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1

Accelerator mass spectrometry of plutonium isotopes  

Microsoft Academic Search

The feasibility of measuring plutonium isotope ratios by accelerator mass spectrometry has been demonstrated. Measurements on a test sample of known composition and on a blank showed that isotope ratios could be determined quantitatively, and that the present limit of detection by AMS is ? 106 atoms of plutonium. For 239Pu, this limit is at least two orders of magnitude

L. K. Fifield; R. G. Cresswell; M. L. di Tada; T. R. Ophel; J. P. Day; A. P. Clacher; S. J. King; N. D. Priest

1996-01-01

2

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.

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

2009-01-01

3

Multiple isotopic labels for quantitative mass spectrometry.  

PubMed

Quantitative mass spectrometry is often performed using isotopically labeled samples. Although 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 nine deuteriums and a light form without deuterium). In the present report, two additional forms containing three and six deuteriums have been synthesized and tested. These additional isotopic tags perform identically to the previously reported tags; peptides labeled with the new TMAB reagents coelute from reversed-phase HPLC columns with peptides labeled with the lighter and heavier TMAB reagents. Altogether, these four 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

2008-12-01

4

Isotope Analysis of Seawater by Mass Spectrometry.  

National Technical Information Service (NTIS)

The review includes a discussion of a suitable mass spectrometer, the isotope dilution technique and the scope of its applicability, a description of analytic procedure, and a case history involving the determination of lead isotopes in sea water.

T. J. Chow

1967-01-01

5

Stable Isotope-Coded Proteomic Mass Spectrometry  

SciTech Connect

The ability to quantify the changes in protein abundance between cells subjected to a variety of extracellular stimuli or the onset of a diseased state remains an extremely active area of proteome research. Although advances in sample preparation, chromatographic separation, mass spectrometry instrumentation and bioinformatics contribute to producing a viable method for comparative proteome-wide analyses, the foundation of quantitation is based in part upon improved methods for chemical and metabolic stable isotope labeling of proteins and peptides. The ability to quantify differences in protein expression and post-translational modifications has been demonstrated, but insights into the biochemical mechanisms that will contribute to the development of new biotechnologies have yet to be realized.

Goshe, Michael B. (BATTELLE (PACIFIC NW LAB)); Smith, Richard D. (BATTELLE (PACIFIC NW LAB))

2003-02-01

6

Hydrogen Isotope Analysis by Quadrupole Mass Spectrometry.  

National Technical Information Service (NTIS)

The analysis of isotopes of hydrogen (H, D, T) and helium ( exp 3 He, exp 4 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 Fusi...

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

1981-01-01

7

Tungsten isotope ratio determinations by negative thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

A precise determination of the isotopic abundances of tungsten with natural isotopic composition is presented. WO-3 ions are generated by negative thermal ionization (NTI) in a double-filament ion source. La2O3 is used as a chemical substance to reduce the electron work function of the rhenium filament material. An ionization efficiency of 1% is obtained for sample loadings of 100 ng. The isotopic abundances are measured with relative standard deviations of 0.2% for the least abundant 180W isotope and 0.02-0.004% for the other tungsten isotopes. These improved isotopic data are used to recalculate the atomic weight of tungsten as 183.8417 ± 0.0001. The new NTI technique is an ideal tool for the application of isotope dilution mass spectrometry to analyse tungsten traces and for the measurement of isotopic shifts of this element in meteorites produced by the decay of 182Hf.

Völkening, Joachim; Köppe, Manfred; Heumann, Klaus G.

1991-07-01

8

Calcium Isotope Analysis by Mass Spectrometry  

Microsoft Academic Search

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

S. Boulyga; S. Richter

2010-01-01

9

High Mass Resolution Plasma Mass Spectrometry of Cr Isotopes  

NASA Astrophysics Data System (ADS)

Natural mass dependent fractionation of Cr isotopes (masses 50, 52, 53 and 54) is associated with redox reactions (Ellis et al., 2002). In reduced aqueous solutions, chromium (VI) is converted to insoluble chromium (III), which is accompanied by a 3 permil isotope effect. Thus the isotopes of Cr may have wide applicability in the earth sciences as a tracer of redox conditions in the solid earth, oceans and atmosphere over time. Our approach for measuring Cr isotopes utilizes the resolving power of the Finnigan Neptune operated in high mass resolution mode. Using a small diameter, high resolution entrance slit and wide diameter collector slits, flat-topped peak shoulders representing the un-interfered Cr isotopes can be located during a mass scan on the low mass side of composite, interfered peaks. Setting the collectors and magnet field to measure on these peak shoulders, near the high mass edge of the Faraday collector, clips the interfering ion beam preventing it from entering the collector. The largest plasma-generated interference is 40Ar14N on mass 54, comprising about 18 percent of the ion bean intensity in a 1 ppm Cr solution. Molecular interferences on the other isotopes of Cr are less than 0.1 percent, and are negligible in >10ppm Cr solutions. All experiments utilize the Finnigan stable introduction system and a PFA microflow nebulizer. Preliminary results show that about 4 permil of the ArN interference on mass 54 remains despite the peak shoulder measurement. This may be due to peak tailing from the ArN interference, which is a composite peak with an additional interference on the low mass side that is part of the HNO3 blank, and may accentuate tailing of the 54Cr peak. The 4 permil effect is easily removed by performing a blank subtraction. Normalized to a 50/52 ratio of 0.051859, we obtained ratios of 0.113452 and 0.028223 on 53/52 and 54/52, respectively, in 3 to 10 ppm solutions. Results thus far show that a reproducibility of better than +/-50 ppm (2 standard deviations) on the 53/52 ratio is easily achieved from Cr solutions of 3 to 10 ppm. To measure natural Cr isotope variations in nature requires sample-standard-bracketing or double spike addition to correct for instrumental mass fractionation. Experiments with a 50-54 double spike are currently underway, and these results will also be reported. Ellis et al., Science, V. 295, p. 2060

Holmden, C.; Eglington, B. M.

2003-12-01

10

Mass spectrometry and isotopes: a century of research and discussion.  

PubMed

In 1815, the British physician William Prout had advanced the theory that the molecular masses of elements were multiples of the mass of hydrogen. This "whole number rule" (and especially deviations from it) played an important role in the discussion whether elements could be mixtures of isotopes. F. Soddy's discovery (1910) that lead obtained by decay of uranium and of thorium differed in mass was considered a peculiarity of radioactive materials. The question of the existence of isotopes came up when the instruments developed by J.J. Thomson and by W. Wien to study cathode and canal rays by deflection in electric and magnetic fields were steadily improved. In 1913, Thomson mentioned a weak line at mass 22 accompanying the expected one at mass 20 when he analyzed the mass spectrum of neon. Subsequently Aston obtained the mass spectrum of chlorine with masses at 35 and 37. Still in 1921, Thomson objected heavily to the idea of isotopes. The isotope problem was finally settled, but more accurate mass measurements showed that even isotopic weights differed to some extent from the whole numbers. Based on earlier ideas of P. Langevin and J.-L. Costa, F.W. Aston and A.J. Dempster developed the idea of packing fractions and mass defects due to the transformation of a portion of the matter comprising the atomic nucleus into energy. While the determination of the exact isotopic masses had improved over the years, the accurate determination of isotopic abundances remained a problem as long as photographic recording was used. Here especially A.O. Nier pioneered using dual collectors and compensation measurements. This was the prerequisite for the discovery that isotopic ratios varied somewhat in nature. M. Dole discovered the fractionation of oxygen isotopes by photosynthesis and respiration. Today 13C/12C-ratios are employed to detect adulterations of food and in doping analysis, and 14C/13C-ratios obtained by accelerator mass spectrometry are used for dating historical objects, just to give some examples. PMID:16134128

Budzikiewicz, Herbert; Grigsby, Ronald D

11

The optimal amount of isotopic spike solution for ultratrace analysis by isotope dilution mass spectrometry  

Microsoft Academic Search

Inductively coupled plasma mass spectrometry (ICP-MS) and high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS)\\u000a are powerful methods of determining metallic impurities in the low- and sub-ppt level in process media such as ultra-pure\\u000a water used in semiconductor and wafer manufacturing. By using mass spectrometers for analysis, an isotope dilution analysis\\u000a (IDMS) is possible. The reproducibility of an IDMS is

R. Hoelzl; Christian Hoelzl; Ludwig Kotz; Lazlo Fabry

1998-01-01

12

Analysis of polyunsaturated aminophospholipid molecular species using isotope-tagged derivatives and tandem mass spectrometry\\/mass spectrometry\\/mass spectrometry  

Microsoft Academic Search

When aminophospholipids with only saturated and monounsaturated fatty acids esterified to the glycerol backbone were labeled with isotopically enriched N-methylpiperazine acetic acid N-hydroxysuccinimide ester reagents, it was found that they could be readily detected as N-methylpiperazine-amide-tagged aminophospholipids using a precursor scan of the stable isotope reporter ion (m\\/z 114–117) formed by tandem mass spectrometry\\/mass spectrometry. However, it was found in

Karin A. Zemski Berry; Robert C. Murphy

2006-01-01

13

Improved Isotopic Measurement of Plutonium by Thermal Ionization Mass Spectrometry  

SciTech Connect

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

Shick, C. Jr.

2002-02-07

14

U-Th isotopic measurements using secondary ion mass spectrometry  

SciTech Connect

A technique for Th isotopic analyses by SIMS (secondary ion mass spectrometry) has been developed using the Lamont Isolab 54. The high ionization efficiency afforded by SIMS, compared to thermal ionization (TIMS) permit analyses of [sup 230]Th/[sup 232]Th ratios at the 5% 2[sigma] level with 5 to 10 ng of total Th. Relative to TIMS and [alpha]-spectrometry, sample preparation times are markedly reduced, and contamination problems are minimized. The technique is being used to investigate the temporal evolution of young volcanoes, by obtaining U-Th mineral isochrons on individual lava flows, and U-Th fractionations in the sub-ridge mantle via the study of MORBs and young, near-ridge seamount basalts. Results of these topics will be presented and discussed at the meeting.

Zindler, A. (Lamont-Doherty Geologic Observatory, Palisades, NY (United States))

1993-03-01

15

High Precision Isotope Petrography by Secondary Ion Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Since Shimizu et al. (GCA 1978) have demonstrated that in-situ micro-scale analyses of isotopes and trace elements in minerals were succeeded by secondary ion mass spectrometry (SIMS), geochemists develop the SIMS methods towards isotope mapping with spatial resolution of electron microscopy level. At present, high spatial resolution imaging by SIMS has been succeeded by scanning methods using ion-probe and by projection methods using stigmatic secondary ion optics. For high precision isotope analysis with high spatial resolution, intense secondary ions are indispensable for each pixel in the image. However, one of the major instrumental problems is that there were no adequate detectors for this purpose. In order to solve the problem, we proposed a two-dimensional solid-state ion detector called SCAPS (Takayanagi et al., IEEE Trans. 2003). The development is still continued and performances of recent SCAPS detector is achieved to: (1) direct sensitive for ions from single ion, (2) no dead time, and (3) perfect linearity of five orders of magnitude dynamic range. Installing the SCAPS detector into a stigmatic SIMS of Cameca ims-1270, we obtained oxygen isotope (delta-O-17 and delta-O-18) images of about 100 micrometer field with ~500 nm resolution and ~5 permil precision. The performance of high precision isotope imaging have might not be matured, but overcome a hurdle towards isotope petrography (Isotopography). We apply this isotopography to research fields of (a) survey of isotope anomalous micrograins and (b) isotope micro-distribution in rocks and minerals. In the application (a), we found in-situ presolar grains in meteorites (Nagashima et al., Nature 2004) and cosmic symplectite (COS) from a meteorite (Sakamoto et al., Science 2007). In the application (b), we showed how distribute oxygen isotopic compositions in micro-scale within CAI minerals (Yurimoto et al., Rev. Mineral. 2008; Fagan et al., in prep.). In combination fields of (a) and (b), we demonstrated how preserves Martian water and how contaminates terrestrial water in Martian meteorites (Greenwood et al., GRL 2008). These new knowledge from isotopography provides novel perspective of earth and planetary sciences.

Yurimoto, H.

2009-12-01

16

Ultra-sensitive isotopic analysis by resonance ionization mass spectrometry  

SciTech Connect

A high-powered pulsed dye laser has been interfaced to a commerical ion microprobe mass analyzer. This combination should provide ultra-high sensitivity for isotope ratio measurements of selected elements in environmental samples. The technique is an outgrowth of resonance ionization mass spectrometry which has demonstrated high precision for isotope ratio determinations of uranium and plutonium using thermal filament atomization. Sputter atomization using a pulsed argon ion beam represents a significant improvement in efficiency because the temporal overlap between the atom cloud and the laser pulse can approach 100%. This, coupled with the high ionization efficiency of laser induced resonance ionization methods, promises an analytical sensitivity which is significantly better than other microprobe techniques. A description of the experimental set-up is given along with the modifications to the ion microprobe instrument which were necessary to obtain acceptable ion extraction efficiency. Also shown are results for samarium and uranium demonstrating the optical and mass spectra obtained. 21 refs., 7 figs., 1 tab.

Donohue, D.L.; Christie, W.H.; Goeringer, D.E.; McKown, H.S.

1984-01-01

17

Quantitation of DNA adducts by stable isotope dilution mass spectrometry  

PubMed Central

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

Tretyakova, Natalia; Goggin, Melissa; Janis, Gregory

2012-01-01

18

Quantitative determination of oxidative base damage in DNA by stable isotope-dilution mass spectrometry.  

PubMed

For understanding of the role of oxidative DNA damage in biological processes such as mutagenesis and carcinogenesis, it is essential to identify and quantify this type of DNA damage in cells. This can be achieved by gas chromatography/mass spectrometry. The present study describes the quantification of modified bases in DNA by isotope-dilution mass spectrometry with the use of stable isotope-labeled analogues as internal standards. A number of isotopically labeled DNA bases were synthesized. The mass spectra of their trimethylsilyl derivatives were recorded. Calibration plots were obtained for known quantities of modified bases and their isotope-labeled analogues. Quantification of various modified DNA bases by isotope-dilution mass spectrometry was demonstrated in isolated chromatin exposed to ionizing radiation. The results indicate that gas chromatography/stable isotope-dilution mass spectrometry is an ideally suited technique for selective and sensitive quantification of modified bases in DNA. PMID:8416801

Dizdaroglu, M

1993-01-01

19

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

Microsoft Academic Search

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

Matthew S. Fantle; Thomas D. Bullen

2009-01-01

20

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.

Bluck, Les; Volmer, Dietrich A.

2013-01-01

21

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

22

Zinc isotope fractionation analyses by thermal ionization mass spectrometry and a double spiking technique  

Microsoft Academic Search

The aim of this work was to develop thermal ionization mass spectrometry (TIMS) isotopic procedures to measure Zn isotope fractionation (?Zn) in natural materials. This work represents the most recent development of Zn isotope measurements and the first ?Zn identification in terrestrial materials using TIMS and a double spike technique. The developed procedures evaluate and solve several critical analytical issues

Osama Y. Ghidan; Robert D. Loss

23

Determination of porphyrin carbon isotopic composition using gas chromatography-isotope ratio monitoring mass spectrometry.  

PubMed

Carbon isotopic compositions of aetio I occurring in the form of free-base, nickel, demetallation, dihydroxysilicon(IV) and bis(tert.-butyldimethylsiloxy)silicon(IV) [(tBDMSO)2Si(IV)] have shown that it has experienced no obvious isotope fractionation during the synthesis of [(tBDMSO)2Si(IV)] porphyrin from aetio I. Here, aetio I porphyrin species such as free-base, nickel, demetallated and dihydroxysilicon were analyzed by the conventional method, namely it is combusted in sealed system, and followed by isotope ratio monitoring mass spectrometric analysis. [(tBDMSO)2Si(IV)] aetio I was assayed by gas chromatography-isotope ratio monitoring mass spectrometry (GC-IRMS). A porphyrin mixture of [(tBDMSO)2Si(IV)] aetio I and octaethylporphyrin was also prepared. Their carbon isotopic compositions measured by GC-IRMS indicate that no isotope exchange took place between the porphyrins during the synthesis of [(tBDMSO)2Si(IV)] porphyrins. This method is employed for delta13C determination of geoporphyrins from the Maoming and Jianghan oil shales. PMID:11153940

Yu, Z; Sheng, G; Fu, J; Peng, P

2000-12-01

24

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

25

Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry  

Microsoft Academic Search

The stable isotope geochemistry of Cu and Zn is poorly known because of the lack of a suitable analytical technique. We present a procedure for the analysis of Cu and Zn isotope compositions by plasma-source mass spectrometry (Plasma 54) together with a method to purify Cu and Zn from natural samples of silicates, ores, and biological material. A plasma-source mass

Chloé Nadia Maréchal; Philippe Télouk; Francis Albarède

1999-01-01

26

Measurement equations for the determination of the Si molar mass by isotope dilution mass spectrometry  

NASA Astrophysics Data System (ADS)

A new method applying isotope dilution mass spectrometry to determine the molar mass of a silicon sample, highly enriched with respect to 28Si, has been proposed recently. This paper describes a different way of calculating the molar mass by solving an equation linking the measurement results to the ratio between the amount-of-substance fractions of 28Si and 30Si in the sample. The mathematical model and the final measurement equation are much more straightforward than those previously reported, though fully equivalent.

Mana, G.; Rienitz, O.; Pramann, A.

2010-08-01

27

Prospects for large dynamic range isotope analysis using photon burst mass spectrometry  

SciTech Connect

Photon Burst Mass Spectrometry is a relatively new and untried method which may complement and extend the impressive achievements of Resonance Ionization Mass Spectrometry and Accelerator Mass Spectrometry in the field of large dynamic range isotope analysis. Theoretical predictions indicate that measurements in the 10/sup /minus/11/ to 10/sup /minus/15/ range are possible in a reasonable period of time with zero background. Experimentally only the very first demonstrations of PBMS with stable isotopes have been completed. 8 refs., 1 fig., 1 tab.

Fairbank, W.M. Jr.; LaBelle, R.D.; Keller, R.A.; Miller, C.M.; Poths, J.; Fearey, B.L.

