, and isobar suppression has been compared to conventional thermal ionization mass spectrometry (TIMS). Measurements to determine the chronological age of a burn-up sample have been performed using both methods.

Pibida, L.; Nortershauser, W.; Hutchinson, J.M.R.; Bushaw, Bruce A.

2001-01-01

325

Isotopic Analysis of OS and RE with Negative Thermal Ion Mass Spectrometry and Application to the Age and Evolution of Iron Meteorites  

NASA Astrophysics Data System (ADS)

The ^187Re-^187Os isotope system has long been recognized as a method by which the age of iron meteorites can be directly determined (Herr et al., 1961). Pioneering work by Luck and Allegre (1983) established a whole-rock isochron for iron meteorites and the results, were used to determine indirectly the half-life of ^187Re. We have developed: a) high ionization efficiency mass spectrometry techniques for platinum group elements, including both Re and Os separated from iron meteorites (Creaser et al., 1991, 1992); b) low filament loading blanks for both Re and Os (<0.1 picogram, each); c) high yield and low blanks for the chemical separation techniques (yields 70-80%; blanks 1 pg for Os, <10 pg for Re). We have developed a new method for the rapid, clean and efficient separation of Os and Re from 10^-2 g samples of iron meteorites. This will permit taking advantage of variations of Re/Os on a small scale. The chemical separation scheme involves acid dissolution, preconcentration of Os and Re from Fe-Ni, oxidative solvent extraction of Os and ion exchange chromatography to recover Re. We have established that Os and Re thus chemically separated from iron meteorites show the same ionization efficiency as Os and Re from standard solutions, namely ~20% for each element. Of primary importance is the degree of isotope exchange and equilibration between sample and spike for Os. By analyzing the isotopic composition of Os at different stages of the chemical separation we are able to demonstrate that isotopic equilibration can be achieved to the level of +-1o/oo. However, this is not yet a routinely resolved issue. We believe, based on experience during the development of this technique, that isotope equilibration for Os prior to chemical separation is a critical issue that needs further attention. The results we have obtained so far from iron meteorites are given in Table 1. We have started analyses of the large magmatic group of IIA irons, which are little shocked and little metamorphosed, in order to attempt to establish a high precision isochron for these objects. For two samples, where we have high precision data for both Os and Re, the slope indicated is 0.077, which yields an age of 4530 Ma using the best estimate of the ^187Re half-life by direct measurement (Lindner et al., 1989). These results are in close agreement with the revised data of Horan et al. (1992) but markedly different from published iron meteorite data using the lower precision techniques where slopes of 0.070-0.074 indicate apparent ages of 4150-4350 Ma. We believe that previously reported data, including the data on the half-life of ^187Re, require confirmation using the current high-precision and high- sensitivity techniques, before the reliability and utility of the Re-Os technique can be ascertained. Acknowledgement. This work was supported by NASA, Grant NAG 943. Contribution No. 779. References Creaser, R. A., Papanastassiou, D. A., and Wasserburg, G. J. (1991a) Geochim. Cosmochim. Acta 55, 397-401. Creaser, R. A., Papanastassiou, D. A., and Wasserburg, G. J. (1992) Lunar Planet. Sci. XXIII (abstract), 255-256. Herr, W., Hoffmeister, W., Hirt, B., Geiss, J., and Houtermans, F. G. (1961) Z. Naturforsch. 16a, 1053-1058. Horan, M. F., Morgan, J. W., Walker, R. J., and Grossman, J. N. (1992) Science 255, 1118-1121. Lindner, M., Leich, D. A., Russ, G. P., Bazan, J. M., and Borg, R. J. (1989) Geochim. Cosmochim. Acta 53, 1597-1606. Luck, J. M. and Allegre, C. J. (1983) Nature 302, 130-132. Table 1. Re-Os isotopic data from iron meteorites. Os ppm Re ppb 187Os/188Os 187Re/188Os Bennett County IIA 59.6+-0.1 0.12503+-5 Coahuila IIA 9.87+-0.02 0.14158+-7 Tocopilla IIA 1.062+-0.002 207.9 0.16913+-15 0.9451 Negrillos IIA 69.4+-0.1 5022.7 0.12315+-2 0.3497 Cape York IIIA 0.13374+-9 Canyon Diablo IA 0.13464+-11 Tlacotepc IVB 0.12068+-8 Osmium standard (NHr)2OsCl6 0.14911+-3

Creaser, R. A.; Papanastassiou, D. A.; Wasserburg, G. J.

1992-07-01

326

Electrophoresis-mass spectrometry probe  

DOEpatents

The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface. 8 figs.

Andresen, B.D.; Fought, E.R.

1987-11-10

327

Electrophoresis-mass spectrometry probe  

DOEpatents

The invention involves a new technique for the separation of complex mixtures of chemicals, which utilizes a unique interface probe for conventional mass spectrometers which allows the electrophoretically separated compounds to be analyzed in real-time by a mass spectrometer. This new chemical analysis interface, which couples electrophoresis with mass spectrometry, allows complex mixtures to be analyzed very rapidly, with much greater specificity, and with greater sensitivity. The interface or probe provides a means whereby large and/or polar molecules in complex mixtures to be completely characterized. The preferred embodiment of the probe utilizes a double capillary tip which allows the probe tip to be continually wetted by the buffer, which provides for increased heat dissipation, and results in a continually operating interface which is more durable and electronically stable than the illustrated single capillary tip probe interface.

Andresen, Brian D. (Pleasanton, CA); Fought, Eric R. (Livermore, CA)

1987-01-01

328

Measurements of 59Ni in meteorites by accelerator mass spectrometry  

Microsoft Academic Search

Isotopic abundances of the radionuclide 59Ni (T1\\/2 = 76000 yr) were measured by accelerator mass spectrometry with the 14UD Pelletron tandem accelerator at the Australian National University and a detection system solely based on a multianode ionization chamber. The sensitivity limit in the measurement of 59Ni isotopic abundances is 5 × 10-13, as determined by residual interferences from isobaric 59Co

M. Paul; L. K. Fifield; D. Fink; A. Albrecht; G. L. Allan; G. Herzog; C. Tuniz

1993-01-01

329

Raman spectroscopic and mass spectrometric investigations of the hydrogen isotopes and isotopically labelled methane  

Microsoft Academic Search

Suitable analytical methods must be tested and developed for monitoring the individual process steps within the fuel cycle of a fusion reactor and for tritium accountability. The utility of laser-Raman spectroscopy accompanied by mass spectrometry with an Omegatron was investigated using the analysis of all hydrogen isotopes and isotopically labeled methanes as an example. The Omegatron is useful for analyzing

Fluor Daniel Hanford

1997-01-01

330

On-line monitoring of benzene air concentrations while driving in traffic by means of isotopic dilution gas chromatography/mass spectrometry.  

PubMed

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

1996-01-01

331

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

PubMed

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

2014-03-01

332

Fourier Transform Mass Spectrometry Lab  

NSDL National Science Digital Library

This Web site discusses Boston University's Fourier Transform Mass Spectrometry (FTMS) Lab's devotion to the improvement of FTMS instrumentation and methods for its everyday biochemical functions. After discovering the importance of FTMS, visitors can find out about the lab's work in the enhancement of electrospray ion source and Cryogenic FTMS. Students can learn about the modern biochemistry's utilization of both traditional instrumentation such as gel electrophoresis and the latest devices including high performance chromatography, nuclear magnetic resonance, and X-ray crystallography. By downloading the Boston University Data Analysis (B.U.D.A.), researchers can participate in the development of analysis software for FTMS.

333

Resonant Laser Ionization Mass Spectrometry: An Alternative to AMS?  

SciTech Connect

Resonant laser ionization mass spectrometry (RIMS) has developed into a versatile experimental method particularly concerning applications for highly selective ultratrace analaysis. Apart from providing nearly complete isobaric suspression and high overall efficiency, the possibolility for combining optical isotpic selectivity with that of hte mass spectrometer leads to remarkable specifications. The widespread analytical potential and applicability of different techniques based on resonant laser ionization is demonstrated in investigations on stable and radioactive ultratrace isotopes with the focus on applications which require high selectivity, concerning, e.g., the noble gas isotopes, 81,85KR, PU isotopes, 89,90SR, 99Tc and 41Ca. Selective ultratrace determination of these radioisotopes proved access to a variety of fundamental research problems in environmental sciences, geo- and cosmochemistry, archaeology, and biomedicine, which previously were often an exclusive domain for accelerator mass spectrometry (AMS).

Wendt, Klaus; Trautmann, N.; Bushaw, Bruce A.

2001-02-15

334

Laser ablation inductively coupled plasma mass spectrometry for the trace, ultratrace and isotope analysis of long-lived radionuclides in solid samples  

Microsoft Academic Search

The capability of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) for determination of long-lived radionuclides in different materials (e.g., in geological samples, high-purity graphite and nonconducting concrete matrix) was investigated. The main problem in the quantification of the analytical results of long-lived radionuclides is that (except for geological samples) no suitable standard reference materials are available. Therefore, synthetic laboratory

Johanna Sabine Becker; Carola Pickhardt; Hans-Joachim Dietze

2000-01-01

335

Mass independent bias in W isotopes in MC-ICP-MS instruments Naoki Shiraiab  

E-print Network

Mass independent bias in W isotopes in MC-ICP-MS instruments Naoki Shiraiab and Munir Humayun of natural mass independent isotope variations by precise isotopic measurements of elements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) requires a detailed understanding of the instrumental

Weston, Ken

336

MASS SPECTROMETRY OF FATTY ALDEHYDES  

PubMed Central

Fatty aldehydes are important components of the cellular lipidome. Significant interest has been developed towards the analysis of the short chain ?,?-unsaturated and hydroxylated aldehydes formed as a result of oxidation of polyunsaturated fatty acids. Multiple gas chromatography-mass spectrometry (GC/MS) and subsequently liquid chromatography-mass spectrometry (LC/MS) approaches have been developed to identify and quantify short-chain as well as long-chain fatty aldehydes. Due to the ability to non-enzymaticaly form Schiff bases with amino groups of proteins, lipids, and with DNA guanidine, free aldehydes are viewed as a marker or metric of fatty acid oxidation and not the part of intracellular signaling pathways which has significantly limited the overall attention this group of molecules have received. This review provides an overview of current GC/MS and LC/MS approaches of fatty aldehyde analysis as well as discusses technical challenges standing in the way of free fatty aldehyde quantitation. PMID:21930240

Berdyshev, Evgeny V.

2011-01-01

337

MSDash: mass spectrometry database and search.  

PubMed

Along with the wide application of mass spectrometry in proteomics, more and more mass spectrometry data are becoming publicly available. Several public mass spectrometry data repositories have been built on the Internet. However, most of these repositories are devoid of effective searching methods. In this paper we describe a new mass spectrometry data library, and a novel method to efficiently index and search in the library for spectra that are similar to a query spectrum. A public online server have been set up and demonstrated outstanding speed and scalability of our methods. Together with the mass spectrometry library, our searching method can improve the protein identification confidence by comparing a spectrum with the ones that are already characterized in the database. The searching method can also be used alone to cluster the similar spectra in a mass spectrometry dataset together, in order to to improve the speed and accuracy of the protein identification or quantification. PMID:19642269

Wu, Zhan; Lajoie, Gilles; Ma, Bin

2008-01-01

338

Secondary Ion Mass Spectrometry of Environmental Aerosols  

SciTech Connect

Atmospheric particles influence many aspects of climate, air quality and human health. Understanding the composition, chemistry and behavior of atmospheric aerosols is a key remaining challenge in improving climate models. Furthermore, particles may be traced back to a particular source based on composition, stable isotope ratios, or the presence of particular surface chemistries. Finally, the characterization of atmospheric particles in the workplace plays an important role in understanding the potential for exposure and environmental and human health effects to engineered and natural nanoscale particles. Secondary ion mass spectrometry (SIMS) is a useful tool in determining any of several aspects of the structure, composition and chemistry of these particles. Often used in conjunction with other surface analysis and electron microscopy methods, SIMS has been used to determine or confirm reactions on and in particles, the presence of particular organic species on the surface of atmospheric aerosols and several other interesting and relevant findings. Various versions of SIMS instruments – dynamic SIMS, time of flight secondary ion mass spectrometry or TOF-SIMS, nanoSIMS – have been used to determine specific aspects of aerosol structure and chemistry. This article describes the strengths of each type of SIMS instrument in the characterization of aerosols, along with guidance on sample preparation, specific characterization specific to the particular information sought in the analysis. Examples and guidance are given for each type of SIMS analysis.

Gaspar, Daniel J.; Cliff, John B.

2010-08-01

339

Resonance ionization mass spectrometry for precise measurements of iostope ratios.  

SciTech Connect

Resonance ionization mass spectrometry offers extremely high sensitivity and elemental selectivity in microanalysis, but the isotopic precision attainable by this technique has been limited. Measured isotope ratios are sensitive to small fluctuations in the pointing, pulse timing, and wavelength of the resonance lasers. We show that, by minimizing these fluctuations using feedback controls and by power-broadening the optical transitions, we are able to measure chromium isotope ratios with statistics-limited precision better than 1%. Small additional improvements in reproducibility come from careful shaping of the electric field in the region where atoms are photoionized and from minimizing pulse-to-pulse variations in the time-of-flight mass spectrometer through which the photoions travel. The increased reproducibility of isotopic measurements on standard materials has enabled us to detect anomalous chromium isotopic abundances in presolar SiC grains extracted from primitive meteorites.

Levine, J.; Savina, M. R.; Stephan, T.; Dauphas, N.; Davis, A. M.; Knight, K. B.; Pellin, M. J.; Materials Science Division; Chicago Center for Cosmochemistry; Univ.of Chicago; Univ. of California at Berkeley; LLNL

2009-11-01

340

Analysis of household ignitable liquids and their post-combustion weathered residues using compound-specific gas chromatography-combustion-isotope ratio mass spectrometry.  