1988-01-01

28

Determination of Cyanide in Blood by Isotope Dilution Gas Chromatography-Mass Spectrometry  

Microsoft Academic Search

Background: Cyanide (CN) is a lethal toxin. Quantifi- cation in blood is necessary to indicate exposure from many sources, including food, combustion byproducts, and terrorist activity. We describe an automated proce- dure based on isotope-dilution gas chromatography- mass spectrometry (ID GC\\/MS) for the accurate and rapid determination of CN in whole blood. Methods: A known amount of isotopically labeled po-

Karen E. Murphy; Michele M. Schantz; Therese A. Butler; Bruce A. Benner; Laura J. Wood; Gregory C. Turk

29

Combination of magneto-optical trapping and mass spectrometry for calcium-isotope analysis  

NASA Astrophysics Data System (ADS)

A method using a combination of a magneto-optical trap and a mass spectrometer, referred to as atom trap-mass spectrometry (ATMS), is employed for calcium-isotope analysis. A calcium magneto-optical trap with a Zeeman slower is used in the first isotope-selection stage of the ATMS. The trapped calcium isotope is ionized by using a frequency-doubled Nd:YAG laser, and the photoions are analyzed using a time-of-flight mass spectrometer. The isotope-selection characteristics of the combination method and further improvements in the method are discussed in this work.

Ko, Kwang-Hoon; Kim, Yonghee; Lee, Lim; Kim, Taek-Soo; Park, Hyunmin; Jeong, Do-Young; Jang, Kyu-Ha; Park, Gun-Sik

2013-08-01

30

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

31

Uranium and thorium isotopic and concentration measurements by magnetic sector inductively coupled plasma mass spectrometry  

Microsoft Academic Search

We have developed techniques by sector-field inductively coupled plasma mass spectrometry (ICP-MS) for measuring the isotopic composition and concentration of uranium and thorium, focusing on the rare isotopes, 230Th and 234U. These isotopes have been widely used as tracers in earth sciences, e.g., chronology, paleoclimatology, archeology, hydrology, geochemistry, and oceanography. Measurements made on reference materials demonstrate that the analytical precision

Chuan-Chou Shen; R Lawrence Edwards; Hai Cheng; Jeffrey A Dorale; Rebecca B Thomas; S Bradley Moran; Sarah E Weinstein; Henrietta N Edmonds

2002-01-01

32

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

2012-10-13

33

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

2012-08-23

34

Cooling of radioactive isotopes for Schottky mass spectrometry  

SciTech Connect

Nuclear masses of radioactive isotopes can be determined by measurement of their revolution frequency relative to the revolution frequency of reference ions with well-known masses. The resolution of neighboring frequency lines and the accuracy of the mass measurement is dependent on the achievable minimum longitudinal momentum spread of the ion beam. Electron cooling allows an increase of the phase space density by several orders of magnitude. For high intensity beams Coulomb scattering in the dense ion beam limits the beam quality. For low intensity beams a regime exists in which the diffusion due to intrabeam scattering is not dominating any more. The minimum momentum spread {delta}p/p=5x10{sup -7} which is observed by Schottky noise analysis is considerably higher than the value expected from the longitudinal electron temperature. The measured frequency spread results from fluctuations of the magnetic field in the storage ring magnets. Systematic mass measurements have started and can be presently used for ions with half-lives of some ten seconds. For shorter-lived nuclei a stochastic precooling system is in preparation.

Steck, M.; Beckert, K.; Eickhoff, H.; Franzke, B.; Nolden, F.; Reich, H.; Schlitt, B.; Winkler, T. [Gesellschaft fuer Schwerionenforschung, Planckstr. 1, D-64291 Darmstadt (Germany)

1999-01-15

35

Cooling of radioactive isotopes for Schottky mass spectrometry  

NASA Astrophysics Data System (ADS)

Nuclear masses of radioactive isotopes can be determined by measurement of their revolution frequency relative to the revolution frequency of reference ions with well-known masses. The resolution of neighboring frequency lines and the accuracy of the mass measurement is dependent on the achievable minimum longitudinal momentum spread of the ion beam. Electron cooling allows an increase of the phase space density by several orders of magnitude. For high intensity beams Coulomb scattering in the dense ion beam limits the beam quality. For low intensity beams a regime exists in which the diffusion due to intrabeam scattering is not dominating any more. The minimum momentum spread ?p/p=5×10-7 which is observed by Schottky noise analysis is considerably higher than the value expected from the longitudinal electron temperature. The measured frequency spread results from fluctuations of the magnetic field in the storage ring magnets. Systematic mass measurements have started and can be presently used for ions with half-lives of some ten seconds. For shorter-lived nuclei a stochastic precooling system is in preparation.

Steck, M.; Beckert, K.; Eickhoff, H.; Franzke, B.; Nolden, F.; Reich, H.; Schlitt, B.; Winkler, T.

1999-01-01

36

Selective isotope determination of lanthanum by diode-laser-initiated resonance-ionization mass spectrometry  

Microsoft Academic Search

A diode-laser step has been incorporated into a resonance-ionization mass spectrometry optical excitation process to enhance the isotopic selectivity of the technique. Lanthanum isotope ratio enhancements as high as 10³ were achieved by use of a single-frequency cw diode laser tuned to excite the first step of a three-step excitation--ionization optical process; the subsequent steps were excited by use of

J. P. Young; R. W. Shaw

1995-01-01

37

A method for determining isotopic composition of elements by thermal ionization source mass spectrometry  

Microsoft Academic Search

It is shown that in thermal ionization source mass spectrometry, if isotope fractionation of the element in the sample follows a linear law, straight-line distributions in xm versus xm\\/ym diagrams are observed, where xm and ym are two measured isotope ratios. The slopes and y-intercepts of these linear distributions are functions of the ‘true’ (starting) values xt and yt of

Giancarlo Cavazzini

2005-01-01

38

Performance of an electron cyclotron resonance ion source designed for isotope ratio mass spectrometry  

SciTech Connect

We have designed, built, and tested an electron cyclotron resonance ion source suited to the needs of an experimental program examining new methods of isotope ratio mass spectrometry using multiply charged ions. Contaminant levels have been reduced to low levels. Sample absorption and desorption effects are under investigation and preliminary results are presented.

Hotchkis, M. A. C.; Buckley, D.; Button, D. [Australian Nuclear Science and Technology Organisation, PMB 1, Menai, New South Wales 2234 (Australia)

2008-02-15

39

Performance of an electron cyclotron resonance ion source designed for isotope ratio mass spectrometry  

Microsoft Academic Search

We have designed, built, and tested an electron cyclotron resonance ion source suited to the needs of an experimental program examining new methods of isotope ratio mass spectrometry using multiply charged ions. Contaminant levels have been reduced to low levels. Sample absorption and desorption effects are under investigation and preliminary results are presented.

M. A. C. Hotchkis; D. Buckley; D. Button

2008-01-01

40

Carbon isotope ratio measurements of glyphosate and AMPA by liquid chromatography coupled to isotope ratio mass spectrometry.  

PubMed

The interest in compound-specific isotope analysis for product authenticity control and source differentiation in environmental sciences has grown rapidly during the last decade. However, the isotopic analysis of very polar analytes is a challenging task due to the lack of suitable chromatographic separation techniques which can be used coupled to isotope ratio mass spectrometry. In this work, we present the first method to measure carbon isotope compositions of the widely applied herbicide glyphosate and its metabolite aminomethylphosphonic acid (AMPA) by liquid chromatography coupled to isotope ratio mass spectrometry. We demonstrate that this analysis can be carried out either in cation exchange or in reversed-phase separation modes. The reversed-phase separation yields a better performance in terms of resolution compared with the cation exchange method. The measurement of commercial glyphosate herbicide samples show its principal applicability and reveals a wide range of ?(13)C values between -24 and -34 ‰ for different manufacturers. The absolute minimum amounts required to perform a precise and accurate determination of carbon isotope compositions of glyphosate and AMPA were in the sub-microgram range. The method proposed is sensitive enough to further perform the experiments that are necessary to better understand the carbon isotope fractionation associated to the natural degradation of glyphosate into AMPA. Furthermore, it can be used for contaminant source allocation and product authenticity as well. PMID:23322349

Kujawinski, Dorothea M; Wolbert, J Benjamin; Zhang, Lijun; Jochmann, Maik A; Widory, David; Baran, Nicole; Schmidt, Torsten C

2013-01-16

41

Determination of chromium species in dietary supplements using speciated isotope dilution mass spectrometry with mass balance.  

PubMed

In order to determine the health impact of chromium in dietary supplements, the Cr(III) and Cr(VI) must be independently measured and verified with mass balance (sum of both species equaling independent measurements of total chromium), as both may be present in finished products. Because Cr(III) is stable in acidic conditions and Cr(VI) in alkaline conditions, interconversions between species may occur in complex matrices and during analytical extraction, increasing the difficulty of quantification. A study was conducted to determine Cr(VI) and Cr(III) in dietary supplements. EPA Method 3060A extraction protocol was performed to extract Cr(VI), and EPA Method 3052 was performed on the extracted residue to digest the remaining Cr(III). Speciated isotope dilution mass spectrometry (SIDMS), as described in the EPA Method 6800 (update V), was implemented with ion-exchange chromatography inductively coupled plasma mass spectrometry (IC-ICP-MS). Method 6800 uniquely enables tracking and correcting for the bidirectional chromium interspecies conversions that occur during extraction and sample handling prior to instrumental analysis. Mass balance results indicated that the off-the-shelf dietary supplements analyzed during this study contained hexavalent chromium ranging from

Martone, Naudia; Rahman, G M Mizanur; Pamuku, Matt; Kingston, H M Skip

2013-10-07

42

Precision in Strontium Isotope Measurements by Laser Ablation Assisted Resonance Ionization Mass Spectrometry  

SciTech Connect

We have investigated the precision of strontium isotope analysis by Laser Ablation-assisted Resonance Ionization Mass Spectrometry(LA-RIMS). We have confirmed that the mass discrimination effect on the {sup 87}Sr/{sup 86}Sr measurement was reduced by the internal correction method. For the present system, the precision of the isotope ratio of {sup 87}Sr/{sup 86}Sr has been estimated to be 0.6%(1{sigma}). The precision has been limited by the fluctuations with a time scale of less than 10 s.

Sasada, S.; Tomita, H.; Watanabe, K.; Higuchi, Y.; Kawarabayashi, J.; Iguchi, T. [Graduate School of Engineering, Nagoya University, Nagoya, Aichi 464-8603 (Japan)

2009-03-17

43

Illustrating the Concepts of Isotopes and Mass Spectrometry in Introductory Courses: A MALDI-TOF Mass Spectrometry Laboratory Experiment  

ERIC Educational Resources Information Center

|Mass spectrometry is a widely used and versatile tool for scientists in many different fields. Soft ionization techniques such as matrix-assisted laser desorption/ionization (MALDI) allow for the analysis of biomolecules, polymers, and clusters. This article describes a MALDI mass spectrometry experiment designed for students in introductory…

Dopke, Nancy Carter; Lovett, Timothy Neal

2007-01-01

44

In-Vivo Zinc Metabolism by Isotope Ratio Mass Spectrometry  

Technology Transfer Automated Retrieval System (TEKTRAN)

The purpose of this chapter is to highlight some of the methodological and technical issues surrounding the in vivo use of stable isotopes and to provide examples of how such studies have advanced our knowledge of human zinc metabolism. The advantages and disadvantages of the currently available in...

45

Determination of uranium and thorium concentrations in soils: Comparison of isotope dilution-secondary ion mass spectrometry and isotope dilution-thermal ionization mass spectrometry  

SciTech Connect

The purpose of the present study existed in making a comparison between isotope dilution-thermal ionization mass spectrometry (ID-TIMS) and isotope dilution-secondary ion mass spectrometry (ID-SIMS) on the basis of their precision and accuracy. Three different sets of soils were therefore analyzed to determine their uranium and thorium contents. An analysis of variance (ANOVA) demonstrated that the precision of TIMS was about 6 times better than that of SIMS. It was clear in the case of TIMS that the overall precision can almost completely be explained by the variation in composition between samples, while for the SIMS analyses, the instrumental error plays an important role in determining the precision. The overall SIMS/TIMS ratio for all data and for both elements equals 0.994 with a standard error of 0.004. As a result of this, it is statistically not fully proven that there is a systematic difference in accuracy between the two techniques. For the chemical separation of the analytes, a new element-specific resin was used and evaluated. The newer resin was able to remove metals such as iron, lead, and bismuth better than that traditional strong anion resin, but the uranium fraction obtained using the newer resin contained a larger amount of thorium. 14 refs., 7 figs., 4 tabs.

Adriaens, A.G.; Adams, F.C. (Univ. of Antwerp, Wilrijk (Belgium)); Fassett, J.D.; Kelly, W.R.; Simons, D.S. (National Inst. of Standards and Technology, Gaithersburg, MD (United States))

1992-12-01

46

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

47

Determination of stable isotopes of calcium in biological fluids by fast atom bombardment mass spectrometry  

Microsoft Academic Search

High-resolution fast atom bombardment mass spectrometry was used to measure the isotopic abundances of calcium in plasma and urine. Since the method is very sensitive (>5 x 10¹° ions\\/..mu..g of calcium), only 2 to 5 ..mu..L of sample is required. Repetitive measurements of the ⁴²Ca\\/⁴°Ca ratio in plasma and urine require about 3 min and typically have a relative standard

David L. Smith

1983-01-01

48

Improving precision in resonance ionization mass spectrometry : influence of laser bandwidth in uranium isotope ratio measurements.  

SciTech Connect

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 by resonance ionization mass spectrometry (RIMS) to decrease laser-induced isotopic fractionation. By broadening the bandwidth of the first laser in a three-color, three-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.

Isselhardt, B. H.; Savina, M. R.; Knight, K. B.; Pellin, M. J.; Hutcheon, I. D.; Prussin, S. G. (Materials Science Division); (Univ. California at Berkeley); (LLNL)

2011-03-01

49

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

50

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

PubMed

Information on plutonium isotope ratios in individual particles is of great importance for nuclear safeguards, nuclear forensics and so on. Although secondary ion mass spectrometry (SIMS) is successfully utilized for the analysis of individual uranium particles, the isobaric interference of americium-241 to plutonium-241 makes difficult to obtain accurate isotope ratios in individual plutonium particles. In the present work, an analytical technique by a combination of chemical separation and inductively coupled plasma mass spectrometry (ICP-MS) is developed and applied to isotope ratio analysis of individual sub-micrometer plutonium particles. The ICP-MS results for individual plutonium particles prepared from a standard reference material (NBL SRM-947) indicate that the use of a desolvation system for sample introduction improves the precision of isotope ratios. In addition, the accuracy of the (241)Pu/(239)Pu isotope ratio is much improved, owing to the chemical separation of plutonium and americium. In conclusion, the performance of the proposed ICP-MS technique is sufficient for the analysis of individual plutonium particles. PMID:21111176

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

2010-10-08

51

Ultra Trace Isotope Determination in Environmental, BioMedical and Fundamental Research by High Resolution Laser-Mass Spectrometry  

Microsoft Academic Search

The introduction of resonance ionization using continuous wave narrowband lasers into mass spectrometry has lead to the successful development of an efficient technique for ultra trace atom determination with outstanding specifications regarding isobaric and isotopic selectivity. Due to these features this compact laser-based method is just becoming competitive to conventional ultra trace detection techniques like accelerator mass spectrometry or low

Klaus D. A. WENDT; Christopher GEPPERT; Masabumi MIYABE; Wilfried NÖRTERSHÄUSER; Norbert TRAUTMANN

2002-01-01

52

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

SciTech Connect

A new method that allows rapid preconcentration and separation of plutonium and neptunium in water samples was developed for the measurement of {sup 237}Np and Pu isotopes by inductively-coupled plasma mass spectrometry (ICP-MS) and alpha spectrometry; a hybrid approach. {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 peak tailing. The method provide enhanced removal of uranium by separating Pu and Np initially on TEVA Resin, then moving Pu to DGA resin for additional removal of uranium. The decontamination factor for uranium from Pu is almost 100,000 and the decontamination factor for U from Np is greater than 10,000. This method uses stacked extraction chromatography cartridges and vacuum box technology to facilitate rapid separations. Preconcentration is performed using a streamlined calcium phosphate precipitation method. Purified solutions are split between ICP-MS and alpha spectrometry so that long and short-lived Pu isotopes can be measured successfully. The method allows for simultaneous extraction of 20 samples (including QC samples) in 4 to 6 hours, and can also be used for emergency response. {sup 239}Pu, {sup 242}Pu and {sup 237}Np were measured by ICP-MS, while {sup 236}Pu, {sup 238}Pu, and {sup 239}Pu were measured by alpha spectrometry.

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

2010-06-23

53

Sources of uncertainty in isotope ratio measurements by inductively coupled plasma mass spectrometry.  

PubMed

A model is presented describing the effects of dead time and mass bias correction factor uncertainties, flicker noise, and counting statistics on isotope ratio measurement precision using inductively coupled plasma mass spectrometry (ICPMS) with a single collector. Noise spectral analysis is exploited to enable estimation of the flicker noise parameters. For the instrument used, the flicker noise component exhibited a fairly weak frequency (t) dependence (is proportional to f -0.33+/-0.12), but was directly proportional to the total number of counts, Q. As white noise, determined by counting statistics, is given by Q0.5, the isotope ratio measurement uncertainties will actually cease to improve when Q exceeds a certain threshold. This would suggest that flicker noise could become the limiting factor for the precision with which isotope ratios can be determined by ICPMS. However, under most experimental conditions, uncertainties associated with mass discrimination and dead time correction factors are decisive. For ratios up to approximately 22 (115In/113In), optimum major isotope count rates are generally below 0.3 MHz, for which precision in the mass discrimination factor is limiting. The model derived could be used as a starting point for determining optimum conditions and understanding the limitations of single-collector ICPMS for precise isotope ratio measurements. PMID:11467535

Appelblad, P K; Rodushkin, I; Baxter, D C

2001-07-01

54

Sector field inductively coupled plasma mass spectrometry, another tool for plutonium isotopes and plutonium isotope ratios determination in environmental matrices.  