PubMed

The continuing rise in home and vehicular arson cases involving the use of ignitable liquids continues to be an area of concern for criminal and civil investigators. In this study, the compound-specific ?(13)C values of various components of four flammable household chemicals were measured using a single quadrupole mass spectrometer and an isotope ratio mass spectrometer as simultaneous detectors for a gas chromatograph. Whereas compound-specific carbon isotope ratios were able to discriminate between different sources of neat (pre-combustion) ignitable liquids, analyses of the post-combustion residues were problematic. Weathering caused by combustion resulted in a significant increase in the (13)C content of specific peaks relative to the neat liquids (i.e. less negative delta values) such that the isotopic comparison of pre- and post-combustion residues resulted in fractionation ranging from 0 to +10‰. Because of the current lack of understanding of isotopic fractionation during combustion, and because of problems encountered with co-elution in the more complex samples, compound-specific IRMS does not appear to be suitable for fire debris analysis. The comparison of non-combusted or non-weathered ignitable liquids is much more reliable, especially for relatively simple mixtures, and is best suited for exclusionary purposes until such time as a comprehensive database of samples is developed. Without a measure of the population variance, one cannot presently predict the false positive identification rate for the comparison of two ignitable liquids; i.e. the probability that two random ignitable liquid samples have indistinguishable isotope ratios. PMID:24314542

Schwartz, Zeland; An, Yan; Konstantynova, Kateryna I; Jackson, Glen P

2013-12-10

341

Assessment of ultrasound-assisted extraction as sample pre-treatment for the measurement of lead isotope ratios in marine biological tissues by multicollector inductively coupled plasma-mass spectrometry  

NASA Astrophysics Data System (ADS)

In this work, ultrasound-assisted extraction (UAE) was evaluated as a sample preparation procedure for lead isotope ratio measurements in marine biological tissues by multicollector inductively coupled plasma-mass spectrometry. 20 mg of marine biological tissue and 1 mL of acid extractant were sonicated for 3 min at 60% ultrasound amplitude. Matrix separation was performed in the supernatant using a chromatographic exchange resin (Sr-Spec™). Total elimination of organic matter was achieved during the separation step. Microwave-assisted digestion and dry-ashing were used for comparative purposes. No significant differences were found in lead isotope ratios at 95% of confidence level. UAE emerges as an advantageous alternative to classical methods for sample preparation owing to its simplicity and rapidity ( i.e. operation steps were reduced), low reagent consumption and low contamination risks.

Costas-Rodríguez, M.; Lavilla, Isela; Bendicho, Carlos

2011-06-01

342

Compact hydrogen/helium isotope mass spectrometer  

DOEpatents

The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently, no fieldable D or molecular speciation detectors exist. Furthermore, the present spectrometer has a significant advantage over traditional T detectors: no confusion of the measurements by other beta-emitters, and complete separation of atomic and molecular species of equivalent atomic mass (e.g., HD and .sup.3 He).

Funsten, Herbert O. (Los Alamos, NM); McComas, David J. (Los Alamos, NM); Scime, Earl E. (Morgantown, WV)

1996-01-01

343

International Journal of Mass Spectrometry 229 (2003) 5560 High resolution mass spectrometry using a  

E-print Network

their mass spectra with high resolution. The instrument is compared to time-of-flight mass, as well as to ion of the earliest types of mass spectrometers is the time-of-flight mass spectrometer (TOFMS) [1,2]. AlthoughInternational Journal of Mass Spectrometry 229 (2003) 55­60 High resolution mass spectrometry using

Savin, Daniel Wolf

344

Cadmium measurements in coral skeleton using isotope dilutioninductively coupled plasmamass spectrometry  

E-print Network

Cadmium measurements in coral skeleton using isotope dilution­inductively coupled plasma for the precise analysis of Cd/Ca in coral skeleton using inductively coupled plasma­ mass spectrometry (ICP. McDonough, and A. G. Grottoli (2006), Cadmium measurements in coral skeleton using isotope dilution

Mcdonough, William F.

345

Laser Ablation Inductively Coupled Plasma Mass Spectrometry: Principles and Applications  

Microsoft Academic Search

The application of laser ablation inductively plasma mass spectrometry (LA?ICP?MS) to the determination of major, minor, and trace elements as well as isotope?ratio measurements offers superior technology for direct solid sampling in analytical chemistry. The advantages of LA?ICP?MS include direct analysis of solids; no chemical dissolution is necessary, reduced risk of contamination, analysis of small sample mass, and determination of

N. S. Mokgalaka; J. Gardea-Torresdey

2006-01-01

346

Development and validation of a new analytical method for the determination of 1,4-dichlorobenzene in honey by gas chromatography-isotope dilution mass spectrometry after steam-distillation.  

PubMed

A simple, fast, sensitive and robust analytical method using gas chromatography (GC)-isotope dilution mass spectrometry (MS) was developed and validated for the identification and quantification of 1,4-dichlorobenzene (p-DCB) residues in honey samples. The proposed methodology is based on steam-distillation using a Clevenger-type apparatus followed by gas chromatography-mass spectrometry (GC-MS) in the selected ion monitoring (SIM) mode employing the isotopically labeled analogue d4-1,4-dichlorobenzene (d4-p-DCB) as internal standard (IS). Validation of the method was performed in two different GC-MS systems, using quadrupole MS (QMS) and ion-trap MS (ITMS) detectors, with no statistically significant differences between two. Recoveries were better than 91% with percent relative standard deviations lower than 12%. The instrumental limits of detection were 1 microg kg(-1) in the GC-ITMS system and 0.6 microg kg(-1) in the GC-QMS system. The expanded uncertainty was estimated as 17% at the currently accepted "action level" of 10 microg kg(-1). The method was applied to the analysis of 310 honey samples in an extensive national monitoring study. A quality control (QC) system applied during the assays has demonstrated a good performance and long-term stability over a period of more than 8 months of continuous operation. PMID:17723727

Botitsi, E V; Kormali, P N; Kontou, S N; Economou, A; Tsipi, D F

2006-10-01

347

Counting Molecules by Desorption Ionization and Mass Spectrometry/Mass Spectrometry.  

ERIC Educational Resources Information Center

Discusses two newer methods in mass spectrometry and shows how they can increase signal and signal-to-noise ratios, respectively. The first method, desorption ionization (DI), increases sensitivity while the second method, mass spectrometry/mass spectrometry (MS/MS), increases specificity. Together, the two methods offer improved analytical…

Cooks, R. G.; Busch, K. L.

1982-01-01

348

Gas Chromatography-Mass Spectrometry Experiment  

NSDL National Science Digital Library

Gas Chromotography-Mass Spectrometry (GC-MS) is an analysis used in many laboratory testing situations. This laboratory exercise explains this method and uses this method to analyse DMSO. This exercise includes images and screenshots, as well as group discussion questions and questions for individual exploration of mass spectrometry online. Users may download this experiment in Microsoft Word doc file format.

Solow, Mike

2013-07-19

349

PROTEIN ANALYSIS BY HYDROGEN EXCHANGE MASS SPECTROMETRY  

Microsoft Academic Search

? Abstract Mass spectrometry has provided a powerful method for monitoring hydrogen exchange of protein backbone amides with deuterium from solvent. In com- parison to popular NMR approaches, mass spectrometry has the advantages of higher sensitivity, wider coverage of sequence, and the ability to analyze larger proteins. Pro- teolytic fragmentation of proteins following the exchange reaction provides moderate structural resolution,

Andrew N. Hoofnagle; Katheryn A. Resing; Natalie G. Ahn

2003-01-01

350

Advances in the application of mass spectrometry to studies of drug metabolism, pharmacokinetics and toxicology  

NASA Astrophysics Data System (ADS)

Applications of mass spectrometry to studies of drug metabolism, pharmacokinetics and toxicology published from the latter part of 1988 through mid-1991 are reviewed. Current trends and future prospects for mass spectrometry in these fields are discussed, with emphasis on the value of "soft ionization" techniques, on-line LC-MS systems, tandem mass spectrometry and stable isotopes for qualitative, quantitative and mechanistic investigations.

Baillie, Thomas A.

1992-09-01

351

Atomic spectrometry update - atomic mass spectrometry.  

SciTech Connect

The MS and XRF updates have been published together since their introduction in 1988. In the last few years, however, the two sections have been prepared independently of each other and it therefore seemed appropriate to publish the two sections separately. With effect from this issue, the MS Update will appear in the October issue of JAAS and the XRF Update in the November issue. The format used for the MS section is broadly similar to that used last year, with some additional sub-headings. This Update is intended to cover all atomic and stable isotopic MS techniques, but not those used in studies of fundamental nuclear physics and exotic nuclei far from stability. Also excluded are those reports in which MS is used as a tool in the study of molecular processes and of gaseous components. the review is based on critical selection of developments in instrumentation and methodology, notable for their innovation, originality or achievement of significant advances, and is not intended to be comprehensive in its coverage. Conference papers are only included if they contain enough information to show they meet these criteria, and our policy in general remains one of waiting for a development to appear in a full paper before inclusion in the review. a similar policy applies to foreign language papers unlikely to reach a wide audience. Routine applications of atomic MS are not included in this Update and the reader is referred to the Updates on Industrial Analysis: Metals, Chemicals and Advanced Materials (96/416), Environmental Analysis (96/1444) and Clinical and Biological Materials, Food and Beverages (96/2479). Also excluded are those applications, even if not routine, which use atomic spectroscopy as a tool for the study of a non-atomic property, for example, the use of stable isotope labeling of carbon or nitrogen in biomolecules in metabolic studies. There have been few general reviews on atomic MS of note in the period covered by this update. That of Colodner et al.(95/3890) gave a general review of ion sources, in particular GDMS, ICP-MS, SIMS and TIMS, and that of Blades (95/2568 and 95/3077) was a very general overview of some of the techniques covered in this Update. The review of the literature in the period covered by this Update reveals strong advances in all areas, with a continuing push to achieve better analyses on smaller samples and in less time. Most advances generally require more sophisticated instrumentation, improved sample preparation methods or new methods of sample introduction. This is typified by advances in ICP-MS, which see considerable emphasis on sample introduction techniques and a move towards magnetic sector instruments. Most applications of ICP-MS are now highly routine. There is still, however, a desire to achieve affordable analysis with simplified and cost-effective instruments, as illustrated by the development of mobile, in-situ isotope MS for environmental studies.

Bacon, J.; Crain, J. S.; McMahon, A. W.; Williams, J. G.; Analytical Chemistry Laboratory; The Macaulay Land Use Research Inst.; Manchester Metropolitan Univ.; Imperial Coll.

1996-10-01

352

Testing the limits of micro-scale analyses of Si stable isotopes by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry with application to rock weathering  

NASA Astrophysics Data System (ADS)

An analytical protocol for accurate in-situ Si stable isotope analysis has been established on a new second-generation custom-built femtosecond laser ablation system. The laser was coupled to a multicollector inductively coupled plasma mass spectrometer (fsLA-MC-ICP-MS). We investigated the influence of laser parameters such as spot size, laser focussing, energy density and repetition rate, and ICP-MS operating conditions such as ICP mass load, spectral and non-spectral matrix effects, signal intensities, and data processing on precision and accuracy of Si isotope ratios. We found that stable and reproducible ICP conditions were obtained by using He as aerosol carrier gas mixed with Ar/H2O before entering the plasma. Precise ?29Si and ?30Si values (better than ± 0.23‰, 2SD) can be obtained if the area ablated is at least 50 × 50 ?m; or, alternatively, for the analysis of geometric features down to the width of the laser spot (about 20 ?m) if an equivalent area is covered. Larger areas can be analysed by rastering the laser beam, whereas small single spot analyses reduce the attainable precision of ?30Si to ca. ± 0.6‰, 2SD, for < 30 ?m diameter spots. It was found that focussing the laser beam beneath the sample surface with energy densities between 1 and 3.8 J/cm2 yields optimal analytical conditions for all materials investigated here. Using pure quartz (NIST 8546 aka. NBS-28) as measurement standard for calibration (standard-sample-bracketing) did result in accurate and precise data of international reference materials and samples covering a wide range in chemical compositions (Si single crystal IRMM-017, basaltic glasses KL2-G, BHVO-2G and BHVO-2, andesitic glass ML3B-G, rhyolitic glass ATHO-G, diopside glass JER, soda-lime glasses NIST SRM 612 and 610, San Carlos olivine). No composition-dependent matrix effect was discernible within uncertainties of the method. The method was applied to investigate the Si isotope signature of rock weathering at the micro-scale in a corestone sampled from a highly weathered roadcut profile in the tropical Highlands of Sri Lanka. The results show that secondary weathering products accumulated in cracks and grain boundaries are isotopically lighter than their unweathered plagioclase host, consistent with isotopically heavy dissolved Si found in rivers.

Schuessler, Jan A.; von Blanckenburg, Friedhelm

2014-08-01

353

Standard test method for analysis of isotopic composition of uranium in nuclear-grade fuel material by quadrupole inductively coupled plasma-mass spectrometry  

E-print Network

1.1 This test method is applicable to the determination of the isotopic composition of uranium (U) in nuclear-grade fuel material. The following isotopic weight percentages are determined using a quadrupole inductively coupled plasma-mass spectrometer (Q-ICP-MS): 233U, 234U, 235U, 236U, and 238U. The analysis can be performed on various material matrices after acid dissolution and sample dilution into water or dilute nitric (HNO3) acid. These materials include: fuel product, uranium oxide, uranium oxide alloys, uranyl nitrate (UNH) crystals, and solutions. The sample preparation discussed in this test method focuses on fuel product material but may be used for uranium oxide or a uranium oxide alloy. Other preparation techniques may be used and some references are given. Purification of the uranium by anion-exchange extraction is not required for this test method, as it is required by other test methods such as radiochemistry and thermal ionization mass spectroscopy (TIMS). This test method is also described i...

American Society for Testing and Materials. Philadelphia

2000-01-01

354

Versatile inlet system for on-line compound-specific deltaD and delta13C gas chromatography-oxidation/reduction-isotope ratio mass spectrometry analysis of gaseous mixtures.  