PubMed

The transfer of radio nuclides into the different compartments of the environment are widely studied and leads to the elaboration of transfer models in order to evaluate potential impact onto the environment and humans. Accurate experimental data are needed to validate these models for all types of matrices (air, water, sediments, soils, biota and food...). Among these radionuclides, 238Pu, 239Pu, 240Pu and 241Pu, are often mentioned. They have been released into the environment by nuclear weapon tests, nuclear facilities, reactors or satellite accidents. These different sources have different 240Pu/239Pu ratios and therefore this ratio is used to provide information on the source of contamination into the environment. The most conventional analytical tools used for plutonium isotope determination are liquid scintillation and alpha spectrometry, and thermal ionisation mass spectrometry (TIMS) is still considered as the primary method for determination of plutonium isotope ratios. During the last decade, mass spectrometers equipped with plasma ion sources and sector field analysers were developed and can offer now another alternative method for the accurate determination of isotope content and ratios of long-lived radionuclides in environmental samples. This paper presents and discusses the results obtained for 239Pu, 240Pu and 241Pu content and isotope ratios by sector field ICP-MS in different environmental matrices. PMID:15162869

Agarande, M; Benzoubir, S; Neiva-Marques, A M; Bouisset, P

2004-01-01

55

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

56

Quantitation of stable isotopic tracers of calcium by fast atom bombardment mass spectrometry  

SciTech Connect

Instrumentation and methodology developed for quantitation of stable isotopic traces in urine are described. Calcium is isolated from urine as the insoluble oxalate salt which is subsequently dissolved in hydrochloric acid. The isotopic content of the acid solution is determined by use of a conventional mass spectrometer equipped with a fast atom bombardment ion source. Calcium ions are desorbed from the sample surface by a beam of high-energy xenon atoms and detected with a high-resolution mass spectrometer. A data acquisition system has been developed to control the mass spectrometer and record the ion signals. Detailed analysis of potential sources of error indicates that the precision of the method is presently limited primarily by an isotope effect that occurs during ion desorption. Results presented here demonstrate that the relative abundances of calcium isotopes in urine can be determined with high precision (coefficient of variation < 0.2%) and that the method is a viable alternative to conventional thermal ionization mass spectrometry. The method is especially attractive because it uses a conventional high-resolution mass spectrometer which is routinely used for analysis of organic substances.

Jiang, X.; Smith, D.L.

1987-11-01

57

Structure elucidation of four possible biogenic organohalogens using isotope exchange mass spectrometry  

Microsoft Academic Search

The molecular structures of four unknown bioaccumulating halogenated compounds, C10H6N2Br3Cl3, C10H6N2Br4Cl2, C10H6N2Br5Cl, and C10H6N2Br6 were characterized using isotope exchange positive chemical ionization (IE–PCI) mass spectrometry (MS) and identified by comparison to synthesized standards. NH3 and ND3 were used as reagent gases for the IE–PCI–MS experiment. The shift in mass of the quasimolecular ion between the NH3 and ND3 PCI obtained

Sheryl A Tittlemier; David H Blank; Gordon W Gribble; Ross J Norstrom

2002-01-01

58

Detection of plutonium isotopes at lowest quantities using in-source resonance ionization mass spectrometry.  

PubMed

The in-source resonance ionization mass spectrometry technique was applied for quantification of ultratrace amounts of plutonium isotopes as a proof of principle study. In addition to an overall detection limit of 10(4) to 10(5) atoms, this method enables the unambiguous identification and individual quantification of the plutonium isotopes (238)Pu and (241)Pu which are of relevance for dating of radiogenic samples. Due to the element-selective ionization process, these isotopes can be measured even under a high surplus of isobaric contaminations from (238)U or (241)Am, which considerably simplifies chemical preparation. The technique was developed, tested, and characterized on a variety of synthetic and calibration samples and is presently applied to analyze environmental samples. PMID:22865006

Raeder, S; Hakimi, A; Stöbener, N; Trautmann, N; Wendt, K

2012-08-03

59

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

NASA Astrophysics Data System (ADS)

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

Wieser, Michael Eugene

1998-09-01

60

High precision Penning trap mass spectrometry of rare isotopes produced by projectile fragmentation  

NASA Astrophysics Data System (ADS)

The Low Energy Beam and Ion Trap (LEBIT) is the only present facility to combine high precision Penning trap mass spectrometry with fast beam projectile fragmentation. Located at the National Superconducting Cyclotron Laboratory (NSCL), LEBIT is able to measure radionuclides produced in a chemically independent process with minimal decay losses. Recent exotic mass measurements include 66As, 63-66Fe, and 32Si. 66As is a new candidate to test the Conserved Vector Current (CVC) hypothesis. The masses of the neutron-rich iron isotopes provide additional information about the mass surface and the subshell closure at N = 40. 32Si is a member of the A = 32, T = 2 quintet; its measurement permits the most stringent test of the validity of the isobaric multiplet mass equation (IMME). An overview of some recent measurements will be presented as well as advanced techniques for ion manipulation.

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

2011-09-01

61

High precision Penning trap mass spectrometry of rare isotopes produced by projectile fragmentation  

NASA Astrophysics Data System (ADS)

The Low Energy Beam and Ion Trap (LEBIT) facility combines high precision Penning trap mass spectrometry with fast beam projectile fragmentation and high pressure gas stopping techniques. Advanced ion manipulation, such as high efficiency continuous mass selection in an ion-guide and radio-frequency ion accumulation and bunching, are used to purify, cool, and pulse the beam. Recent mass measurements include ^63-66Fe, ^66As, and ^32Si. The neutron-rich iron isotopes access the N = 40 subshell closure. The new significantly lower mass uncertainty makes ^66As a candidate to test the CVC hypothesis. ^32Si, member of the A = 32, T = 2 quintet, provides the most precise test of the isobaric multiplet mass equation . An overview of the various aspects of ion manipulation and some of the resulting measurements will be presented.

Kwiatkowski, Anna; Bachelet, C.; Barquest, B. R.; Bollen, G.; Campbell, C. M.; Ferrer, R.; Guenaut, C.; Lincoln, D.; Morrissey, D. J.; Pang, G. K.; Prinke, A. M.; Ringle, R.; Savory, J.; Schwarz, S.; Block, M.; Schury, P.; Folden, C. M., III; Melconian, D.; Sjue, S. K. J.

2009-10-01

62

New method of determining very slight traces of nitrogen peroxide (NOâ) in polluted atmospheres, by isotope dilution and mass spectrometry  

Microsoft Academic Search

The authors propose a new method of determining nitrogen peroxide ; (NOâ) in the atmosphere or the stratosphere at very low concentrations, of ; the order of pp10⁹ by volume or even less. This method employs isotopic ; dilution with ¹⁵NOâ followed by conversion into Nâ and isotopic ; analysis by mass spectrometry. It consists of mixing homogeneously a known

C. M. Stevens; F. Barat; H. Nguyen-Nghi

1975-01-01

63

Can gas chromatography combustion isotope ratio mass spectrometry be used to quantify organic compound abundance?  

PubMed

Quantifying the concentrations of organics such as phospholipid fatty acids (PLFAs) and n-alkanes and measuring their corresponding (13)C/(12)C isotope ratios often involves two separate analyses; (1) quantification by gas chromatography flame ionisation detection (GC-FID) or gas chromatography/mass spectrometry (GC/MS), and (2) (13)?C-isotope abundance analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC-C-IRMS). This requirement for two separate analyses has obvious disadvantages in terms of cost and time. However, there is a history of using the data output of isotope ratio mass spectrometers to quantify various components; including the N and C concentrations of solid materials and CO(2) concentrations in gaseous samples. Here we explore the possibility of quantifying n-alkanes extracted from sheeps' faeces and fatty acid methyl esters (FAMEs) derivatised from PLFAs extracted from grassland soil, using GC-C-IRMS. The results were compared with those from GC-FID analysis of the same extracts. For GC-C-IRMS the combined area of the masses for all the ions (m/z 44, 45 and 46) was collected, referred to as 'area all', while for the GC-FID analysis the peak area data were collected. Following normalisation to a common value for added internal standards, the GC-C-IRMS 'area all' values and the GC-FID peak area data were directly compared. Strong linear relationships were found for both n-alkanes and FAMEs. For the n-alkanes the relationships were 1:1 while, for the FAMEs, GC-C-IRMS overestimated the areas relative to the GC-FID results. However, with suitable reference material 1:1 relationships were established. The output of a GC-C-IRMS system can form the basis for the quantification of certain organics including FAMEs and n-alkanes. PMID:21818802

Thornton, Barry; Zhang, Zulin; Mayes, Robert W; Högberg, Mona N; Midwood, Andrew J

2011-09-15

64

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

65

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

66

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

SciTech Connect

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 not be detected by hydrogen flame ionization, but could be monitored readily by NH/sub 3/ chemical ionization mass spectrometry. The derivatization reaction occurred partially on-column and required optimization of injection conditions. Using stable isotope ratiometry multiple ion detection, (M + 2 + H)/sup +//(M + H)/sup +/ ion ratio of natural abundance taurine was determined with a standard deviation of less than +-0.07% of the ratio. The (1,2-/sup 13/C)taurine/taurine mole ratios of standard mixtures could be accurately determined to 0.001. This stable isotope gc-ms method is suitable for studying the plasma kinetics of (1,2-/sup 13/C)taurine in infants who are at risk with respect to taurine depletion.

Irving, C.S.; Klein, P.D.

1980-09-01

67

A gas chromatograph\\/mass spectrometry method for determining isotopic distributions in organic compounds used in the chemical approach to stable isotope separation  

Microsoft Academic Search

A variety of gas chromatograph\\/mass spectrometry (GC\\/MS) methods have been developed to resolve benzene, benzophenone, anthracene, fluorenone, and their respective stable isotope analogs from other components by gas chromatography. The ratio of stable isotope-labeled material to natural isotopic abundance compounds is determined from the mass spectra averaged across the chromatographic peak. Both total ion and selective ion chromatographic approaches were

A. M. Martinez; W. D. Spall; B. F. Smith

1990-01-01

68

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

69

Candidate reference method: Determination of valproic acid in serum by isotope-dilution mass spectrometry  

Microsoft Academic Search

Summary  A method has been developed for the determination of valproic acid, without derivatization, in human serum by isotope-dilution\\u000a mass spectrometry using labelled 2-propyl[3,3,3-d3] valeric[5,5,5-d3] acid as internal standard for accurate quantification of the concentration of valproic acid in the sample. After acidification,\\u000a the analyte and internal standard are extracted withn-hexane. The amounts of valproic acid in the serum are calculated

F. Susanto; H. Reinauer

1995-01-01

70

Candidate reference method: Determination of valproic acid in serum by isotope-dilution mass spectrometry  

Microsoft Academic Search

Summary  A method has been developed for the determination of valproic acid, without derivatization, in human serum by isotope-dilution\\u000a mass spectrometry using labelled 2-propyl[3,3,3-d3]valeric[5,5,5-d3] acid as internal standard for accurate quantification of the concentration of valproic acid in the sample. After acidification,\\u000a the analyte and internal standard are extracted withn-hexane. The amounts of valproic acid in the serum are calculated from

F. Susanto; H. Reinauer

1995-01-01

71

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

72

Determination of stable isotopes of calcium in biological fluids by fast atom bombardment mass spectrometry  

SciTech Connect

High-resolution fast atom bombardment mass spectrometry was used to measure the isotopic abundances of calcium in plasma and urine. Since the method is very sensitive (>5 x 10/sup 10/ ions/..mu..g of calcium), only 2 to 5 ..mu..L of sample is required. Repetitive measurements of the /sup 42/Ca//sup 40/Ca ratio in plasma and urine require about 3 min and typically have a relative standard deviation of 0.2-0.5%. No sample preparation is necessary and measurements are made by using instrumentation that is often available in larger research laboratories.

Smith, D.L.

1983-12-01

73

Isotopic analysis of single uranium and plutonium particles by chemical treatment and mass spectrometry  

NASA Astrophysics Data System (ADS)

The isotopic composition of single uranium and plutonium particles was measured with an inductively coupled plasma mass spectrometer (ICP-MS) and a thermal ionization mass spectrometer (TIMS). Particles deposited on a carbon planchet were first analyzed with an energy dispersive X-ray spectrometer (EDX) attached to a scanning electron microscope (SEM) and then transferred on to a silicon wafer using a manipulator. The particle on the silicon wafer was dissolved with nitric acid and the isotopic ratios of U and Pu were measured with ICP-MS and TIMS. The results obtained by both methods for particles of certified reference materials showed good agreement with the certified values within the expected uncertainty. The measurement uncertainties obtained in this study were similar for both mass spectrometric methods. This study was performed to establish the method of particle analysis with SEM, EDX, the particle manipulation and chemical preparation technique, and the measurement of isotopic ratios of U and Pu in a single particle by mass spectrometry.

Shinonaga, T.; Esaka, F.; Magara, M.; Klose, D.; Donohue, D.

2008-11-01

74

Adsorption in gas mass spectrometry II. Effects on the measurement of isotope amount ratios  

NASA Astrophysics Data System (ADS)

Gas adsorption in the mass spectrometer inlet system (equipped with molecular leak) causes a deviation from linearity of the measured lnRi/1 data versus time, which affects the extrapolation to time t = 0 required to obtain the isotope amount ratios of a sample. The model first presented in (R. Gonfiantini, S. Valkiers, P.D.P. Taylor, P. De Bievre, Adsorption in gas mass spectrometry. I. Effects on the measurement of individual isotopic species, Int. J. Mass Spectrom. Ion Proc. (1997) in press) is further developed in order to show the effects of adsorption on the data obtained in long measurements of SiF4 samples and improve the extrapolation InRi/1 values to t D 0. The model enables to estimate the isotope fractionation factors for the processes of gas effusion through the molecular leak, and for adsorption and desorption on the inlet system walls. The fractionation factors obtained for gas effusion and adsorption are close to the expected value of (M1/Mi)1/2, where M1 and Mi are the molar masses of the isotopic species considered. The isotope fractionation factor for desorption, which can be evaluated only indirectly from the data fitting, indicates that the heavy isotopes are preferentially retained in the adsorbate. Model extrapolation of data obtained during the first 10 hours of measurement gives values of Ri/10 which are slightly but significantly smaller than those given by linear extrapolation of the first two hour data. The difference is, in relative terms, -(1.88 +/- 0.23) x 10-4 for the 29Si/28Si ratio and -(3.25 +/- 0.47) x 10-4 for the 30Si/28Si ratio. The resulting molar mass for silicon is (1.0 +/- 0.1) x 10-6 parts lower than that obtained with the isotope amount ratios of the linear extrapolation. This effect is not negligible but it cancels by using synthetic isotope mixtures for the measurement calibration. The model does not match the data after 15 h of measurement. This may imply that more than one adsorption mode occurs. Effects related to molecule fragmentation and the space charge distribution in the ion source are discussed.

Gonfiantini, Roberto; Valkiers, Staf; Taylor, Philip D. P.; de Bievre, Paul

1997-12-01

75

Selective ultra trace isotope determination in environmental and biomedical studies by high-resolution resonance ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

The precise determination of relative abundances of ultra trace isotopes in the range below 10-9 is of importance for a wide spectrum of applications in fields like environmental protection, cosmo-chemistry, bio-medical tracer studies or geological and geo-chronological investigations. The necessary high isotopic selectivity, rather complete isobaric suppression and good overall efficiency for these investigations is provided by high-resolution resonance ionization mass spectrometry. Multi-step continuous wave laser excitation and ionization using diode lasers at a compact quadrupole mass spectrometer has been optimized to become a powerful and reliable experimental method, which is just becoming competitive to accelerator mass spectrometry. With this technique we have performed measurements with high isotopic selectivity above 1010 on the isotopes 90Sr and 41Ca while further studies concern Gd and Pu isotopes. In all cases extensive atomic spectroscopic investigations were required as basis for analytical studies.

Wendt, Klaus; Blaum, K.; Geppert, Ch.; Mueller, P.; Trautmann, N.

2002-03-01

76

Precise Re isotope ratio measurements by negative thermal ionization mass spectrometry (NTI-MS) using total evaporation technique  

Microsoft Academic Search

High precision rhenium isotope ratios, 187Re\\/185Re, have been determined by negative thermal ionization mass spectrometry (NTI-MS) using a total evaporation technique. The salient features of this method are evaporation of the entire sample and simultaneous integration of the signal from each isotope, which effectively eliminates isotope fractionation effects during the evaporation process. The 187Re\\/185Re ratio is obtained with a high

Katsuhiko Suzuki; Yoshiki Miyata; Nobuyuki Kanazawa

2004-01-01

77

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

78

Selective isotope determination of lanthanum by diode-laser-initiated resonance-ionization mass spectrometry  

SciTech Connect

A diode-laser step has been incorporated into a resonance-ionization mass spectrometry optical excitation process to enhance the isotopic selectivity of the technique. Lanthanum isotope ratio enhancements as high as 10{sup 3} were achieved by use of a single-frequency cw diode laser tuned to excite the first step of a three-step excitation--ionization optical process; the subsequent steps were excited by use of a pulsed dye laser. Applying the same optical technique, we measured atomic hyperfine constants for the high-lying even-parity {sup 4}{ital D}{sub 5/2} state of lanthanum at 30 354 cm{sup --1}. The general utility of this spectral approach is discussed.

Young, J.P.; Shaw, R.W. [Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831-6142 (United States)

1995-08-01

79

High Spatial Resolution Isotopic Abundance Measurements by Secondary Ion Mass Spectrometry: Status and Prospects  

NASA Astrophysics Data System (ADS)

Secondary Ion Mass Spectrometry, SIMS or ion microprobe analysis, has become an important tool for geochemistry because of its ability study the distributions of elemental and isotopic abundances in situ on polished samples with high (typically a few microns to sub-micron) spatial resolution. In addition, SIMS exhibits high sensitivity for a wide range of elements (H to Pu) so that isotope analyses can sometimes be performed for elements that comprise only trace quantities of some mineral phase (e.g., Pb in zircon) or on major and/or minor elements in very small samples (e.g., presolar dust grains). Offsetting these positive attributes are analytical difficulties due to the complexity of the sputtering source of analyte ions: (1) relatively efficient production of molecular ion species (especially from a complex matrix such as most natural minerals) that cause interferences at the same nominal mass as atomic ions of interest, and (2) quantitation problems caused by variations in the ionization efficiencies of different elements and/or isotopes depending upon the chemical state of the sample surface during sputtering--the so-called "matrix effects". Despite the availability of high mass resolution instruments (e.g., SHRIMP II/RG, CAMECA 1270/1280/NanoSIMS), the molecular ion interferences effectively limit the region of the mass table that can be investigated in most samples to isotope systems at Ni or lighter or at Os or heavier. The matrix effects and the sensitivity of instrumental mass discrimination to the physical state of the sample surface can hamper reproducibility and have contributed to a view that SIMS analyses, especially for so- called stable isotopes, are most appropriate for extraterrestrial samples which are often small, rare, and can exhibit large magnitude isotopic effects. Recent improvements in instrumentation and technique have extended the scope of SIMS isotopic analyses and applications now range from geochronology to paleoclimatology to volcanology to biogeochemistry and cosmochemistry. Multiple collector (static magnetic field) measurements at high mass resolving power have enabled high precision (sub-permil) for several stable isotopes systems (e.g., C, O, Mg, S). Applied to geochronology, the multiple collector approach permits very rapid survey of zircon Pb-Pb ages to identify candidate Hadean grains for further detailed analysis. Ion imaging has been used to correlate isotope compositions with biochemistry (e.g., FISH-SIMS) or to search for especially rare samples among larger populations (e.g., supernova grains of Stardust). For favorable sample geometries with lateral homogeneity, SIMS isotope analyses may be conducted in depth-profiling mode which brings spatial resolution into the tens of nm range. Applications of this approach include experimental petrology, thermochronology, and isotopic analyses of shallowly-implanted solar wind ions. New approaches to removal of molecular ion interferences include reverse- geometry instrumentation and accelerator-based SIMS. There always exists trade-offs between microanalysis and trace analysis on the one hand, and high precision on the other. In this contribution, I will review current status for isotope precision and accuracy of SIMS for applications in stable and radiogenic isotopes as a function of spatial scale. A discussion of current limits and future prospects for improvement in understanding matrix effects will be given. Examples from ion imaging/ depth profiling/ geochronology and cosmochemistry will be provided.