PubMed

Compound-specific deltaD and delta13C analyses of gas mixtures are useful indicators of geochemical and environmental factors. However, the relative concentrations of individual components in gas mixtures (e.g., H2, CO2, methane, ethane, propane, i-butane, n-butane) may vary over several orders of magnitude. The determination of hydrogen and carbon compound-specific stable isotope ratios requires that the hydrogen and carbon dioxide produced from each separated component has a concentration adjusted to match the dynamic range of the stable isotope mass spectrometer. We present a custom-built gas sampling and injection system (GASIS) linked with a Delta Plus XP mass spectrometer that provides flexibility, ease of operation, and economical use of small gas samples with wide ranges of analyte concentrations. The overall on-line GC-ox/red-IRMS (Gas Chromatography - oxidation/reduction - Isotope Ratio Mass Spectrometry) system consists of (i) a customized GASIS inlet system and (ii) two alternative reactors, namely an oxidative Cu-Ni-Pt reactor at 950 degrees C for production of CO2 and a reductive graphitized Al2O3 reactor at 1420 degrees C for production of H2. In addition, the system is equipped with (iii) a liquid nitrogen spray-cooling unit for cryo-GC-focusing at -20 degrees C, and (iv) a Nafion dryer for removal of water vapor from product CO2. The three injection loops of the GASIS inlet allow flexibility in the volume of injected analyte gas (e.g., from 0.06 to 500 microL) in order to measure reproducible deltaD and delta13C values for gases at concentrations ranging from 100% down to 10 ppm. We calibrate our GC-ox/red-IRMS system with two isotopically distinct methane references gases that are combusted off-line and characterized using dual-inlet IRMS. PMID:17577874

Henning, Mark; Strapo?, Dariusz; Lis, Grzegorz P; Sauer, Peter; Fong, Jon; Schimmelmann, Arndt; Pratt, Lisa M

2007-01-01

355

Statistical characterization of multiple-reaction monitoring mass spectrometry (MRM-MS) assays for quantitative proteomics  

E-print Network

Multiple reaction monitoring mass spectrometry (MRM-MS) with stable isotope dilution (SID) is increasingly becoming a widely accepted assay for the quantification of proteins and peptides. These assays have shown great ...

Mani, D R

356

Highly Sensitive 14C and 3H Quantification of Biochemical Samples Using Accelerator Mass Spectrometry  

Microsoft Academic Search

Accelerator Mass Spectrometry (AMS) is an isotope ratio mass spectrometer that quantifies low levels of rare isotopes with half-lives between 10 and 10 years. Typical sensitivities are 10 atoms in a milligram-sized sample. AMS was originally developed for use in the geosciences as a tool to carbon date archaeological artifacts, but has applications in many fields. In the biosciences, the

T J Ognibene; J S Vogel

2003-01-01

357

Broadband Analysis of Bioagents by Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Mass spectrometry was first reported to provide analysis of intact metabolite biomarkers from whole cells in 1975.1 Since then advances in ionization techniques have extended our capabilities to polar lipids and, eventually, to proteins.2, 3 Mass spectrometry provides a broadband detection system, which, however, has great specificity. Bioinformatics plays an important role in providing flexible and rapid characterization of species, based on protein and peptide mass spectra collected in the field.

Fenselau, Catherine; Wynne, Colin; Edwards, Nathan

358

Establishing Drug Resistance in Microorganisms by Mass Spectrometry  

NASA Astrophysics Data System (ADS)

A rapid method to determine drug resistance in bacteria based on mass spectrometry is presented. In it, a mass spectrum of an intact microorganism grown in drug-containing stable isotope-labeled media is compared with a mass spectrum of the intact microorganism grown in non-labeled media without the drug present. Drug resistance is determined by predicting characteristic mass shifts of one or more microorganism biomarkers using bioinformatics algorithms. Observing such characteristic mass shifts indicates that the microorganism is viable even in the presence of the drug, thus incorporating the isotopic label into characteristic biomarker molecules. The performance of the method is illustrated on the example of intact E. coli, grown in control (unlabeled) and 13C-labeled media, and analyzed by MALDI TOF MS. Algorithms for data analysis are presented as well.

Demirev, Plamen A.; Hagan, Nathan S.; Antoine, Miquel D.; Lin, Jeffrey S.; Feldman, Andrew B.

2013-08-01

359

Mass spectrometry of proteins of known mass Andrew D. Miranker*  

E-print Network

Commentary Mass spectrometry of proteins of known mass Andrew D. Miranker* Department of Molecular measurements in biochemistry are as fundamental as mass. Whereas the mass of a macromolecule is often in- ferred by its migration through polymer gels, direct measure may only be deter- mined by mass

Miranker, Andrew

360

Cross contamination in dual inlet isotope ratio mass spectrometers  

Microsoft Academic Search

Since the early days of geochemical isotope ratio mass spectrometry there has always been the problem of cross contamination, i.e. the contamination of the sample gas with traces of reference gas (and vice versa) in a dual inlet system and the analyzer itself. This was attributable to valve leakages and could be corrected for. In modern leak-free machines this problem

H. A. J. Meijer; R. E. M. Neubert; G. H. Visser

2000-01-01

361

Detection and quantification of 1,N6-ethenoadenine in human urine by stable isotope dilution capillary gas chromatography/negative ion chemical ionization/mass spectrometry.  

PubMed

1,N(6)-Ethenoadenine (epsilonAde) is a promutagenic lesion detected in tissue DNA; it has been shown that epsilonAde can be repaired by human DNA glycosylases, and it is expected to be excreted in urine. In this paper, we present for the first time detection and accurate quantification of epsilonAde in human urine samples by a highly sensitive and specific stable isotope dilution gas chromatography/negative ion chemical ionization/mass spectrometric assay (GC/NICI/MS). Analysis by GC/NICI/MS includes adduct enrichment by a solid phase extraction column, followed by electrophore labeling and postderivatization cleanup. Using selective ion monitoring mode, the assay allows quantification of 0.5 pg of epsilonAde in as little as 0.1 mL of the urine sample, which is equivalent to corresponding concentration quantification limit of 31 pM. Using this assay, concentrations of epsilonAde in the 24 h urine samples of 23 healthy individuals were determined, which ranged from 0 to 124 pg/mL. After we adjusted for creatinine, a statistically significant correlation was found between epsilonAde excretion and cigarette smoking in males (p = 0.03). Thus, this stable isotope dilution GC/NICI/MS assay offers a sensitive and accurate quantification of urinary epsilonAde as a potential biomarker for oxidative damage of DNA and repair. PMID:12971797

Chen, Hauh-Jyun Candy; Chiu, Wei-Loong

2003-09-01

362

The forensic analysis of office paper using carbon isotope ratio mass spectrometry--part 1: understanding the background population and homogeneity of paper for the comparison and discrimination of samples.  

PubMed

Isotope Ratio Mass Spectrometry (IRMS) has been shown to be a useful tool in the comparison of materials that are chemically identical either through man-made production processes or for materials that have been naturally produced. Paper therefore, is an ideal material for this type of measurement given that it is manufactured from a naturally produced product that can be difficult to discriminate based on physical feature comparison alone. To determine whether carbon isotopes are useful for discriminating document papers, 125 samples from Australia and New Zealand were collected over a 24-month period. When measured, a range of 8‰ was observed. A homogeneity study was undertaken to examine the range of values expected from paper sources including single sheets, single reams and multiple reams from the same brand. These results can also be used to suggest how best to sample from these different sources. After characterizing the natural variation of the material, a range of 1‰ was defined for use as a benchmark for discrimination. Utilizing this threshold, 68% of the 125 collected samples (when paired against each other) could be discriminated using the carbon isotope abundances alone. Additionally, correlation was observed when measured values were plotted against their production region of origin. PMID:23623249