McKeegan, K. D.

2007-12-01

80

Particle Detectors Used in Isotope Ratio Mass Spectrometry, with Applications in Geology, Environmental Science and Nuclear Forensics  

NASA Astrophysics Data System (ADS)

This chapter introduces the reader to mass spectrometry and the instruments used to determine high-precision isotope ratios. These instruments separate ion beams, of charged atomic particles with kinetic energies of several keV, by mass-to-charge ratio. Quantitative detection of these energetic charged particles is a key technology in mass spectrometry. For isotope ratio determination the main detector types are Faraday cups, the Daly detector, and discrete dynode secondary electron multiplier (SEM) ion counters. For high-precision applications, arrays of these detectors are arranged to collect several ion beams simultaneously. Examples are given for the application of these detectors in geology, environmental sciences, and nuclear safeguards.

Lloyd, Nicholas S.; Schwieters, Johannes; Horstwood, Matthew S. A.; Parrish, Randall R.

81

Stable isotope labeling of Arabidopsis thaliana cells and quantitative proteomics by mass spectrometry.  

PubMed

Quantitative analysis of protein expression is an important tool for the examination of complex biological systems. Albeit its importance, quantitative proteomics is still a challenging task because of the high dynamic range of protein amounts in the cell and the variation in the physical properties of proteins. Stable isotope labeling by amino acids in cell culture (SILAC) has been successfully used in yeast and mammalian cells to measure relative protein abundance by mass spectrometry. Here we show for the first time that proteins from Arabidopsis thaliana cell cultures can be selectively isotope-labeled in vivo by growing cells in the presence of a single stable isotope-labeled amino acid. Among the tested amino acids ([2H3]-leucine, [13C6]arginine, and [2H4]lysine), [13C6]arginine proved to be the most suitable. Incorporation of [13C6]arginine into the proteome was homogeneous and reached efficiencies of about 80%. [13C6]Arginine-labeled A. thaliana suspension cells were used to study the regulation of glutathione S-transferase expression in response to abiotic stress caused by salicylic acid and to identify proteins that bind specifically to phosphorylated 14-3-3 binding motifs on synthesized bait peptides in affinity purification experiments. In conclusion, the combination of stable isotope labeling of plant cells and mass spectrometry is a powerful technology that can be applied to study complex biological processes that involve changes in protein expression such as cellular responses to various kinds of stress or activation of cell signaling. PMID:16088002

Gruhler, Albrecht; Schulze, Waltraud X; Matthiesen, Rune; Mann, Matthias; Jensen, Ole N

2005-08-08

82

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

PubMed

Small-mass-difference modifications to proteins are obscured in mass spectrometry by the natural abundance of stable isotopes such as (13)C 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. PMID:23247967

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

2012-12-18

83

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

84

Quantitative determination of formaldehyde in cosmetics using a combined solid-phase microextraction–isotope dilution mass spectrometry method  

Microsoft Academic Search

Solid-phase microextraction (SPME) in conjunction with isotope dilution mass spectrometry (ID-MS) was employed for the analysis of formaldehyde in cosmetic products. The formaldehyde is derivatized in situ with pentafluorophenyl hydrazine. The formed hydrazone is adsorbed over a poly(dimethylsiloxane)–divinylbenzene-coated fiber and analyzed using gas chromatography–mass spectrometry. The adsorption–time profiles and salting effect were studied. The quantitation was performed by using a

René Thomas Rivero; Vinod Topiwala

2004-01-01

85

Iron isotope ratio measurements by negative thermal ionisation mass spectrometry using FeF 4 ? molecular ions  

Microsoft Academic Search

Based on the formation of molecular FeF4? ions under thermal ion source conditions, a negative thermal ionisation technique for iron was developed. Compared with the widely used iron isotopic analysis by positive thermal ionisation mass spectrometry, a better control of mass-dependent isotopic fractionation is possible by generating molecular FeF4? ions instead of an atomic Fe+ ion beam at comparable ionisation

Thomas Walczyk

1997-01-01

86

Stable carbon isotopic analyses of lignin-derived CuO oxidation products by isotope ratio monitoring-gas chromatography-mass spectrometry (irm-GC-MS)  

Microsoft Academic Search

In this paper, we evaluate compound-specific isotope analyses of lignin reaction products through the combined application of alkaline CuO oxidation and isotope ratio monitoring-gas chromatography-mass spectrometry (irm-GC-MS). Analyses of phenol standards as trimethylsilyl ethers\\/esters by irm-GC-MS yield accurate (±0.5‰) estimates of their isotopic signatures after correcting for added derivative carbon with precisions ?1‰. CuO oxidation of purified lignin polymers yields

Miguel A. Goñi; Timothy I. Eglinton

1996-01-01

87

Gas chromatography carbon isotope ratio mass spectrometry applied to the detection of neutral alcohol in Scotch whisky: an internal reference approach  

Microsoft Academic Search

Ethanol and the volatile congeners of Scotch whisky have been analysed by GC–combustion stable isotope ratio mass spectrometry (GC–C–IRMS). Ethanol, propan-1-ol, 2-methylpropan-1-ol and methylbutan-1-ol (2- and 3-methylbutan-1-ol) have been separated using gas chromatography and their ratios of stable isotopes of carbon (13C\\/12C) determined by combustion isotope ratio mass spectrometry. The internal isotopic correlations for the ethanol and the congeners from

Christopher N Rhodes; Karl Heaton; Ian Goodall; Paul A Brereton

2009-01-01

88

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 70W of applied radiofrequency power, 250Pa of pressure, 2ms of pulse width and 4ms 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 81-5770mg/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

2013-06-22

89

Stable oxygen and hydrogen isotopes of brines - comparing isotope ratio mass spectrometry and isotope ratio infrared spectroscopy  

NASA Astrophysics Data System (ADS)

Today's standard analytical methods for high precision stable isotope analysis of fluids are gas-water equilibration and high temperature pyrolysis coupled to isotope ratio mass spectrometers (IRMS). In recent years, relatively new laser-based analytical instruments entered the market that are said to allow high isotope precision data on nearly every media. This optical technique is referred to as isotope ratio infrared spectroscopy (IRIS). The objective of this study is to evaluate the capability of this new instrument type for highly saline solutions and a comparison of the analytical results with traditional IRMS analysis. It has been shown for the equilibration method that the presence of salts influences the measured isotope values depending on the salt concentration (see Lécuyer et al, 2009; Martineau, 2012). This so-called 'isotope salt effect' depends on the salt type and salt concentration. These factors change the activity in the fluid and therefore shift the isotope ratios measured by the equilibration method. Consequently, correction factors have to be applied to these analytical data. Direct conversion techniques like pyrolysis or the new laser instruments allow the measurement of the water molecule from the sample directly and should therefore not suffer from the salt effect, i.e. no corrections of raw values are necessary. However, due to high salt concentrations this might cause technical problems with the analytical hardware and may require labor-intensive sample preparation (e.g. vacuum distillation). This study evaluates the salt isotope effect for the IRMS equilibration technique (Thermo Gasbench II coupled to Delta Plus XP) and the laser-based IRIS instruments with liquid injection (Picarro L2120-i). Synthetic salt solutions (NaCl, KCl, CaCl2, MgCl2, MgSO4, CaSO4) and natural brines collected from the Stassfurt Salt Anticline (Germany; Stadler et al., 2012) were analysed with both techniques. Salt concentrations ranged from seawater salinity up to full saturation. References Lécuyer, C. et al. (2009). Chem. Geol., 264, 122-126. [doi:10.1016/j.chemgeo.2009.02.017] Martineau, F. et al. (2012). Chem. Geol., 291, 236-240. [doi:10.1016/j.chemgeo.2011.10.017] Stadler, S. et al. (2012). Chem. Geol., 294-295, 226-242. [doi:10.1016/j.chemgeo.2011.12.006

Ahrens, Christian; Koeniger, Paul; van Geldern, Robert; Stadler, Susanne

2013-04-01

90

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.

91

Determination of hafnium in zirconium metal and zircaloy 4 metal Standard Reference Materials by isotope dilution spark source mass spectrometry  

SciTech Connect

A procedure has been developed for the determination of microgram per gram concentrations of hafnium in zirconium metal and zircaloy 4 metal Standard Reference Materials (SRM's) by stable isotope dilution spark source mass spectrometry. The concentration of hafnium in these SRM's ranges from 200 ..mu..g/g in SRM 1236 to 32 ..mu..g/g in SRM 1237. One-half-gram samples were spiked with /sup 179/Hf and dissolved in a mixture of hydrofluoric and sulfuric acids and the isotopically altered Hf was separated from Zr by cation exchange chromatography using 0.32 M sulfuric acid as an eluant. The isotopically altered, purified hafnium was evaporated onto 200 mesh gold powder which was subsequently homogenized and pressed into electrodes. The altered isotopic ratios were determined by spark source mass spectrometry using electrical detection. 8 references, 4 tables.

Powell, L.J.; Paulsen, P.J.

1984-03-01

92

Correcting for the effects of natural abundance in stable isotope resolved metabolomics experiments involving ultra-high resolution mass spectrometry  

Microsoft Academic Search

BACKGROUND: Stable isotope tracing with ultra-high resolution Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) can provide simultaneous determination of hundreds to thousands of metabolite isotopologue species without the need for chromatographic separation. Therefore, this experimental metabolomics methodology may allow the tracing of metabolic pathways starting from stable-isotope-enriched precursors, which can improve our mechanistic understanding of cellular metabolism. However, contributions to the

Hunter N. B. Moseley

2010-01-01

93

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

94

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.

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

2013-01-01

95

Determination of dissolved selenium species in environmental water samples using isotope dilution mass spectrometry.  

PubMed

In order to clarify the species composition of selenium in environmental water samples, analytical methods have been developed for the selective determination of different chemical forms of this element (selenite, selenate, and organic species including trimethylselenonium) using isotope dilution mass spectrometry (IDMS). The species analysis was made possible by means of chromatographic separation procedures and an 82Se-enriched selenate, selenite, and trimethylselenonium spike for the isotope dilution process. The total selenium concentration was determined after decomposition of organic compounds with a HNO3/HCIO4 mixture. Selenium was measured in the mass spectrometer by producing negative Se- thermal ions for detection. Precise determination at the parts-per-trillion level was achieved. This new methodology was applied to different types of natural water samples (groundwater, pond water, river water, moorland lake water) with total selenium concentrations in the range of 200 pg/g to 15 ng/g. Selenite and selenate have been the only detected species in most of the investigated samples, with selenate dominating all except one. In samples with high contents of dissolved organic carbon, however, different organoselenium compounds including trimethylselenonium ions were additionally quantified in the range of 10-95 pg/g. In these cases, the sum of all selenium species agreed well with the independently determined total element concentration. PMID:1750700

Tanzer, D; Heumann, K G

1991-09-15

96

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

NASA Astrophysics Data System (ADS)

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

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

2006-12-01

97

Elemental composition and origin of (polyatomic) ions in inductively coupled plasma mass spectrometry disclosed by means of isotope exchange experiments  

Microsoft Academic Search

Stable isotopic labelling is a suitable method for the assignment of the elemental composition of interference ions by comparison of spectra of labelled compounds with those of non-labelled ones. We have used this method for the identification of the low-mass range ions in inductively coupled plasma mass spectrometry (ICP---MS) and for determining their origin. To this end, ICP mass spectra

A. A. van Heuzen; N. M. M. Nibbering

1993-01-01

98

Biomedical applications of accelerator mass spectrometry-isotope measurements at the level of the atom.  

PubMed

Accelerator mass spectrometry (AMS) is a nuclear physics technique developed about twenty years ago, that uses the high energy (several MeV) of a tandem Van de Graaff accelerator to measure very small quantities of rare and long-lived isotopes. Elements that are of interest in biomedicine and environmental sciences can be measured, often to parts per quadrillion sensitivity, i.e. zeptomole to attomole levels (10(-21)-10(-18) mole) from milligram samples. This is several orders of magnitude lower than that achievable by conventional decay counting techniques, such as liquid scintillation counting (LSC). AMS was first applied to geochemical, climatological and archaeological areas, such as for radiocarbon dating (Shroud of Turin), but more recently this technology has been used for bioanalytical applications. In this sphere, most work has been conducted using aluminium, calcium and carbon isotopes. The latter is of special interest in drug metabolism studies, where a Phase 1 adsorption, distribution, metabolism and excretion (ADME) study can be conducted using only 10 nanoCurie (37 Bq or ca. 0.9 microSv) amounts or less of 14C-labelled drugs. In the UK, these amounts of radioactivity are below those necessary to request specific regulatory approval from the Department of Health's Administration of Radioactive Substances Advisory Committee (ARSAC), thus saving on valuable development time and resources. In addition, the disposal of these amounts is much less an environmental issue than that associated with microCurie quantities, which are currently used. Also, AMS should bring an opportunity to conduct "first into man" studies without the need for widespread use of animals. Centre for Biomedical Accelerator Mass Spectrometry (CBAMS) Ltd. is the first fully commercial company in the world to offer analytical services using AMS. With its high throughput and relatively low costs per sample analysis, AMS should be of great benefit to the pharmaceutical and biotechnology industries as well as other life science areas. PMID:10097404

Barker, J; Garner, R C

1999-01-01

99

High-resolution multi-isotope imaging mass spectrometry enables visualisation of stem cell division and metabolism.  

PubMed

MIMS visualises metabolism: A recent publication by Steinhauser and co-workers presents a novel application of multi-isotope mass spectrometry (MIMS) to visualise physiological metabolism in live mammalian organisms, and validate the "immortal strand hypothesis" of asymmetric chromosomal division of stem cells in the small intestine. PMID:22619149

Goto, Kensuke; Waki, Michihiko; Takahashi, Tsukasa; Kadowaki, Makoto; Setou, Mitsutoshi

2012-04-19

100

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

101

The determination of dissolved zirconium and hafnium from seawater using isotope dilution inductively coupled plasma mass spectrometry  

Microsoft Academic Search

This paper describes the development of an analytical technique utilizing isotope dilution and inductively coupled plasma mass spectrometry (ICP\\/MS) to determine the picomolar and femtomolar concentrations of dissolved Zr and Hf found in seawater. Data acquired using this technique are presented to verify the method; in the subarctic North Pacific Zr ranges from 25 to 366 pmol\\/kg and Hf from

Brad A McKelvey; Kristin J Orians

1998-01-01

102

Stable Isotope Peptide Mass Spectrometry To Decipher Amino Acid Metabolism in Dehalococcoides Strain CBDB1  

PubMed Central

Dehalococcoides species are key players in the anaerobic transformation of halogenated solvents at contaminated sites. Here, we analyze isotopologue distributions in amino acid pools from peptides of Dehalococcoides strain CBDB1 after incubation with 13C-labeled acetate or bicarbonate as a carbon source. The resulting data were interpreted with regard to genome annotations to identify amino acid biosynthesis pathways. In addition to using gas chromatography-mass spectrometry (GC-MS) for analyzing derivatized amino acids after protein hydrolysis, we introduce a second, much milder method, in which we directly analyze peptide masses after tryptic digest and peptide fragments by nano-liquid chromatography-electrospray ionization-tandem mass spectrometry (nano-LC-ESI-MS/MS). With this method, we identify isotope incorporation patterns for 17 proteinaceous amino acids, including proline, cysteine, lysine, and arginine, which escaped previous analyses in Dehalococcoides. Our results confirmed lysine biosynthesis via the ?-aminoadipate pathway, precluding lysine formation from aspartate. Similarly, the isotopologue pattern obtained for arginine provided biochemical evidence of its synthesis from glutamate. Direct peptide MS/MS analysis of the labeling patterns of glutamine and asparagine, which were converted to glutamate and aspartate during protein hydrolysis, gave biochemical evidence of their precursors and confirmed glutamate biosynthesis via a Re-specific citrate synthase. By addition of unlabeled free amino acids to labeled cells, we show that in strain CBDB1 none of the 17 tested amino acids was incorporated into cell mass, indicating that they are all synthesized de novo. Our approach is widely applicable and provides a means to analyze amino acid metabolism by studying specific proteins even in mixed consortia.

Marco-Urrea, Ernest; Seifert, Jana; von Bergen, Martin

2012-01-01

103

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

PubMed

A new method for bulk carbon isotope ratio determination of water-soluble samples is presented that is based on flow injection analysis-isotope ratio mass spectrometry (FIA-IRMS) using an LC IsoLink interface. Advantages of the method are that (i) only very small amounts of sample are required (2-5 microL of the sample for up to 200 possible injections), (ii) it avoids complex sample preparation procedures such as needed for EA-IRMS analysis (only sample dilution and injection,) and (iii) high throughput due to short analysis times is possible (approximately 15 min for five replicates). The method was first tested and evaluated as a fast screening method with industrially produced ethanol samples, and additionally the applicability was tested by the measurement of 81 alcoholic beverages, for example, whiskey, brandy, vodka, tequila, and others. The minimal sample concentration required for precise and reproducible measurements was around 50 microL L(-1) ethanol/water (1.71 mM carbon). The limit of repeatability was determined to be r=0.49%. FIA-IRMS represents a fast screening method for beverage authenticity control. Due to this, samples can be prescreened as a decisive criterion for more detailed investigations by HPLC-IRMS or multielement GC-IRMS measurements for a verification of adulteration. PMID:19856915

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

2009-11-25

104

Profiling of urinary formestane and confirmation by isotope ratio mass spectrometry.  

PubMed

Formestane (F, androst-4-en-4-ol-3,17-dione) is an irreversible aromatase inhibitor with the ability to suppress the estrogen production from anabolic steroids. Consequently, F is mentioned on the World Anti-Doping Agency (WADA) prohibited list and because studies have shown that F is produced endogenously in small amounts, a threshold for urinary excreted F of 150ng/mL was introduced. Lower concentrations could be due to endogenous production and need further investigation to prove the exact origin through determination of the carbon isotope ratio. However, because the current screening methods are a lot more sensitive, F is detected in practically every urine sample. A strict implementation of this WADA rule would imply that almost every urine sample needs additional investigation to verify an exogenous or endogenous origin. The main aim of this study was to propose and introduce a lower concentration limit of 25ng/mL beneath which the detected F is considered as being endogenous and no further investigation is needed. The data presented in this paper suggests that this threshold provides a good balance between a sufficiently large detection window and not having to perform isotope ratio mass spectrometry (IRMS) analyses on negative urine samples. PMID:23933120

Polet, Michael; Van Renterghem, Pieter; Van Gansbeke, Wim; Van Eenoo, Peter

2013-08-07

105

Stable Isotope Dilution Multidimensional Liquid Chromatography-Tandem Mass Spectrometry for Pancreatic Cancer Serum Biomarker Discovery  

PubMed Central

A novel approach to pancreatic cancer biomarker discovery has been developed, which employs a stable isotope labeled proteome (SILAP) standard coupled with extensive multidimensional separation coupled with tandem mass spectrometry (MS/MS). Secreted proteins from CAPAN-2 human pancreatic cancer derived cells were collected after conducting stable isotope labeling by amino acids in cell culture (SILAC). The resulting SILAP standard contained <0.5% of individual unlabeled proteins. Pooled sera from patients with early stage pancreatic cancer or controls were prepared, and an equal amount of the SILAP standard was added to each sample. Proteins were separated by isoelectric focusing (IEF) prior to two-dimensional liquid chromatography (2D-LC)–MS/MS analysis. A total of 1065 proteins were identified of which 121 proteins were present at 1.5-fold or greater concentrations in the sera of patients with pancreatic cancer. ELISA validation of these findings was successfully performed for two proteins, ICAM-1 and BCAM. Results of these studies have provided proof of principle that a SILAP standard derived from the CAPAN-2 secreted proteome can be used in combination with extensive multidimensional LC-MS/MS for the identification and relative quantitation of potential biomarkers of pancreatic cancer. This technique allows for the detection of low-abundance proteins, and focuses only on biologically relevant proteins derived from pancreatic cancer cells.

2009-01-01

106

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±0.86ng/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±0.9mg/kg and 70.7±4.5mg/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

2013-05-09

107

Environmental Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Environmental mass spectrometry is an important branch of science because it provides many of the data that underlie policy decisions that can directly influence the health of people and ecosystems. Environmental mass spectrometry is currently undergoing rapid development. Among the most relevant directions are a significant broadening of the lists of formally targeted compounds; a parallel interest in nontarget chemicals; an increase in the reliability of analyses involving accurate mass measurements, tandem mass spectrometry, and isotopically labeled standards; and a shift toward faster high-throughput analysis, with minimal sample preparation, involving various approaches, including ambient ionization techniques and miniature instruments. A real revolution in analytical chemistry could be triggered with the appearance of robust, simple, and sensitive portable mass spectrometers that can utilize ambient ionization techniques. If the cost of such instruments is reduced to a reasonable level, mass spectrometers could become valuable household devices.

Lebedev, Albert T.

2013-06-01

108

Environmental mass spectrometry.  

PubMed

Environmental mass spectrometry is an important branch of science because it provides many of the data that underlie policy decisions that can directly influence the health of people and ecosystems. Environmental mass spectrometry is currently undergoing rapid development. Among the most relevant directions are a significant broadening of the lists of formally targeted compounds; a parallel interest in nontarget chemicals; an increase in the reliability of analyses involving accurate mass measurements, tandem mass spectrometry, and isotopically labeled standards; and a shift toward faster high-throughput analysis, with minimal sample preparation, involving various approaches, including ambient ionization techniques and miniature instruments. A real revolution in analytical chemistry could be triggered with the appearance of robust, simple, and sensitive portable mass spectrometers that can utilize ambient ionization techniques. If the cost of such instruments is reduced to a reasonable level, mass spectrometers could become valuable household devices. PMID:23527549

Lebedev, Albert T

2013-02-28

109

Iridium isotope ratio measurements by negative thermal ionization mass spectrometry and atomic weight of iridium  

NASA Astrophysics Data System (ADS)

A technique of negative thermal ionization mass spectrometry (NTI-MS) for the precise iridium isotope ratio determination is presented. IrO-2 and IrO-3 ions are formed in a double-filament (Pt) ion source using (NH4)2IrCl6 as a sample compound. The IrO-2 ion current always exceeds the IrO-3 current by a factor of about 50-300 depending on the filament temperature and the oxygen gas introduced into the ion source. IrO-3 ion currents of more than 10-11 A can be obtained at the detector side from 100 ng iridium samples. The relative standard deviation of the 191Ir/193 ratio determination is 0.06%, which is much better than the data quoted in past literature. From such data the atomic weight of iridium could be calculated to be 192.21661 ± 0.00029. This value is a great improvement when compared with the iridium atomic weight of 192.22 ± 0.03 recommended by IUPAC. Additionally, an NTI-MS technique has been developed which allows the simultaneous measurement of iridium and osmium isotope ratio from osmiridium samples without any chemical separation. The iridium isotope ratios of three osmiridium samples agree well with the ratios determined from the hexachloroiridate compound. The direct 187Os/186OS determination from osmiridium samples opens the possibility of studying the evolution of osmium in the Earth's mantle due to the radioactive decay of 187Re into 187Os.

Walczyk, Thomas; Heumann, Klaus G.

1993-02-01

110

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

NASA Astrophysics Data System (ADS)

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

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

2006-11-01

111

Sulfur Isotope Variation in Melt Inclusions From Arc Basalts Revealed By Secondary Ion Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Subduction zones are sites where elements once at the Earth’s surface are recycled back to the mantle. Arc volcanoes return volatiles and hydrous melts to the surface. Understanding of sulfur recycling in magmatic arcs is hampered by insufficient data on net sulfur isotopic composition of slab inputs, that range from ?34S of seawater (21‰) to negative ?34S of -70‰ for secondary sulfides, to values of 0 ± 3‰ in relict magmatic sulfides. We lack sufficient knowledge of the sulfur concentration and isotopic composition of the mantle wedge. Degassing and assimilation of crustal sulfur may produce changes to initial sulfur isotope ratios of magmas. To preclude degassing effects, we measured S isotope ratios in mafic melt inclusions by secondary ionization mass spectrometry (SIMS) from three arc volcanoes, Galunggung, and Krakatau in Indonesia, and Augustine, in Alaska. These data provide a view of the variability of initial sulfur isotope ratios of mafic arc magmas and are being evaluated for correlations with sulfur and iron oxidation state, dissolved volatiles, trace elements, and degassing effects in order to determine the origin(s) of dissolved S. Olivine-hosted melt inclusions from a basaltic bomb from the 1982-1983 Galunggung eruption represent the relatively dry adiabatic decompression melting end member of primary arc magma genesis (Sisson and Bronto,1998). New SIMS ?34S measurements of Galunggung melt inclusions yield ratios from -3.0‰ to +5.0‰ with S concentrations of 1950 ppm - 990 ppm. A few Galunggung inclusions have ?34S between 0.5‰ and 1.4‰ with S conc.'s of 1690 - 1760 ppm, that are within the mantle range, and have low water contents of 0.25 to 0.30 wt.% (Kelley et al. 2005). A subgroup of inclusions yield ?34S of 2.8‰ to 5.0‰ and 990 - 1920 ppm S. Pre-1883 basaltic scoria from Krakatau volcano contain olivine-hosted melt inclusions with water and CO2 concentrations from 1.8 - 4.1 wt.% and 79 - 1017 ppm, respectively. Dissolved S conc. in these inclusions ranges from 620-2400 ppm. SIMS isotope measurements yield ?34S ranging from 1.6‰ to 8.7‰ with no obvious correlation with S concentration, but inclusions with greater than 1400 ppm S have ?34S of 3.0‰ to 5.5‰. Tentative positive correlations in ?34S versus dissolved CO2 and H2O may indicate a H2O - and 34S-enriched component entering into the magma source region. A Pleistocene basaltic pyroclastic deposit from Augustine volcano contains olivine-hosted melt inclusions with some of the highest dissolved water (up to 7.5 wt.%), sulfur (6600 ppm) and chlorine (6500 ppm) for mafic magmas worldwide (Plank et al. 2006). SIMS isotope measurements yield ?34S values of 1.5‰ to 14.9‰ for inclusions with 2624 to 4650 ppm S. Most melt inclusion data form a cluster with ?34S ranging from 6.7‰ to 12.7‰. Extreme volatile enrichment coupled with elevated ?34S values indicate a 34S-enriched component in the magma source region. Kelley K A,et al.(2005)Geochim. Cosmochim. Acta, 10S, A743. Plank T, et al. (2006) EOS Trans., AGU, 87(52), Fall Meet. Suppl., Abstract V42B-06. Sisson T, and Bronto S (1998) Nature, 391, 883-886.

Mandeville, C. W.; Shimizu, N.; Kelley, K. A.

2009-12-01

112

Advantages of Secondary Ion Mass Spectrometry (SIMS) for Stable Isotope Microanalysis of Trace Light Elements  

NASA Astrophysics Data System (ADS)

SIMS has several general advantages for the determination of light stable isotopes occurring at trace element concentrations in natural samples. Ion microprobe SIMS instruments sputter nanogram quantities of material from a well defined, micrometer-sized analytical crater. The extremely small quantity of sample extracted allows analysis of very small objects, such as igneous melt inclusions. Sputter ionization of many light elements (e.g.; Li, B, S, Cl) is efficient enough (>>1%) to allow precise determination of isotope ratios at elemental concentrations as low as 1 - 100 ppm. Primary bombardment of the sample is performed in close proximity to the initial extraction optics of the mass spectrometer, enabling very stable control of the ionization process. Consequently, instrumental mass fractionation (IMF) can be maintained at a very consistent and reproducible level. In situ SIMS microanalysis has a particular advantage for samples where the elemental concentration is less than that which would provoke chemical blank problems during preparation of the purified samples necessary for other types of mass spectrometry. B isotopes. Use of SIMS for the determination of delta11B is simplified because compositionally diverse matrices are amenable to calibration for IMF with a single standard; usually a high silica glass containing 100s - 1000s ppm total B1.This attribute is particularly convenient in subduction-related volcanic systems, where tephra sequences may contain a wide spectrum of major element chemistries. The combination of ? 11B and trace element microanalyses has been particularly valuable in these same systems. For example, the inverse correlation of ? 11B with LILE/Nb ratios in Neogene fallout tephra was used to infer the contribution of a metasomatized mantle wedge to the Izu Arc Front volcanics2. Li isotopes. For Li, IMF is more dependent on matrix chemistry, requiring a well-determined suite of standards. IMF may also drift in response to elemental mobility under ion beam charging. Nevertheless, Li ionizes (as Li+) with extremely high efficiency under O- bombardment (>>10%). With careful attention to calibration and sputtering stability, ? 7Li may be quantitatively determined in glass or silicate mineral samples containing as little as 1 ppm total Li. Contrasting aqueous solubility behavior makes ? 7Li a valuable complement to ? 11B in the study of processes involving high temperature hydrothermal fluids. Cl isotopes. ? 37Cl is readily amenable to SIMS microanalysis in a variety of matrices, due to the vigorous ionization of Cl (as Cl-) under bombardment by positive primary ion beams such as Cs+. Determination of ? 37Cl in glassy matrices requires using a Normal Incidence Electron Gun (NEG) to compensate for sample charging. A series of well-typified standards are also essential to calibrate for IMF, which can vary up to 10 per mil relative between basaltic and rhyolitic matrices3. However, precise determinations of ? 37Cl are possible for glasses or silicate minerals with as little as 100 - 200 ppm total Cl. Further, certain natural fluids (e.g., seawater or submarine hydrothermal vent fluids) can be prepared by evaporation/integration with conductive binders, and then sputtered directly for SIMS analysis. In this manner, ? 37Cl can be determined in microliter fluid aliquots, containing as little as 1 microgram of total Cl4. 1Chaussidon, M. et al, 1997, GSNL 21(1), 7-17; 2S.M.Straub and G.D.Layne, 2002, EPSL, 198, 25-39; 3A.V.Godon et al, 2001, EOS, 82(47), F1392; 4W.Bach et al, 2002, EOS, 83(47), V61B-1367.

Layne, G. D.

2003-12-01

113

Isotopic abundance measurements on solid nuclear-type samples by glow discharge mass spectrometry  

Microsoft Academic Search

A double-focusing Glow Discharge Mass Spectrometer (GDMS) installed in a glovebox for nuclear sample screening has been employed for isotopic measurements. Isotopic compositions of zirconium, silicon, lithium, boron, uranium and plutonium which are elements of nuclear concern have been determined. Interferences arising from the matrix sample and the discharge gas (Ar) for each of these elements are discussed. The GDMS

Maria Betti; Gert Rasmussen; Lothar Koch

1996-01-01

114

The Role of Naturally Occurring Stable Isotopes in Mass Spectrometry, Part I: The Theory  

PubMed Central

In this tutorial, the authors explain how naturally occurring stable isotopes are contributing to experimentally determined mass spectra and how this information can be exploited in quantitative experiments, structural elucidation studies and tracer methodologies. The first instalment of this two part series focuses on the theoretical aspects of stable isotopes and the calculation of their distribution patterns.

Bluck, Les; Volmer, Dietrich A.

2013-01-01

115

Quantitation of stable isotopic tracers of calcium by fast atom bombardment mass spectrometry  

Microsoft Academic Search

Instrumentation and methodology developed for quantitation of stable isotopic traces in urine are described. Calcium is isolated from urine as the insoluble oxalate salt which is subsequently dissolved in hydrochloric acid. The isotopic content of the acid solution is determined by use of a conventional mass spectrometer equipped with a fast atom bombardment ion source. Calcium ions are desorbed from

Xiangyu. Jiang; David L. Smith

1987-01-01

116

Cd Isotopic Composition Measured by Plasma Source Mass Spectrometry on Natural and Anthropogenic Materials. A Preliminary Outline of Cd Isotope Systematics  

NASA Astrophysics Data System (ADS)

Cadmium is a trace metal that is used as a geochemical tracer of natural processes, like biological productivity and paleoproductivity, and also of anthropogenic pollution, as Cd is known to be a toxic heavy metal that has become a major environmental and health concern. For these purposes, an outstanding issue is to determine whether Cd, like a number of metallic elements (e.g. Fe, Cu, Zn, Mo, Tl), may display variable isotopic compositions in natural and/or industrial compounds. It is known that Cd may display variable isotopic composition. Indeed, isotopic fractionation processes have been documented in some meteorites and in lunar soils. Consequently, due to its relatively low boiling point (767\\deg C) and also to the large mass range covered by its isotopes (10 mass units), Cd might fractionate isotopically, for example during the outpouring of acidic volcanic magmas and/or the emplacement of granitoids. On another hand, isotopic fractionation could also occur during human activities like refuse incineration or industrial manufacturing, for instance. Finally, biologically-induced isotopic fractionation should not be ruled out, as it is clearly evidenced for other metals, like Fe. A high precision method has been developed for determining the isotopic composition of Cd by plasma source mass spectrometry (Neptune). This method holds on the standard-bracketing technique, owing to the availability of Cd solutions of known isotopic composition provided by the University of M\\H{u}nster. This allows to correct precisely for mass fractionation that occurs in the plasma source mass spectrometer. It is also critical for the analysis to be possible to work with Cd solutions of very high purity. Chemical isolation of Cd involves 3 steps, and may be also suitable for Cd isotopic measurements using solid source mass spectrometry. Preliminary results suggest that Cd is likely to fractionate during smelting activities, as indicated by measurements on mining waste. The calibration of a 110Cd-116Cd double spike is underway for absolute, true isotopic ratios to be derived. The double spike technique allows the isotopic analysis of Cd using a plasma source, but also a solid source mass spectrometer, as Cd ionizes efficiently in such mass spectrometers owing to the standard silicagel technique.

Innocent, C.

2004-05-01

117

PALOMA : an isotope analyzer using static mass spectrometry, coupled with cryogenic and chemical trapping, for the MSL mission to Mars  

NASA Astrophysics Data System (ADS)

The technique of GCMS analysis has to be completed by static mass spectrometry for precise in-situ measurements of the isotopic composition of planetary atmospheres (noble gases, stable isotopes), and volatile outgassed products from solid sample pyrolysis. Static mass spectrometry, coupled with gas separation by cryo-separation and gettering, is commonly used in the laboratory to study volatiles extracted from terrestrial and meteoritic samples. Such an instrument (PALOMA) is presently developed in our laboratories, and it will be coupled with a Pyr-GCMS analyzer (MACE), built by a US consortium of science laboratories and industrials (University of Michigan, Southwest Research Institute, JPL, Ball Aerospace). The MACE/PALOMA experiment will be proposed on the NASA Mars Science Laboratory mission, planned to be launched in 2009. The scientific objectives of PALOMA, coupled with MACE, may be listed as follows : (i) search for isotopic signatures of past life in atmosphere, rock, dust and ice samples, with emphasis on carbon, nitrogen and hydrogen; (ii) accurately measure isotopic composition of atmospheric noble gases, and stable isotopes, in order to better constrain past escape, surface interaction, outgassing history and climate evolution; (iii) precisely measure diurnal/ seasonal variations of isotopic ratios of H2O, CO2, and N2, for improving our understanding of present and past climate, and of the role of water cycle. Main measurement objectives are : (i) C, H, O, N isotopic composition in both organic evolved samples (provided by MACE pyrolysis system) and atmosphere with high accuracy (a few per mil at 1-s level); (ii) noble gas (He, Ne, Ar, Kr, Xe) and stable (C, H, O, N) isotope composition in atmosphere with high accuracy (a few per mil at 1-s level); (iii) molecular and isotopic composition of inorganic evolved samples (salts, hydrates, nitrates, {ldots}), including ices; (iv) diurnal and seasonal monitoring of D/H in water vapor, and water ice.

Chassefiere, E.; Jambon, A.; Berthelier, J.-J.; Goulpeau, G.; Leblanc, F.; Montmessin, F.; Sarda, P.; Agrinier, P.; Fouchet, T.; Waite, H.

118

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

PubMed Central

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

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

2011-01-01

119

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

PubMed

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

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

2010-05-01

120

Quantitative determination of formaldehyde in cosmetics using a combined solid-phase microextraction-isotope dilution mass spectrometry method.  