Jones, Kylie; Benson, Sarah; Roux, Claude

2013-09-10

363

Analysis of Mass Spectrometry Data for Protein Identification  

E-print Network

.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 2.2 Mass Spectrometry Pipeline . . . . . . . . . . . . . . . . . . . 8 2.2.1 Tandem Mass Spectrometry (MS/MS) . . . . . . . . . 9 2.3 From Spectra to Proteins

Mohri, Mehryar

364

Mercury determination in blood by gas chromatography-mass spectrometry  

Microsoft Academic Search

A stable isotope dilution gas chromatography-mass spectrometry method using196Hg as an internal standard is described for determining Hg in blood. In this method, the blood samples are not subjected to\\u000a any digestion to avoid the loss of Hg. A solution of 0.6M HCl is used to free Hg present in blood from proteins. The pH of the solution is adjusted

Suresh K. Aggarwal; Michael Kinter; David A. Herold

1994-01-01

365

Standard test method for analysis of urine for uranium-235 and uranium-238 isotopes by inductively coupled plasma-mass spectrometry  

E-print Network

1.1 This test method covers the determination of the concentration of uranium-235 and uranium-238 in urine using Inductively Coupled Plasma-Mass Spectrometry. This test method can be used to support uranium facility bioassay programs. 1.2 This method detection limits for 235U and 238U are 6 ng/L. To meet the requirements of ANSI N13.30, the minimum detectable activity (MDA) of each radionuclide measured must be at least 0.1 pCi/L (0.0037 Bq/L). The MDA translates to 47 ng/L for 235U and 300 ng/L for 238U. Uranium– 234 cannot be determined at the MDA with this test method because of its low mass concentration level equivalent to 0.1 pCi/L. 1.3 The digestion and anion separation of urine may not be necessary when uranium concentrations of more than 100 ng/L are present. 1.4 Units—The values stated in picoCurie per liter units are to be regarded as standard. The values given in parentheses are mathematical conversions to SI units that are provided for information only and are not considered standard. 1....

American Society for Testing and Materials. Philadelphia

2010-01-01

366

Plasma Desorption Mass Spectrometry: Coming of Age.  

ERIC Educational Resources Information Center

Discusses the history and development of Plasma Desorption Mass Spectrometry to determine molecular weights and structures of proteins and polymers. Outlines theory, instrumentation, and sample preparation commonly used. Gives several examples of resulting spectra. (ML)

Cotter, Robert J.

1988-01-01

367

Imaging mass spectrometry at cellular length scales  

Microsoft Academic Search

Imaging mass spectrometry (IMS) allows the direct investigation of both the identity and the spatial distribution of the molecular content directly in tissue sections, single cells and many other biological surfaces. In this protocol, we present the steps required to retrieve the molecular information from tissue sections using matrix-enhanced (ME) and metal-assisted (MetA) secondary ion mass spectrometry (SIMS) as well

A F Maarten Altelaar; Liam A McDonnell; Sander R Piersma; Ron M A Heeren

2007-01-01

368

Secondary ionization mass spectrometric analysis of impurity element isotope ratios in nuclear reactor materials  

NASA Astrophysics Data System (ADS)

During reactor operations and fuel burn up, some isotopic abundances change due to nuclear reactions and provide sensitive indicators of neutron fluence and fuel burnup. Secondary ion mass spectrometry (SIMS) analysis has been used to measure isotope ratios of selected impurity elements in irradiated nuclear reactor graphite. Direct SIMS measurements were made in graphite samples, following shaping and surface cleaning. Models predicting local fuel burnup based on isotopic measurements of B and Li isotopes by SIMS agreed well with U and Pu isotopic measurements obtained by thermal ionization mass spectrometry (TIMS).

Gerlach, D. C.; Cliff, J. B.; Hurley, D. E.; Reid, B. D.; Little, W. W.; Meriwether, G. H.; Wickham, A. J.; Simmons, T. A.

2006-07-01

369

JOURNAL OF MASS SPECTROMETRY J. Mass Spectrom. 2003; 38: 277282  

E-print Network

-capture dissociation; FTICR, Fourier transform ion cyclotron resonance; Q-TOF, quadrupole time-of-flight nanoelectrospray ionization tandem mass spectra. Owing to the accurate molecular mass of the intact proteinJOURNAL OF MASS SPECTROMETRY J. Mass Spectrom. 2003; 38: 277­282 Published online 24 January 2003

Manstein, Dietmar J.

370

Secondary Ion Mass Spectrometry SIMS XI  

NASA Astrophysics Data System (ADS)

This volume contains 252 contributions presented as plenary, invited and contributed poster and oral presentations at the 11th International Conference on Secondary Ion Mass Spectrometry (SIMS XI) held at the Hilton Hotel, Walt Disney World Village, Orlando, Florida, 7 12 September, 1997. The book covers a diverse range of research, reflecting the rapid growth in advanced semiconductor characterization, ultra shallow depth profiling, TOF-SIMS and the new areas in which SIMS techniques are being used, for example in biological sciences and organic surface characterization. Papers are presented under the following categories: Isotopic SIMS Biological SIMS Semiconductor Characterization Techniques and Applications Ultra Shallow Depth Profiling Depth Profiling Fundamental/Modelling and Diffusion Sputter-Induced Topography Fundamentals of Molecular Desorption Organic Materials Practical TOF-SIMS Polyatomic Primary Ions Materials/Surface Analysis Postionization Instrumentation Geological SIMS Imaging Fundamentals of Sputtering Ion Formation and Cluster Formation Quantitative Analysis Environmental/Particle Characterization Related Techniques These proceedings provide an invaluable source of reference for both newcomers to the field and experienced SIMS users.

Gillen, G.; Lareau, R.; Bennett, J.; Stevie, F.

2003-05-01

371

1912: a Titanic year for mass spectrometry.  

PubMed

The 1912 sinking of the Titanic continues to capture the imagination and fascination of the general public. The year coincides with the birth of mass spectrometry that began with the cathode ray experiments performed by Joseph John (J. J.) Thomson in Cambridge. Modifications made to Thomson's cathode ray apparatus by Francis William Aston, resulted in an increase in the brightness of the positive rays that aided their detection. This led to the discovery of heavy isotopes for many of the chemical elements in the ensuing decades. As the discovery of (22) Ne was reported in 1913, another of Thomson's students was taking part in an expedition to help save future ocean liners from the fate of the Titanic. Geoffrey Ingram Taylor took part in the first ice patrol of the North Atlantic in 1913 aboard the SS Scotia to investigate the formation and position of icebergs. This article, 100?years on, describes Taylor's work and its impact on safe ocean passage across the Atlantic. PMID:22899512

Downard, Kevin M

2012-08-01

372

High-precision simultaneous determination of 147Sm/144Nd and 143Nd/144Nd ratios in Sm-Nd mixtures using multi-collector inductively coupled plasma mass spectrometry and its comparison to isotope dilution analysis  

NASA Astrophysics Data System (ADS)

This work demonstrates, for the first time, the feasibility and capability of the high-precision simultaneous determination of 147Sm/144Nd and 143Nd/144Nd ratios in Sm-Nd mixtures using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) without Nd and Sm separation and without the use of costly enriched spikes. Mass discrimination was exponentially corrected by applying the natural constant of 146Nd/144Nd ratio as an internal standard, after correction of the isobaric interference of 144Sm on 144Nd using interference-free 147Sm/149Sm ratio for Sm mass fractionation, without assuming identical mass bias of Nd and Sm. The accuracy and precision of the present protocol, obtained from replicate analyses of various types of Sm-Nd mixtures encompassing a wide range of Sm/Nd (ca. 0.1-1.0) or 147Sm/144Nd ratios (ca. 0.06-0.62) was found to be comparable to the classic isotope dilution (ID) method. The present method is characterized by a higher sample throughput compared to the ID method, and shows great potential for the simultaneous determination of 147Sm/144Nd and 143Nd/144Nd ratios in real geological samples.