PubMed

Solid-phase microextraction (SPME) in conjunction with isotope dilution mass spectrometry (ID-MS) was employed for the analysis of formaldehyde in cosmetic products. The formaldehyde is derivatized in situ with pentafluorophenyl hydrazine. The formed hydrazone is adsorbed over a poly(dimethylsiloxane)-divinylbenzene-coated fiber and analyzed using gas chromatography-mass spectrometry. The adsorption-time profiles and salting effect were studied. The quantitation was performed by using a stable isotope labeled analogue as an internal standard. The precision, recovery and detection limits were determined with spiked samples. The relative standard deviations from different spiked cosmetic samples were all less than 10% and the recoveries were between 89.00 and 101.23%. The limit of detection was of 0.39 microg/l. Compared with other techniques, the study shown here provides a simple, fast and reliable method for the analysis of formaldehyde in cosmetic products. PMID:15032367

Rivero, René Thomas; Topiwala, Vinod

2004-03-12

121

Identification and quantification of N-linked glycoproteins using hydrazide chemistry, stable isotope labeling and mass spectrometry  

Microsoft Academic Search

Quantitative proteome profiling using stable isotope protein tagging and automated tandem mass spectrometry (MS\\/MS) is an emerging technology with great potential for the functional analysis of biological systems and for the detection of clinical diagnostic or prognostic marker proteins. Owing to the enormous complexity of proteomes, their comprehensive analysis is an as-yet-unresolved technical challenge. However, biologically or clinically important information

Hui Zhang; Xiao-jun Li; Daniel B Martin; Ruedi Aebersold

2003-01-01

122

The application of isotope dilution thermal ionization mass spectrometry to traceability of chemical measurement and interlaboratory comparisons  

Microsoft Academic Search

In this work, the method of isotope dilution thermal ionization mass spectrometry able to trace to SI was developed to accurately\\u000a measure trace amount of Cd, Pb, Zn and Cu in sediment, rice, wine, and human serum samples for interlaboratory comparisons.\\u000a The research focuses on how to apply the primary method correctly, uncertainty evaluation of measurement results, and how\\u000a to

Jun Wang; Motain Zhao; Na Guan; Hai Lu

2006-01-01

123

Protein Cross-Linking Analysis Using Mass Spectrometry, Isotope-Coded Cross-Linkers, and Integrated Computational Data Processing  

Microsoft Academic Search

Distance constraints in proteins and protein complexes provide invaluable information for calculation of 3D structures, identification of protein binding partners and localization of protein-protein contact sites. We have developed an integrative approach to identify and characterize such sites through the analysis of proteolytic products derived from proteins chemically cross-linked by isotopically coded cross-linkers using LC-MALDI tandem mass spectrometry and computer

Jan Seebacher; Parag Mallick; Ning Zhang; James S. Eddes; Ruedi Aebersold; Michael H. Gelb

2006-01-01

124

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

Microsoft Academic Search

Isotope dilution liquid chromatography coupled with electrospray ionization tandem mass spectrometry (LC-MS\\/MS) was applied to the quantification of acrylamide in chocolate matrixes (dark chocolate, milk chocolate, chocolate with nuts, chocolate with almonds, and chocolate with wheat best element). The method included defatting with petroleum ether, extracting with aqueous solution of 2?mol?l sodium chloride and clean-up by solid-phase (SPE) with OASIS

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

2006-01-01

125

Determination of Cd and Zn by isotope dilution–thermal ionisation mass spectrometry using a sequential analysis procedure  

Microsoft Academic Search

Isotope dilution–thermal ionisation mass spectrometry (ID-TIMS) was used to examine the certified Cd and Zn content of 4 Certified Reference Materials (CRMs); 2 soils: GBW07401 and GBW07405, 1 plant CRM060 and an animal tissue SRM1566a. The CRMs were chosen to be of contrasting origin and Cd:Zn content. Three digestion procedures were compared: (i) an open tube aqua regia procedure (ii)

Ahmed S Ayoub; Brian A McGaw; Andrew J Midwood

2002-01-01

126

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

127

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

PubMed Central

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.

2011-01-01

128

Influence of recent vegetation on labile and recalcitrant carbon soil pools in central Queensland, Australia: evidence from thermal analysis-quadrupole mass spectrometry-isotope ratio mass spectrometry.  

PubMed

The effect of a recent vegetation change (<100 years) from C(4) grassland to C(3) woodland in central Queensland, Australia, on soil organic matter (SOM) composition and SOM dynamics has been investigated using a novel coupled thermogravimetry-differential scanning calorimetry-quadrupole.mass spectrometry-isotope ratio mass spectrometry (TG-DSC-QMS-IRMS) system. TG-DSC-QMS-IRMS distinguishes the C isotope composition of discrete SOM pools, showing changes in labile, recalcitrant and refractory carbon in the bulk soil and particle size fractions which track the vegetation changes. Analysis of evolved gases (by QMS) from thermal decomposition, rather than observed weight loss, proved essential in determining the temperature at which SOM decomposes, because smectite and kaolinite clays contribute to observed weight losses. The delta(13)C analyses of the CO(2) evolved at different temperatures for bulk soil and particle size-separates showed that most of the labile SOM under the more recent woody vegetation was C(3)-derived carbon whereas the delta(13)C values in the recalcitrant SOM showed greater C(4) contributions. This indicated a shift from grass (C(4))- to tree (C(3))-derived carbon in the woodland, which was also supported by the two-phase (13)C enrichment with depth, i.e. C(3) vegetation dominated the top soil (0-10 cm), but the C(4) contribution increased with depth (more gradual). This is perturbed by the inclusion of charcoal from forest fires ((14)C age incursions) and by the deep incorporation of C(3) carbon due to root penetration. PMID:18446757

Lopez-Capel, Elisa; Krull, Evelyn S; Bol, Roland; Manning, David A C

2008-06-01

129

Measurement of intact sulfate and glucuronide phytoestrogen conjugates in human urine using isotope dilution liquid chromatography-tandem mass spectrometry with [ 13 C 3] isoflavone internal standards  

Microsoft Academic Search

A method has been developed for the analysis of phytoestrogens and their conjugates in human urine using liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS\\/MS). Stable isotopically labeled [13C3]daidzein and [13C3]genistein were synthesized and used as internal standards for isotope dilution mass spectrometry. Free aglycons and intact glucuronide, sulfate, diglucuronide, disulfate, and mixed sulfoglucuronide conjugates of isoflavones and lignans were

Don B Clarke; Antony S Lloyd; Nigel P Botting; Mark F Oldfield; Paul W Needs; Helen Wiseman

2002-01-01

130

Ultratrace analysis of calcium with high isotopic selectivity by diode laser resonance ionization mass spectrometry  

Microsoft Academic Search

A refined diode laser based resonance ionization mass spectrometer for highly selective ultratrace analysis is presented, which combines coherent narrow-band multistep resonance excitation and ionization with a compact quadruple mass spectrometer. The widespread analytical potential and applicability of this system is demonstrated in the determination of calcium trace and ultratrace isotopes for cosmochemical studies, medical investigations and radiodating. For a

Karen M. Wendt; K. Blaum; Bruce A. Bushaw; P. Mueller; W. Noertershaeuser; A. Schmitt; N. Trautmann; B. Wiche

1998-01-01

131

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

132

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

133

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

134

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

PubMed

On the one hand, 19-norandrosterone (NA) is the most abundant metabolite of the synthetic anabolic steroid 19-nortestosterone and related prohormones. On the other hand, small amounts are biosynthesized by pregnant women and further evidence exists for physiological origin of this compound. The World Anti-Doping Agency (WADA) formerly introduced threshold concentrations of 2 or 5 ng of NA per ml of urine to discriminate 19-nortestosterone abuse from biosynthetic origin. Recent findings showed however, that formation of NA resulting in concentrations in the range of the threshold levels might be due to demethylation of androsterone in urine, and the WADA 2006 Prohibited List has defined NA as endogenous steroid. To elucidate the endogenous or exogenous origin of NA, (13)C/(12)C-analysis is the method of choice since synthetic 19-nortestosterone is derived from C(3)-plants by partial synthesis and shows delta(13)C(VPDB)-values of around -28 per thousand. Endogenous steroids are less depleted in (13)C due to a dietary mixture of C(3)- and C(4)-plants. An extensive cleanup based on two high performance liquid chromatography cleanup steps was applied to quality control and doping control samples, which contained NA in concentrations down to 2 ng per ml of urine. (13)C/(12)C-ratios of NA, androsterone and etiocholanolone were measured by gas chromatography/combustion/isotope ratio mass spectrometry. By comparing delta(13)C(VPDB)-values of androsterone as endogenous reference compound with NA, the origin of NA in doping control samples was determined as either endogenous or exogenous. PMID:17047802

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

2006-07-28

135

Multi-isotope imaging mass spectrometry reveals slow protein turnover in hair-cell stereocilia.  

PubMed

Hair cells of the inner ear are not normally replaced during an animal's life, and must continually renew components of their various organelles. Among these are the stereocilia, each with a core of several hundred actin filaments that arise from their apical surfaces and that bear the mechanotransduction apparatus at their tips. Actin turnover in stereocilia has previously been studied by transfecting neonatal rat hair cells in culture with a ?-actin-GFP fusion, and evidence was found that actin is replaced, from the top down, in 2-3 days. Overexpression of the actin-binding protein espin causes elongation of stereocilia within 12-24 hours, also suggesting rapid regulation of stereocilia lengths. Similarly, the mechanosensory 'tip links' are replaced in 5-10 hours after cleavage in chicken and mammalian hair cells. In contrast, turnover in chick stereocilia in vivo is much slower. It might be that only certain components of stereocilia turn over quickly, that rapid turnover occurs only in neonatal animals, only in culture, or only in response to a challenge like breakage or actin overexpression. Here we quantify protein turnover by feeding animals with a (15)N-labelled precursor amino acid and using multi-isotope imaging mass spectrometry to measure appearance of new protein. Surprisingly, in adult frogs and mice and in neonatal mice, in vivo and in vitro, the stereocilia were remarkably stable, incorporating newly synthesized protein at <10% per day. Only stereocilia tips had rapid turnover and no treadmilling was observed. Other methods confirmed this: in hair cells expressing ?-actin-GFP we bleached fiducial lines across hair bundles, but they did not move in 6 days. When we stopped expression of ?- or ?-actin with tamoxifen-inducible recombination, neither actin isoform left the stereocilia, except at the tips. Thus, rapid turnover in stereocilia occurs only at the tips and not by a treadmilling process. PMID:22246323

Zhang, Duan-Sun; Piazza, Valeria; Perrin, Benjamin J; Rzadzinska, Agnieszka K; Poczatek, J Collin; Wang, Mei; Prosser, Haydn M; Ervasti, James M; Corey, David P; Lechene, Claude P

2012-01-15

136

Cellular lipid extraction for targeted stable isotope dilution liquid chromatography-mass spectrometry analysis.  

PubMed

The metabolism of fatty acids, such as arachidonic acid (AA) and linoleic acid (LA), results in the formation of oxidized bioactive lipids, including numerous stereoisomers(1,2). These metabolites can be formed from free or esterified fatty acids. Many of these oxidized metabolites have biological activity and have been implicated in various diseases including cardiovascular and neurodegenerative diseases, asthma, and cancer(3-7). Oxidized bioactive lipids can be formed enzymatically or by reactive oxygen species (ROS). Enzymes that metabolize fatty acids include cyclooxygenase (COX), lipoxygenase (LO), and cytochromes P450 (CYPs)(1,8). Enzymatic metabolism results in enantioselective formation whereas ROS oxidation results in the racemic formation of products. While this protocol focuses primarily on the analysis of AA- and some LA-derived bioactive metabolites; it could be easily applied to metabolites of other fatty acids. Bioactive lipids are extracted from cell lysate or media using liquid-liquid (l-l) extraction. At the beginning of the l-l extraction process, stable isotope internal standards are added to account for errors during sample preparation. Stable isotope dilution (SID) also accounts for any differences, such as ion suppression, that metabolites may experience during the mass spectrometry (MS) analysis(9). After the extraction, derivatization with an electron capture (EC) reagent, pentafluorylbenzyl bromide (PFB) is employed to increase detection sensitivity(10,11). Multiple reaction monitoring (MRM) is used to increase the selectivity of the MS analysis. Before MS analysis, lipids are separated using chiral normal phase high performance liquid chromatography (HPLC). The HPLC conditions are optimized to separate the enantiomers and various stereoisomers of the monitored lipids(12). This specific LC-MS method monitors prostaglandins (PGs), isoprostanes (isoPs), hydroxyeicosatetraenoic acids (HETEs), hydroxyoctadecadienoic acids (HODEs), oxoeicosatetraenoic acids (oxoETEs) and oxooctadecadienoic acids (oxoODEs); however, the HPLC and MS parameters can be optimized to include any fatty acid metabolites(13). Most of the currently available bioanalytical methods do not take into account the separate quantification of enantiomers. This is extremely important when trying to deduce whether or not the metabolites were formed enzymatically or by ROS. Additionally, the ratios of the enantiomers may provide evidence for a specific enzymatic pathway of formation. The use of SID allows for accurate quantification of metabolites and accounts for any sample loss during preparation as well as the differences experienced during ionization. Using the PFB electron capture reagent increases the sensitivity of detection by two orders of magnitude over conventional APCI methods. Overall, this method, SID-LC-EC-atmospheric pressure chemical ionization APCI-MRM/MS, is one of the most sensitive, selective, and accurate methods of quantification for bioactive lipids. PMID:22127066

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

2011-11-17

137

Precise Re isotope ratio measurements by negative thermal ionization mass spectrometry (NTI-MS) using total evaporation technique  

NASA Astrophysics Data System (ADS)

High precision rhenium isotope ratios, 187Re/185Re, have been determined by negative thermal ionization mass spectrometry (NTI-MS) using a total evaporation technique. The salient features of this method are evaporation of the entire sample and simultaneous integration of the signal from each isotope, which effectively eliminates isotope fractionation effects during the evaporation process. The 187Re/185Re ratio is obtained with a high reproducibility (1.6755+/-0.0014 (2[sigma]), R.S.D.=0.083%, n=28) for 50 pg-1 ng of a Re natural standard using the total evaporation with NTI-MS. This value is within analytical uncertainty of the previously reported accurate 187Re/185Re ratio (1.6740+/-0.0011) adopted by IUPAC as the Re isotopic composition, and is significantly more precise than the ratio obtained from conventional NTI-MS isotopic measurements in our laboratory (1.6772+/-0.0037 (2[sigma]), R.S.D.=0.22%, n=34). Based on these results, the total evaporation technique allows us to precisely determine Re isotope ratios, even for small sample amounts. In addition, this method is effective for highly precise Re abundance determinations using isotope dilution.

Suzuki, Katsuhiko; Miyata, Yoshiki; Kanazawa, Nobuyuki

2004-06-01

138

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

139

Elemental fingerprint analysis of barley (Hordeum vulgare) using inductively coupled plasma mass spectrometry, isotope-ratio mass spectrometry, and multivariate statistics.  

PubMed

Inductively coupled plasma mass spectrometry (ICP-MS) and isotope-ratio mass spectrometry (IR-MS) have been used to examine the multi-elemental composition and (15)N/(14)N and (13)C/(12)C isotope ratios of three spring barley (Hordeum vulgare) genotypes (Orthega, Barke, and Bartok) grown in three typical Danish agricultural soils (North Jutland, West Jutland, and East Zealand) differing in soil fertility. The aim of the study was to examine whether it was possible to generate a unique elemental fingerprint of individual barley genotypes irrespective of the elemental imprint plants had received from soils differing in fertility and agricultural practice. Multivariate statistics were used to analyze the elemental fingerprints of the barley genotypes at different times during a full growing season from early tillering to full maturity of the barley grains. Initially, 36 elements were analyzed in the plant samples but this number was subsequently reduced to 15 elements: B, Ba, C, Ca, Cu, Fe, K, Mg, Mn, N, Na, P, S, Sr, and Zn. These elements exceeded the limit of detection ( LOD) for all genotypes, soil types, and plant growth stages and for these elements the accuracy was better than 90% compared with apple leaf certified reference material (CRM). Principal component analysis (PCA) separated multi-elemental data in accordance with soil type when plants of similar physiological age were compared, whereas this separation disappeared if plants of all ages were compared simultaneously. Isotope ratios (delta(15)N) of plants also proved to be a highly accurate property for classification of samples according to soil type. In contrast, the differences in delta(13)C were too small to enable such classification. The differences in delta(15)N among soils were so pronounced that separation of samples according to the physiological age of plants became redundant. However, delta(15)N and the multi-elemental analysis revealed no differences between the three barley genotypes, indicating that the influence of soil chemistry and possibly also climate and agricultural practice was too large to allow an unique elemental fingerprint for the genotypes. This finding was substantiated by analyzing the multi-elemental composition of grain from two additional genotypes (Otira and Barthos) grown at the north and east locations, respectively. PCA showed not only that the elemental fingerprints of these two genotypes were similar to those of the others, but also that the soil in which the plant had been growing could be accurately predicted on the basis of the PCA scores from the genotypes Orthega, Barke, and Bartok. Similar conclusions could be drawn using delta(15)N data. PMID:14551660

Husted, Søren; Mikkelsen, Birgitte F; Jensen, Jacob; Nielsen, Niels Erik

2003-10-09

140

Attogram measurement of rare isotopes by CW resonance ionization mass spectrometry.  

National Technical Information Service (NTIS)

Three-color double-resonance ionization mass spectrometry, using two single-frequency cw dye lasers and a cw carbon dioxide laser, has been applied to the detection of attogram quantities of rare radionuclides. (sup 210)Pb has been measured in human hair ...

B. A. Bushaw

1992-01-01

141

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

142

Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.  

PubMed

Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1. PMID:16496054

Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

2005-12-01

143

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

144

Measurement of atmospheric trace sulfur gases using combined gas chromatography - mass spectrometry and an isotopically labeled internal standard  

SciTech Connect

A method of combined mass spectrometry/gas chromatography based on an internal standard coupled with the concentration measurements is described for the determination of picogram quantities of certain sulfur gases. The lower level of detection was 4 ppT by volume at a signal-to-noise ratio of 2 for a 1 liter air sample with a precision of 1%. Signal ion overlap between the monitored mass channels was observed and an algorithm was derived to correct the isotopic ratio for this cross contribution. The algorithm defined a linear relationship between the detected isotopic signal ratio and the concentration of the measured compounds. The technique was applied to the determination of carbon disulfide and carbonyl sulfide at the Drexel University campus located in Philadelphia, PA. Two different sampling devices, a glass sampler and a carbosieve B solid adsorbent trap were investigated for collection of air samples, and high efficiency was demonstrated for both samplers. (BLM)

Shalaby, L.M.