Yang, Yue-Heng; Wu, Fu-Yuan; Chu, Zhu-Yin; Xie, Lie-Wen; Yang, Jin-Hui

2013-01-01

373

Cortisol production rates measured by liquid chromatography/mass spectrometry  

SciTech Connect

Cortisol production rates (FPRs) in physiologic and pathologic states in humans have been investigated over the past 30 years. However, there has been conflicting evidence concerning the validity of the currently accepted value of FPRs in humans (12 to 15 mg/m2/d) as determined by radiotracer methodology. The present study reviews previous methods proposed for the measurement of FPRs in humans and discusses the applications of the first method for the direct determination of 24-hour plasma FPRs during continuous administration of a stable isotope, using a thermospray high-pressure liquid chromatography-mass spectrometry technique. The technique is fast, sensitive, and, unlike gas chromatography-mass spectrometry methods, does not require derivatization, allowing on-line detection and quantification of plasma cortisol after a simple extraction procedure. The results of determination of plasma FPRs by stable tracer/mass spectrometry are directly in units of mass/time and, unlike radiotracer methods, are independent of any determination of volume of distribution or cortisol concentration. Our methodology offers distinct advantages over radiotracer techniques in simplicity and reliability since only single measurements of isotope ratios are required. The technique was validated in adrenalectomized patients. Circadian variations in daily FRPs were observed in normal volunteers, and, to date, results suggest a lower FRP in normal children and adults than previously believed. 88 references.

Esteban, N.V.; Yergey, A.L. (National Institute of Child Health and Human Development, Bethesda, MD (USA))

1990-04-01

374

Resonance Ionization Mass Spectrometry System for Measurement of Environmental Samples  

NASA Astrophysics Data System (ADS)

A resonance ionization mass spectrometry (RIMS) system has been developed at the National Institute of Standards and Technology (NIST) for sensitive and selective determination of radio-cesium in the environment. The overall efficiency was determined to be 4×10-7 with a combined (laser and mass spectrometer) selectivity of 108 for both 135Cs and 137Cs with respect to 133Cs. RIMS isotopic ratio measurements of 135Cs/ 137Cs were performed on a nuclear fuel burn-up sample and compared to measurements on a similar system at Pacific Northwest National Laboratory (PNNL) and to conventional thermal ionization mass spectrometry (TIMS). Results of preliminary RIMS investigations on a freshwater lake sediment sample are also discussed.

Pibida, L.; McMahon, C. A.; Nörtershäuser, W.; Bushaw, B. A.

2002-10-01

375

New applications of mass spectrometry in lipid analysis.  

PubMed

Mass spectrometry has emerged as a powerful tool for the analysis of all lipids. Lipidomic analysis of biological systems using various approaches is now possible with a quantitative measurement of hundreds of lipid molecular species. Although availability of reference and internal standards lags behind the field, approaches using stable isotope-labeled derivative tagging permit precise determination of specific phospholipids in an experimental series. The use of reactivity of ozone has enabled assessment of double bond positions in fatty acyl groups even when species remain in complex lipid mixtures. Rapid scanning tandem mass spectrometers are capable of quantitative analysis of hundreds of targeted lipids at high sensitivity in a single on-line chromatographic separation. Imaging mass spectrometry of lipids in tissues has opened new insights into the distribution of lipid molecular species with promising application to study pathophysiological events and diseases. PMID:21632539

Murphy, Robert C; Gaskell, Simon J

2011-07-22

376

Improvements in 230Th dating, 230Th and 234U half-life values, and U-Th isotopic measurements by multi-collector inductively coupled plasma mass spectrometry  

NASA Astrophysics Data System (ADS)

We have developed techniques for measuring 234U and 230Th on Faraday cups with precisions of 1-3 epsilon units (1 ?-unit=1 part in 104) using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Using a Thermo-Scientific Neptune with desolvation nebulization, we obtained ionization/transmission efficiencies of 1-2% for both U and Th. We set up protocols to correct for tailing, prepared U and Th gravimetric standards, tested a Th mass fractionation correction procedure based on U isotopes, and identified natural calcite samples likely to be in U-Th isotopic secular equilibrium. The measured atomic ratios, 234U/238U=54.970 (±0.019)×10-6 and 230Th/238U=16.916 (±0.018)×10-6, for these calcite samples were identical within errors (quoted 2? uncertainties calculated combining all sources of error). Half-life values calculated from these ratios are consistent with previous values, but have much smaller errors: 245,620±260 a for 234U and 75,584±110 a for 230Th (quoted 2? uncertainties calculated using all sources of error). In calculating a 230Th age, some of the systematic errors included in estimating the full error in the half-lives effectively cancel. Removing these uncertainties (uncertainty in the 238U half-life value, uncertainty in our gravimetric uranium and thorium standards, and uncertainty in the absolute isotopic composition of the uranium standard), yields effective uncertainties for the purposes of 230Th dating of ±70 a for the 234U half-life value and ±30 a for the 230Th half-life value. Under ideal circumstances, with our methods, the 2? uncertainty in age, including uncertainty in half-life values is ±10 a at 10 ka, ±100 a at 130 ka, ±300 a at 200 ka, ±1 ka at 300 ka, ±2 ka at 400 ka, ±6 ka at 500 ka, and ±12 ka at 600 ka. The isotopic composition of a sample with an age <800 ka can clearly be resolved from the isotopic composition of a sample in secular equilibrium, assuming closed system behavior. Using these techniques, we analyzed a Sanbao Cave (Hubei, China) stalagmite that formed between 510 and 640 ka ago. As the half-life values were determined independent of the Sanbao Cave ages, the observed co-variation between stalagmite ?18O and Northern Hemisphere summer insolation is consistent with accurate ages and half-life values.

Cheng, Hai; Lawrence Edwards, R.; Shen, Chuan-Chou; Polyak, Victor J.; Asmerom, Yemane; Woodhead, Jon; Hellstrom, John; Wang, Yongjin; Kong, Xinggong; Spötl, Christoph; Wang, Xianfeng; Calvin Alexander, E.

2013-06-01

377

Precise Measurement of Phenylalanine ?15N Values via Elemental Analysis-Isotope Ratio Mass Spectrometry Following Purification with High-Pressure Liquid Chromatography: A New Tool for Fine-Scale Paleo-Nitrogen Cycle Reconstructions  

NASA Astrophysics Data System (ADS)

Compound specific isotope analysis of individual amino acids (CSI-AA) in organic paleoarchives is emerging as a powerful tool for reconstructing the paleo-nitrogen (N) cycle. Because the ?15N of phenylalanine (Phe) remains almost unchanged with diagenesis or trophic transfer it has been demonstrated to be the most promising AA proxy for the ?15N of primary production. However, the precise measurement of AA ?15N values is currently limited by the standard gas chromatography-isotope ratio mass spectrometer (GC-IRMS) approach. The key problem with this approach is that GC-IRMS ?15N precision (±1‰) is almost an order of magnitude lower than typical bulk ?15N measurements (±0.1‰), posing a significant problem for assessing fine scale changes within paleo-climate records. Additionally, required instrumentation is both expensive, and not widely available. Here we present an offline approach in which Phe is purified via high-pressure liquid chromatography (HPLC), using an analytical scale, mixed-phase column and automated fraction collection. ?13C and ?15N values of the fractions are then determined via standard elemental analysis-isotope ratio mass spectrometry (EA-IRMS). We evaluate the precision of this HPLC-EA-IRMS method vs. traditional GC-IRMS for Phe ?15N values of isotopic AA standards and various proteinaceous marine samples (marine coral, sediment, and cyanobacteria). Typical HPLC-EA-IRMS ?15N precision is ±0.1‰ for isotopic AA standards and ±0.5‰ for marine coral, sediment, and cyanobacteria samples compared to ±0.5‰ and ±1.0‰ for AA standards and samples analyzed by GC-IRMS. In order to demonstrate the viability of our approach, we present a comparison of a Phe ?15N record produced from a deep-sea bamboo coral specimen from Monterey Bay, CA, using our offline HPLC-EA-IRMS method vs. standard GC-IRMS. Each method produced equivalent Phe ?15N values within error, however, the HPLC-EA-IRMS method produced Phe ?15N values with over twice the precision of the traditional GC-IRMS method (HPLC-EA-IRMS standard deviation = 0.27‰ ± 0.14‰, GC-IRMS standard deviation = 0.60‰ ± 0.20‰). Our results suggest that this HPLC-EA-IRMS method represents a powerful, yet widely available tool for reconstructing fine scale N-cycling processes within paleoceanographic records.

Broek, T.; Walker, B. D.; Batista, F. C.; Andreasen, D.; Hill, T. M.; Guilderson, T. P.; McCarthy, M.

2012-12-01

378

??13C and ??18O isotopic composition of CaCo3 measured by continuous flow isotope ratio mass spectrometry: Statistical evaluation and verification by application to Devils Hole core DH-11 calcite  

USGS Publications Warehouse

A new method was developed to analyze the stable carbon and oxygen isotope ratios of small samples (400 ?? 20 ??g) of calcium carbonate. This new method streamlines the classical phosphoric acid/calcium carbonate (H3PO4/CaCO3) reaction method by making use of a recently available Thermoquest-Finnigan GasBench II preparation device and a Delta Plus XL continuous flow isotope ratio mass spectrometer. Conditions for which the H3PO4/CaCO3 reaction produced reproducible and accurate results with minimal error had to be determined. When the acid/carbonate reaction temperature was kept at 26??C and the reaction time was between 24 and 54 h, the precision of the carbon and oxygen isotope ratios for pooled samples from three reference standard materials was ???0.1 and ???0.2 per mill or %0, respectively, although later analysis showed that materials from one specific standard required reaction time between 34 and 54 h for ??18O to achieve this level of precision. Aliquot screening methods were shown to furthei minimize the total error. The accuracy and precision of the new method were analyzed and confirmed by statistical analysis. The utility of the method was verified by analyzing calcite from Devils Hole, Nevada, for which isotope-ratio values had previously been obtained by the classical method. Devils Hole core DH-11 recently had been re-cut and re-sampled, and isotope-ratio values were obtained using the new method. The results were comparable with those obtained by the classical method with correlation = +0.96 for both isotope ratios. The consistency of the isotopic results is such that an alignment offset could be identified in the re-sampled core material, and two cutting errors that occurred during re-sampling then were confirmed independently. This result indicates that the new method is a viable alternative to the classical reaction method. In particular, the new method requires less sample material permitting finer resolution and allows automation of some processes resulting in considerable time savings.

Revesz, K.M.; Landwehr, J.M.

2002-01-01

379

Tandem mass spectrometry of airborne particles  

SciTech Connect

Most manufacturing or processing activity produces solid emissions in the form of particulates. Low vapor pressure liquids condensed on ambient particulate matter is indicative of the materials and processes being used. Laser Desorption mass spectrometry of single microparticles in an ion trap provides a capability to analyze the airborne particles as well as condensed phase materials on a microparticle surface without any instrument manipulation. On-line, single particle analysis allows detection of microscopic variations in sample compositions in real time. In this experiment, a quadrupole ion trap mass spectrometer coupled with a particle injection system is demonstrated for laser desorption mass spectrometry and MS/MS analysis of single microparticles. The device can be used for detection of controlled substances and investigation of harmful airborne particles such as pollens, fibers, microorganisms, etc. Chemical analysis of individual microparticles using laser desorption mass spectrometry in this ion trap system has been described elsewhere.

Ramsey, J.M.; Yang, Mo.; Reilly, P.T.; Whitten, W.B. [Oak Ridge National Lab., TN (United States)

1995-12-31

380

Analysis of natural-occurring and synthetic sexual hormones in sludge-amended soils by matrix solid-phase dispersion and isotope dilution gas chromatography-tandem mass spectrometry.  

PubMed

A sensitive analytical method is presented for the simultaneous determination of four synthetic estrogens and six steroid hormones in sludge-amended soil. The method employs matrix solid-phase dispersion (MSPD) followed by isotope dilution gas chromatography-tandem mass spectrometry injecting a large volume sample (10?L) after trimethylsilyl derivatization, using the solvent vent mode. It affords good resolution, high sensitivity and reproducibility and freedom from interferences even from complex matrices as soil amended with sewage sludge. The limits of detection (LODs) ranged from 10 to 300pgg(-1) with testosterone and progesterone having the highest limits. Soil amended with sewage sludge was spiked at 2, 10, 25 and 50ngg(-1) and the recoveries after MSPD with acetonitrile:methanol (90:10, v/v), ranged from 80 to 110% with relative standard deviations ?9%. The method was applied to the analysis of six soil samples collected from agricultural plots and forested fields that had been amended with sewage sludge using isotopically labeled surrogates. Three of the synthetic estrogens studied were found at least in one of the six samples analyzed and trans-androsterone and estrone were the only natural hormones detected, although at very low levels (?0.4ngg(-1)). PMID:23465128

Albero, Beatriz; Sánchez-Brunete, Consuelo; Miguel, Esther; Pérez, Rosa A; Tadeo, José L

2013-03-29

381

CHARACTERIZATION OF DOXYLAMINE AND PYRILAMINE METABOLITES VIA THERMOSPRAY/MASS SPECTROMETRY AND TANDEM MASS SPECTROMETRY  

EPA Science Inventory

Analysis of doxylamine N-oxide and pyrilamine N-oxide as synthetic standards and biologically derived metabolites by thermospray mass spectrometry (TSP/MS) provided (M + H)+ ions for each metabolite. TSP/tandem mass spectrometry (TSP/MS/MS) of the (M + H)+ ions provided fragment ...

382

Quantifying Ocean Productivity using 15N and Continuous-Flow Mass Spectrometry  

Microsoft Academic Search

15 N, a stable isotope of nitrogen, has an important application in the estimation of oceanic export productivity but less concentration of nitrogen in the samples posses serious problems in marine applications.