1982-01-01

145

A method for determining isotopic composition of elements by thermal ionization source mass spectrometry: Application to strontium  

NASA Astrophysics Data System (ADS)

It is shown that in thermal ionization source mass spectrometry, if isotope fractionation of the element in the sample follows a linear law, straight-line distributions in xm versus xm/ym diagrams are observed, where xm and ym are two measured isotope ratios. The slopes and y-intercepts of these linear distributions are functions of the [`]true' (starting) values xt and yt of the element in the sample and of the masses of the isotopes involved in ratios x and y. Since the masses of the nuclides are known, true ratios xt and yt can be calculated. This theoretical result is used to determine the non-radiogenic part of the isotopic composition of strontium in NBS SRM 987, one 84Sr-enriched isotopic tracer prepared at the Oak Ridge National Laboratory, and two natural samples (rocks from the metamorphic basement of the Italian Eastern Alps) without any assumption about the isotopic composition itself. Strontium was loaded as nitrate on single tungsten filaments, and 88Sr/86Sr and 84Sr/86Sr ratios were measured up to a fractionation of ~1% u-1 in a single-collector VG 54E mass spectrometer. For each run, 86Sr/88Sr, 84Sr/86Sr and 84Sr/88Sr ratios were calculated for all useful xm versus xm/ym distributions. The respective weighted average values are considered the true values of the isotope ratios in the sample. Four runs of isotopic standard NBS SRM 987 and one run of the isotopic tracer gave accurate and reproducible results which are identical, within error limits, to the respective certified values. The four determinations of NBS 987 resulted in the following weighted average values: 86Sr/88Sr = 0.11942 +/- 0.00018; 84Sr/86Sr = 0.056485 +/- 0.000075; 84Sr/88Sr = 0.006746 +/- 0.000017 (error at 2[sigma] level). The values of the natural 86Sr/88Sr ratio (two rocks: 0.11956 +/- 0.00017 and 0.11957 +/- 0.00008; NBS 987: 0.11942 +/- 0.00018) are identical within error limits, and identical or very close to the recommended value of 0.1194, the worldwide assumed [`]true' 86Sr/88Sr value in the commonly used procedure of determining 87Sr/86Sr ratio by normalization. However, due to the accuracy of the above determinations, it is suggested that, in nature, significant differences exist in the non-radiogenic part of the isotopic composition of strontium.

Cavazzini, Giancarlo

2005-01-01

146

Application of isotope dilution gas chromatography-mass spectrometry in analysis of organochlorine pesticide residues in ginseng root.  

PubMed

A highly accurate and precise method based on isotope dilution gas chromatography-mass spectrometry was developed for the determination of five matrix-bound organochlorine pesticides, namely, hexachlorobenzene and hexachlorocyclohexanes (alpha-, beta-, delta-, and gamma- isomers), in a reference sample of Panax gingseng. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant ion fragments within the specific time windows (+/-1% of the relative retention time with respect to the calibration standards) and matching of relative ion intensities of the concerned ions in samples and calibration standards (within +/-5%). Quantification was based on the measurement of concentration ratios of the natural and isotopic analogues in the sample and calibration blends. To circumvent the tedious iterative process of exact isotope matching that is often used in isotope dilution mass spectrometry analysis, a single-point calibration procedure was adopted with the isotopic amount ratios in the sample and calibration blends close to unity (0.9-1.1). Under the described approach, intraday and interday repeatability of replicate analyses of organochlorine pesticides in the ginseng root sample were below 1.4%. The expanded relative uncertainty ranging from 4.0 to 6.5% at a coverage factor of 2 was significantly lower than those of conventional gas chromatographic methods using other calibration techniques (internal or external standards). A deviation of less than 2.0% from the certified values was achieved when applying the developed method to determine hexachlorobenzene, alpha-, and beta-hexachlorocyclohexane in a certified reference material (CRM), BCR-CRM 115. Because of the unavailability of relevant CRMs of herbal origins, the concerned ginseng root sample, after verification of the "true values" of the concerned organochlorine pesticides by the valid primary method, is suitable for serving as an in-house reference material for quality assurance and method validation purposes. PMID:17407316

Chan, Serena; Kong, Mei-Fong; Wong, Yiu-Chung; Wong, Siu-Kay; Sin, Della W M

2007-04-04

147

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

148

Low blank rhenium isotope ratio determinations by V2O5 coated nickel filaments using negative thermal ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

Thenium isotope ratio determinations are, in principle, possible by negative thermal ionization mass spectrometry (NTI-MS). Relatively high rhenium blanks from the commonly-used filament materials prevent accurate isotope ratio determinations, especially for small rhenium sample amounts which are of importance, for example, in geochronology in connection with the Re/Os dating method. Platinum and nickel filaments were tested by different preparation techniques to reduce the rhenium blank contribution from the filament material. The lowest rhenium blank of less than 1 pg was achieved by coating nickel filaments with V2O5 prior to degassing under high vacuum conditions at 850°C. Obviously, the vanadium--nickel oxide layer formed on the surface of the filament during this process prevents further emission of rhenium ions from the filament material. Using Ba(OH)2 for the enhancement of negative thermal ions, 1 ng of rhenium resulted in ion currents at the detector side of about 10-11 A with an ionization efficiency of up to 20%. The 185Re/187Re isotope ratio of a sample of natural isotopic composition could be determined to be 0.59818 ± 0.00026 with a relative precision of 0.04%. The isotope ratio determination for an 187Re spike was comparable in precision but the relative standard deviation of an 185Re spike was significantly higher, which could be explained by mass fractionations of oxygen in the measured ReO-4 ion. The ReO-4 ion is about 200 to 2500 times more abundant than the only other detectable rhenium ion in NTI-MSReO-3. The ReO-4/ReO-4 ratio decreases with increasing temperature. By the low blank NTI-MS technique described in this work, more precise and accurate determinations of the rhenium isotope ratio and the rhenium concentration by isotope dilution analysis from nanogramme samples are possible.

Walczyk, Thomas; Hebeda, Erhard H.; Heumann, Klaus G.

1994-02-01

149

Analysis of geological Sr isotope markers in fish otoliths with subannual resolution using laser ablation-multicollector-ICP-mass spectrometry  

Microsoft Academic Search

In this pilot study, laser ablation-multicollector-inductively coupled plasma-mass spectrometry (LA-MC-ICP-MS) and Sr isotope geochemistry were applied to fish life-history studies through the micro-analysis of Sr abundance and 87Sr\\/86Sr in the otoliths of an anadromous fish. With a laser sampling area of 70-µm diameter, LA-MC-ICP-MS of a deep-sea coral gave precision values for 87Sr\\/86Sr determination of approximately 0.04% relative standard deviation

P. Outridge; S. Chenery; J. Babaluk; J. Reist

2002-01-01

150

Assessment of the amount of body water in the Red Knot (Calidris canutus): an evaluation of the principle of isotope dilution with 2H, (17)O, and (18)O as measured with laser spectrometry and isotope ratio mass spectrometry.  

PubMed

We have used the isotope dilution technique to study changes in the body composition of a migratory shorebird species (Red Knot, Calidris canutus) through an assessment of the amount of body water in it. Birds were quantitatively injected with a dose of water with elevated concentrations of 2H, (17)O, and (18)O. Thereafter, blood samples were taken and distilled. The resulting water samples were analysed using an isotope ratio mass spectrometry (for 2H and (18)O only) and a stable isotope ratio infrared laser spectrometry (2H, (17)O, and (18)O) to yield estimates of the amount of body water in the birds, which in turn could be correlated to the amount of body fat. Here, we validate laser spectrometry against mass spectrometry and show that all three isotopes may be used for body water determinations. This opens the way to the extension of the doubly labelled water method, used for the determination of energy expenditure, to a triply labelled water method, incorporating an evaporative water loss correction on a subject-by-subject basis or, alternatively, the reduction of the analytical errors by statistically combining the (17)O and (18)O measurements. PMID:16500750

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

2006-03-01

151

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

152

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)  

SciTech Connect

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samples and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.; Farmer, Orville T.

2006-05-09

153

Segmentation of Multi-Isotope Imaging Mass Spectrometry Data for Semi-Automatic Detection of Regions of Interest  

PubMed Central

Multi-isotope imaging mass spectrometry (MIMS) associates secondary ion mass spectrometry (SIMS) with detection of several atomic masses, the use of stable isotopes as labels, and affiliated quantitative image-analysis software. By associating image and measure, MIMS allows one to obtain quantitative information about biological processes in sub-cellular domains. MIMS can be applied to a wide range of biomedical problems, in particular metabolism and cell fate [1], [2], [3]. In order to obtain morphologically pertinent data from MIMS images, we have to define regions of interest (ROIs). ROIs are drawn by hand, a tedious and time-consuming process. We have developed and successfully applied a support vector machine (SVM) for segmentation of MIMS images that allows fast, semi-automatic boundary detection of regions of interests. Using the SVM, high-quality ROIs (as compared to an expert's manual delineation) were obtained for 2 types of images derived from unrelated data sets. This automation simplifies, accelerates and improves the post-processing analysis of MIMS images. This approach has been integrated into “Open MIMS,” an ImageJ-plugin for comprehensive analysis of MIMS images that is available online at http://www.nrims.hms.harvard.edu/NRIMS_ImageJ.php.

Poczatek, J. Collin; Turck, Christoph W.; Lechene, Claude

2012-01-01

154

Fundamentals of Accelerator Mass Spectrometry  

NASA Astrophysics Data System (ADS)

The extension of high-sensitivity mass spectrometry to isotope ratios in the range 10-12-10-15 has been called accelerator mass spectrometry (AMS) because of the use of an additional stage of acceleration that facilitates the removal of molecular interferences and the separation of isobars. In some cases the ultra-high sensitivity is obtained by exploiting the instability of the negative ion of the interfering isobar. It is now possible to measure such isotopes as 14C at natural abundances as low as one atom in 10+15 12C atoms. The ideas behind this significant extension of mass spectrometric techniques will be discussed.

Litherland, A. E.

1987-08-01

155

delta34S measurements on organic materials by continuous flow isotope ratio mass spectrometry.  

PubMed

Sulfur (S) isotope ratios of thoroughly dried organic samples were measured by direct thermal decomposition in an elemental analyzer coupled to an isotope ratio mass spectrometer in continuous flow mode (EA-CF-IRMS). For organic samples of up to 13 mg weight and with total S contents of more than 10 microg, the reproducibility of the delta34S(organic) values was +/-0.4 per thousand or better. However, the delta34S values of organic samples measured directly by online EA-CF-IRMS analysis were between 0.3 and 2.9 per thousand higher than those determined on BaSO4 precipitates produced by Parr Bomb oxidation from the same sample material. Our results suggest that structural oxygen in organic samples influences the oxygen isotope ratios of the SO2 produced from organic samples. Consequently, SO2 generated from organic samples appears to have different 18O/16O ratios than SO2 generated from BaSO4 precipitates and inorganic reference materials, resulting in a deviation from the true delta34S values because of 32S16O18O contributions to mass 66. It was shown that both the amount of structural oxygen in the organic sample, and the difference of the oxygen isotope ratios between organic samples and tank O2, influenced the magnitude of the observed deviation from the true delta34S value after direct EA-CF-IRMS analysis of organic samples. Suggestions are made to correct the difference between measured delta34S(organic) and true delta34S values in order to obtain not only reproducible, but also accurate S isotope ratios for organic materials by EA-CF-IRMS. PMID:15880637

Yun, Misuk; Mayer, Bernhard; Taylor, Stephen W

2005-01-01

156

Adsorption in gas mass spectrometry. I. Effects on the measurement of individual isotopic species  

NASA Astrophysics Data System (ADS)

The adsorption-desorption process of gas molecules on the walls of the mass spectrometer inlet system was studied in order to assess quantitatively its influence on measurement results. The effects on individual isotopic species in SiF4 measurements required for the re-determination of the Avogadro constant are discussed in this paper, while the effects on isotope amount ratio determinations will be discussed in a companion paper. A model based on the Langmuir adsorption isotherm is developed, which fits well the experimental observations and provides the means to investigate adsorption and desorption kinetics in the inlet system. A parameter called the [`]apparent leak-rate coefficient' is introduced; this represents the relative variation with time of any isotopic species in the inlet system. All the adsorption parameters appearing in the balance equations are derived from the apparent leak-rate coefficient. Application of the model to long mass-spectrometric measurements of SiF4 yields a rate constant of 6.5 × 10-5 s-1 for SiF4 effusion through the molecular leak of the inlet system. Adsorption and desorption rate-constants are equal to 20-25% of the leak rate-constant, and the adsorption sites are about two orders of magnitude lower than the number of Ni and Cu atoms present on the inlet system walls.

Gonfiantini, Roberto; Valkiers, Staf; Taylor, Philip D. P.; de Bièvre, Paul

1997-05-01

157

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

158

Mass spectrometry with accelerators.  

PubMed

As one in a series of articles on Canadian contributions to mass spectrometry, this review begins with an outline of the history of accelerator mass spectrometry (AMS), noting roles played by researchers at three Canadian AMS laboratories. After a description of the unique features of AMS, three examples, (14)C, (10)Be, and (129)I are given to illustrate the methods. The capabilities of mass spectrometry have been extended by the addition of atomic isobar selection, molecular isobar attenuation, further ion acceleration, followed by ion detection and ion identification at essentially zero dark current or ion flux. This has been accomplished by exploiting the techniques and accelerators of atomic and nuclear physics. In 1939, the first principles of AMS were established using a cyclotron. In 1977 the selection of isobars in the ion source was established when it was shown that the (14)N(-) ion was very unstable, or extremely difficult to create, making a tandem electrostatic accelerator highly suitable for assisting the mass spectrometric measurement of the rare long-lived radioactive isotope (14)C in the environment. This observation, together with the large attenuation of the molecular isobars (13)CH(-) and (12)CH?2(-) during tandem acceleration and the observed very low background contamination from the ion source, was found to facilitate the mass spectrometry of (14)C to at least a level of (14)C/C ~ 6 × 10(-16), the equivalent of a radiocarbon age of 60,000 years. Tandem Accelerator Mass Spectrometry, or AMS, has now made possible the accurate radiocarbon dating of milligram-sized carbon samples by ion counting as well as dating and tracing with many other long-lived radioactive isotopes such as (10)Be, (26)Al, (36)Cl, and (129)I. The difficulty of obtaining large anion currents with low electron affinities and the difficulties of isobar separation, especially for the heavier mass ions, has prompted the use of molecular anions and the search for alternative methods of isobar separation. These techniques are discussed in the latter part of the review. PMID:22031277

Litherland, A E; Zhao, X-L; Kieser, W E

2010-12-23

159

Determination of molybdenum isotope fractionation by double-spike multicollector inductively coupled plasma mass spectrometry  

NASA Astrophysics Data System (ADS)

Molybdenum isotopic compositions are precisely determined by MC-ICP-MS measurements using a Mo double spike. The double spike is added prior to chemical purification, so that laboratory and instrumental mass fractionations are separated from natural mass-dependent fractionation. Fractionation is determined on four Mo mass ratios, providing an internal consistency check. The external standard reproducibility is at 0.06 per mil on the 98Mo/95Mo ratio (2 standard deviation)). Using a normal microconcentric nebuliser with a cyclonic spray chamber, the minimum quantity of Mo is ˜1 ?g for high-precision results. A hydrothermal molybdenite shows fractionation of -0.3 per mil on the 98Mo/95Mo ratio relative to our standard (Johnson Matthey, 1000 ?g/mL (±0.3%) ICP standard solution, lot 602332B). Fine-grained sediments show fractionation of 0.1 and -0.3 per mil on the 98Mo/95Mo ratio. The observed Mo isotope fractionation is small but resolvable with the presented high-resolution technique.

Siebert, Christopher; NäGler, Thomas F.; Kramers, Jan D.

2001-07-01

160

Osmium isotopic ratio measurements by inductively coupled plasma source mass spectrometry  

Microsoft Academic Search

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 ¹⁹°Os\\/¹⁹²Os, ¹⁸⁹Os\\/¹⁹²Os, and ¹⁸⁸Os\\/¹⁹²Os were determined to better than +\\/-

G. Price. Russ; Jeanne M. Bazan; Alan R. Date

1987-01-01

161

Fission track-secondary ion mass spectrometry as a tool for detecting the isotopic signature of individual uranium containing particles.  

PubMed

A fission track technique was used as a sample preparation method for subsequent isotope abundance ratio analysis of individual uranium containing particles with secondary ion mass spectrometry (SIMS) to measure the particles with higher enriched uranium efficiently. A polycarbonate film containing particles was irradiated with thermal neutrons and etched with 6M NaOH solution. Each uranium containing particle was then identified by observing fission tracks created and a portion of the film having a uranium containing particle was cut out and put onto a glassy carbon planchet. The polycarbonate film, which gave the increases of background signals on the uranium mass region in SIMS analysis, was removed by plasma ashing with 200 W for 20 min. In the analysis of swipe samples having particles containing natural (NBL CRM 950a) or low enriched uranium (NBL CRM U100) with the fission track-SIMS method, uranium isotope abundance ratios were successfully determined. This method was then applied to the analysis of a real inspection swipe sample taken at a nuclear facility. As a consequence, the range of (235)U/(238)U isotope abundance ratio between 0.0276 and 0.0438 was obtained, which was higher than that measured by SIMS without using a fission track technique (0.0225 and 0.0341). This indicates that the fission track-SIMS method is a powerful tool to identify the particle with higher enriched uranium in environmental samples efficiently. PMID:22405310

Esaka, Fumitaka; Lee, Chi-Gyu; Magara, Masaaki; Kimura, Takaumi

2012-02-10

162

Elemental composition and origin of (polyatomic) ions in inductively coupled plasma mass spectrometry disclosed by means of isotope exchange experiments  

NASA Astrophysics Data System (ADS)

Stable isotopic labelling is a suitable method for the assignment of the elemental composition of interference ions by comparison of spectra of labelled compounds with those of non-labelled ones. We have used this method for the identification of the low-mass range ions in inductively coupled plasma mass spectrometry (ICP—MS) and for determining their origin. To this end, ICP mass spectra of H216O, D216O and H218O, and also of H14NO3 and H15NO3 diluted in the labelled water have been compared. A number of polyatomic ions, such as H2+·, H3+, 12CH+ and 14NH+, of which the existence had not been reported previously, was found to be present according to the ICP—MS spectra. In addition, the isotopic labelling experiments have provided information on the processes taking place in ICP—MS. For example, the amount of nitrogen gas arising from air entrainment in the plasma and/or from contamination of the argon has been established. Moreover, in comparing the H2O and D2O spectra, differences in relative intensities of the peaks at masses m/z 16, 17 and 18 (O+·, OH+ and H2O+·) could only be explained by assuming that the water injected into the ICP is not completely dissociated. Ionization of the undissociated water molecules may occur via a charge transfer process, which is considered to be certainly possible.

van Heuzen, A. A.; Nibbering, N. M. M.

1993-07-01

163

MASS SPECTROMETRY  

DOEpatents

method is described for operating a mass spectrometer to improve its resolution qualities and to extend its period of use substantially between cleanings. In this method, a small amount of a beta emitting gas such as hydrogen titride or carbon-14 methane is added to the sample being supplied to the spectrometer for investigation. The additive establishes leakage paths on the surface of the non-conducting film accumulating within the vacuum chamber of the spectrometer, thereby reducing the effect of an accumulated static charge on the electrostatic and magnetic fields established within the instrument. (AEC)

Friedman, L.

1962-01-01

164

Peptide Production and Decay Rates Affect the Quantitative Accuracy of Protein Cleavage Isotope Dilution Mass Spectrometry (PC-IDMS)*  

PubMed Central

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.

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

2012-01-01

165

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

NASA Astrophysics Data System (ADS)

Stable carbon isotope analysis of methane (?13C of CH4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in ?13C of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged 86Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in ?13C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

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

2013-05-01

166

Regression analysis for comparing protein samples with 16O\\/18O stable-isotope labeled mass spectrometry  

Microsoft Academic Search

Motivation: Using stable isotopes in global proteome scans, labeled molecules from one sample are pooled with unlabeled molecules from anothersampleandsubsequentlysubjectedtomass-spectralanalysis. Stable-isotope methodologies make use of the fact that identical molecules of different stable-isotope compositions are differentiated in a mass spectrometer and are represented in a mass spectrum as distinct isotopic clusters with a known mass shift. We describe two multivariable

J. E. Ecker-passow; Ann L. Oberg; Terry M. Therneau; C. J. Mason; Douglas W. Mahoney; K. L. Johnson; J. E. Olson; H. R. Bergen III

2006-01-01

167

Electrohydrodynamic mass spectrometry  

SciTech Connect

A review of the principles, development, and status of electrohydrodynamic mass spectrometry, with 111 references, is presented. Areas discussed include: Electrospray; Electrohydrodynamic ion emission; Electrohydrodynamic ionization mass spectrometry; Electrohydrodynamic mass spectrometry of organic compounds; The role of solvation; Emission stability; Comparison with field desorption; Liquid chromatography interfaces; Polymer molecular-weight distributions; Solution chemistry; Sampling efficiencies.

Cook, K.D.

1986-01-01

168

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

169

Use of inductively coupled plasma-mass spectrometry in boron-10 stable isotope experiments with plants, rats, and humans.  

PubMed Central

The commercial availability of inductively coupled plasma-mass spectrometry technology (ICP-MS) has presented the opportunity to measure the boron concentrations and isotope ratios in a large number of samples with minimal sample preparation. A typical analytical sequence for fecal samples consists of 25 acid blanks, 1 digestion blank, 5 calibration solutions, 4 standard reference material solutions, 10 samples, and 4 natural abundance bias standards. Boron detection limits (3 x 1 sigma) for acid blanks are 0.11 ppb for 10B, and 0.40 ppb for 11B. Isotope ratios were measured in fecal samples with 20 to 50 ppb boron with < 2% relative standard deviation. Rapid washout and minimal memory effects were observed for a 50 ppb beryllium internal standard, but a 200 ppb boron biological sample had a 1.0 ppb boron memory after a 6-min washout. Boron isotope ratios in geological materials are highly variable; apparently this variability is reflected in plants of a fixed natural abundance value for boron requires that a natural abundance ratio be determined for each sample or related data set. The natural abundance variability also prevents quantitation and calculation of isotope dilution by instrument-supplied software. To measure boron transport in animal systems, 20 micrograms of 10B were fed to a fasted rat. During the 3 days after a 10B oral dose, 95% of the 10B was recovered from the urine and 4% from the feces. Urinary isotope ratios, 11B/10B, changed from a natural abundance of 4.1140 to an enriched value of 0.95077, a 77% change.(ABSTRACT TRUNCATED AT 250 WORDS)

Vanderpool, R A; Hoff, D; Johnson, P E

1994-01-01

170

Use of inductively coupled plasma-mass spectrometry in boron-10 stable isotope experiments with plants, rats, and humans.  

PubMed

The commercial availability of inductively coupled plasma-mass spectrometry technology (ICP-MS) has presented the opportunity to measure the boron concentrations and isotope ratios in a large number of samples with minimal sample preparation. A typical analytical sequence for fecal samples consists of 25 acid blanks, 1 digestion blank, 5 calibration solutions, 4 standard reference material solutions, 10 samples, and 4 natural abundance bias standards. Boron detection limits (3 x 1 sigma) for acid blanks are 0.11 ppb for 10B, and 0.40 ppb for 11B. Isotope ratios were measured in fecal samples with 20 to 50 ppb boron with < 2% relative standard deviation. Rapid washout and minimal memory effects were observed for a 50 ppb beryllium internal standard, but a 200 ppb boron biological sample had a 1.0 ppb boron memory after a 6-min washout. Boron isotope ratios in geological materials are highly variable; apparently this variability is reflected in plants of a fixed natural abundance value for boron requires that a natural abundance ratio be determined for each sample or related data set. The natural abundance variability also prevents quantitation and calculation of isotope dilution by instrument-supplied software. To measure boron transport in animal systems, 20 micrograms of 10B were fed to a fasted rat. During the 3 days after a 10B oral dose, 95% of the 10B was recovered from the urine and 4% from the feces. Urinary isotope ratios, 11B/10B, changed from a natural abundance of 4.1140 to an enriched value of 0.95077, a 77% change.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7889873

Vanderpool, R A; Hoff, D; Johnson, P E

1994-11-01

171

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

PubMed

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

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

2013-01-07

172

Measurement of 15N\\/ 14N Isotopic Composition in Individual Plasma Free Amino Acids of Human Adults at Natural Abundance by Gas Chromatography–Combustion Isotope Ratio Mass Spectrometry  

Microsoft Academic Search

We describe a high-precision methodology to determine the15N\\/14N isotopic composition of 13 plasma free amino acids out of 500 ?l plasma, measured asN-pivaloyl-i-propyl amino acid esters by gas chromatography–isotope ratio mass spectrometry. It is now possible to measure15N isotopic natural abundances in plasma free amino acids, which has not been the case previously because of the minimum requirement of 60

Cornelia C. Metges; Klaus J. Petzke

1997-01-01

173

Analytical Laboratories Method No. 6005 - the Determination of the Uranium Isotopes (Wt %) by Thermal Ionization Mass Spectrometry (TMS).  

National Technical Information Service (NTIS)

Uranium isotopic analyses at all levels of isotopic concentrations can be performed on microgram quantities of uranium using this solid sample mass spectrometric technique. The uranium, extracted from the matrix material, must be purified prior to perform...

1987-01-01

174

New untargeted metabolic profiling combining mass spectrometry and isotopic labeling: application on Aspergillus fumigatus grown on wheat.  

PubMed

Characterization of fungal secondary metabolomes has become a challenge due to the industrial applications of many of these molecules, and also due to the emergence of fungal threats to public health and natural ecosystems. Given that, the aim of the present study was to develop an untargeted method to analyze fungal secondary metabolomes by combining high-accuracy mass spectrometry and double isotopic labeling of fungal metabolomes. The strain NRRL 35693 of Aspergillus fumigatus , an important fungal pathogen, was grown on three wheat grain substrates: (1) naturally enriched grains (99% (12)C), (2) grains enriched 96.8% with (13)C, (3) grains enriched with 53.4% with (13)C and 96.8% with (15)N. Twenty-one secondary metabolites were unambiguously identified by high-performance liquid chromatography-high-resolution mass spectrometry (HPLC-HRMS) analysis. AntiBase 2012 was used to confirm the identity of these metabolites. Additionally, on the basis of tandem mass spectrometry (MS(n)) experiments, it was possible to identify for the first time the formula and the structure of fumigaclavine D, a new member of the fumigaclavines family. Post biosynthesis degradation of tryptoquivaline F by methanol was also identified during HPLC-HRMS analysis by the detection of a carbon atom of nonfungal origin. The interest of this method lies not only on the unambiguous determination of the exact chemical formulas of fungal secondary metabolites but also on the easy discrimination of nonfungal products. Validation of the method was thus successfully achieved in this study, and it can now be applied to other fungal metabolomes, offering great possibilities for the discovery of new drugs or toxins. PMID:23901908

Cano, Patricia M; Jamin, Emilien L; Tadrist, Souria; Bourdaud'hui, Pascal; Péan, Michel; Debrauwer, Laurent; Oswald, Isabelle P; Delaforge, Marcel; Puel, Olivier

2013-08-20

175

Simultaneous determination of mass-dependent isotopic fractionation and radiogenic isotope variation of strontium in geochemical samples by multiple collector-ICP-mass spectrometry.  

PubMed

We present a method to determine (88)Sr/(86)Sr and (87)Sr/(86)Sr simultaneously. The former variation reflects the mass-dependent isotopic fractionation through the physico-chemical processes, and the latter originates from beta(-)-decay of the parent nuclide (87)Rb as well as the mass-dependent isotopic fractionation. In order to determine the mass-dependent isotopic fractionation, the mass-discrimination effect on (88)Sr/(86)Sr was externally corrected by an exponential law using Zr. For the radiogenic growth of (87)Sr/(86)Sr, the mass-dependent isotopic fractionation effect on (87)Sr/(86)Sr was corrected by a conventional correction technique using the (88)Sr/(86)Sr ratio. The reproducibility of the (88)Sr/(86)Sr and (87)Sr/(86)Sr measurements for a high-purity Sr chemical reagent was 0.06 per thousand (2SD, n = 20) and 0.07 per thousand (2SD, n = 20), respectively. Strontium isotopic ratios ((88)Sr/(86)Sr and (87)Sr/(86)Sr) were measured on six geochemical reference materials (igneous rock: JB-1a and JA-2; carbonate mineral: JLs-1, JDo-1, JCp-1 and JCt-1) and one seawater sample. The resulting (87)Sr/(86)Sr ratios obtained here were consistent with previously published data within the analytical uncertainties. The resulting (88)Sr/(86)Sr ratios for igneous rock samples did not vary significantly within the samples, whereas the carbonate samples showed enrichments of the lighter Sr isotopes over the seawater sample. The (88)Sr/(86)Sr ratio of geochemical samples could reflect the physico-chemical processes for the sample formation. Also, a combined discussion of (88)Sr/(86)Sr and (87)Sr/(86)Sr of samples will render multi-dimensional information on geochemical processes. PMID:17998744

Ohno, Takeshi; Hirata, Takafumi

2007-11-01

176

External calibration in Gas Chromatography–Combustion–Isotope Ratio Mass Spectrometry measurements of endogenous androgenic anabolic steroids in sports doping control  

Microsoft Academic Search

An alternative calibration procedure for the Gas Chromatography–Combustion–Isotope Ratio Mass Spectrometry (GC–C–IRMS) measurements of the World Antidoping Agency (WADA) Accredited Laboratories is presented. To alleviate the need for externally calibrated CO2 gas for GC–C–IRMS analysis of urinary steroid metabolites, calibration using an external standard mixture solution of steroids with certified isotopic composition was investigated. The reference steroids of the calibration

Maroula K. Kioussi; Yiannis S. Angelis; Adam T. Cawley; Michalis Koupparis; Rymantas Kazlauskas; J. Thomas Brenna; Costas G. Georgakopoulos

2011-01-01

177

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

Microsoft Academic Search

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

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

2005-01-01

178

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

SciTech Connect

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

Huang, L.Q.

1989-03-01

179

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

180

Isotope pattern deconvolution for peptide mass spectrometry by non-negative least squares/least absolute deviation template matching  

PubMed Central

Background The robust identification of isotope patterns originating from peptides being analyzed through mass spectrometry (MS) is often significantly hampered by noise artifacts and the interference of overlapping patterns arising e.g. from post-translational modifications. As the classification of the recorded data points into either ‘noise’ or ‘signal’ lies at the very root of essentially every proteomic application, the quality of the automated processing of mass spectra can significantly influence the way the data might be interpreted within a given biological context. Results We propose non-negative least squares/non-negative least absolute deviation regression to fit a raw spectrum by templates imitating isotope patterns. In a carefully designed validation scheme, we show that the method exhibits excellent performance in pattern picking. It is demonstrated that the method is able to disentangle complicated overlaps of patterns. Conclusions We find that regularization is not necessary to prevent overfitting and that thresholding is an effective and user-friendly way to perform feature selection. The proposed method avoids problems inherent in regularization-based approaches, comes with a set of well-interpretable parameters whose default configuration is shown to generalize well without the need for fine-tuning, and is applicable to spectra of different platforms. The R package IPPD implements the method and is available from the Bioconductor platform (http://bioconductor.fhcrc.org/help/bioc-views/devel/bioc/html/IPPD.html).

2012-01-01

181

Discovery of histone modification crosstalk networks by stable isotope labeling of amino acids in cell culture mass spectrometry (SILAC MS).  

PubMed

In this paper we describe an approach that combines stable isotope labeling of amino acids in cells culture, high mass accuracy liquid chromatography tandem mass spectrometry and a novel data analysis approach to accurately determine relative peptide post-translational modification levels. This paper describes the application of this approach to the discovery of novel histone modification crosstalk networks in Saccharomyces cerevisiae. Yeast histone mutants were generated to mimic the presence/absence of 44 well-known modifications on core histones H2A, H2B, H3, and H4. In each mutant strain the relative change in H3 K79 methylation and H3 K56 acetylation were determined using stable isotope labeling of amino acids in cells culture. This approach showed relative changes in H3 K79 methylation and H3 K56 acetylation that are consistent with known histone crosstalk networks. More importantly, this study revealed additional histone modification sites that affect H3 K79 methylation and H3 K56 acetylation. PMID:23592332

Guan, Xiaoyan; Rastogi, Neha; Parthun, Mark R; Freitas, Michael A

2013-04-15

182

"Do it yourself" reference materials for ?13C determinations by isotope ratio mass spectrometry.  

PubMed

A method is described to prepare inexpensive organic reference materials for routine stable isotope work. The method blends isotope-enriched and isotope-depleted materials to match closely international measurement standards. Examples are presented showing how (13)C-enriched and (13)C-depleted glucose were blended to match the isotopic compositions of the international carbon isotope standards, NBS 19 and L-SVEC. Preparation of the blended standards was straightforward, and the prepared solutions proved easy to dispense into tin capsules and easy to combust in a conventional isotope analysis system. The blended materials allow a laboratory to perform a two-point calibration for isotopic composition on a daily basis, with the use of an international reference material recommended for routine quality assurance. The blending method can be applied widely to make isotope standards for other elements and compounds. PMID:23512187

Carter, J F; Fry, B

2013-03-20

183

Quantitation of asparagine deamidation by isotope labeling and liquid chromatography coupled with mass spectrometry analysis.  

PubMed

Nonenzymatic asparagine (Asn) deamidation is one of the commonly observed posttranslational modifications of proteins. Recent development of several specific analytical methods has allowed for efficient identification and differentiation of the deamidation products (i.e., isoaspartate [isoAsp] and aspartate [Asp]). Isotope labeling of isoAsp and Asp that are generated during sample preparation by 18O has been developed and can differentiate isoAsp and Asp as analytical artifacts from those present in the samples prior to sample preparation for an accurate quantitation. However, the 18O labeling procedure has a limitation due to the additional incorporation of up to two 18O atoms into the peptide C-terminal carboxyl groups. Variability in the incorporation of 18O atoms into the peptide C-terminal carboxyl groups results in complicated mass spectra and hinders data interpretation. This limitation can be overcome by the dissection of the complicated mass spectra using a calculation method presented in the current study. The multiple-step calculation procedure has been successfully employed to determine the levels of isoAsp and Asp that are present in the sample prior to sample treatment. PMID:23017877

Liu, Hongcheng; Wang, Fengqiang; Xu, Wei; May, Kimberly; Richardson, Daisy

2012-09-24

184

Androstanediol and 5-androstenediol profiling for detecting exogenously administered dihydrotestosterone, epitestosterone, and dehydroepiandrosterone: Potential use in gas chromatography isotope ratio mass spectrometry  

Microsoft Academic Search

The basis of a potential method for confirming intake of four natural androgens (testosterone, epitestosterone, dihydrotestosterone, and dehydroepiandrosterone is presented. The method relies on isolating from urine a steroid fraction containing androstenediol and androstanediol metabolites of these natural steroids and analyzing their 13C content by gas chromatography, combustion, isotope ratio mass spectrometry. The steroids were recovered from urine by conjugate

Cedric H. L. Shackleton; Esther Roitman; Andy Phillips; Tony Chang

1997-01-01

185

Stable isotopic analysis of pyrogenic organic matter in soils by liquid chromatography-isotope-ratio mass spectrometry of benzene polycarboxylic acids.  

PubMed

Pyrogenic organic matter (PyOM), the incomplete combustion product of organic materials, is considered stable in soils and represents a potentially important terrestrial sink for atmospheric carbon dioxide. One well-established method of measuring PyOM in the environment is as benzene polycarboxylic acids (BPCAs), a compound-specific method, which allows both qualitative and quantitative estimation of PyOM. Until now, stable isotope measurement of PyOM carbon involved measurement of the trimethylsilyl (TMS) or methyl (Me) polycarboxylic acid derivatives by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). However, BPCA derivatives can contain as much as 150% derivative carbon, necessitating post-analysis correction for the accurate measurement of ?¹³C values, leading to increased measurement error. Here, we describe a method for ?¹³C isotope ratio measurement and quantification of BPCAs from soil-derived PyOM, based on ion-exchange chromatography (IEC-IRMS). The reproducibility of the ?¹³C measurement of individual BPCAs by IEC-IRMS was better than 0.35‰ (1?). The ?¹³C-BPCA analysis of PyOM in soils, including at natural and artificially enriched ¹³C-abundance, produced accurate and precise ?¹³C measurements. Analysis of samples that differed in ?¹³C by as much as 900‰ revealed carryover of <1‰ between samples. The weighted sum of individual ?¹³C-BPCA measurements was correlated with previous isotopic measurements of whole PyOM, providing complementary information for bulk isotopic measurements. We discuss potential applications of ?¹³C-BPCA measurements, including the study of turnover rates of PyOM in soils and the partitioning of PyOM sources based on photosynthetic pathways. PMID:22468329

Yarnes, Christopher; Santos, Fernanda; Singh, Nimisha; Abiven, Samuel; Schmidt, Michael W I; Bird, Jeffrey A

2011-12-30

186

Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry  

SciTech Connect

An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

Beals, D.M.

1992-09-01

187

Determination of technetium-99 in aqueous samples by isotope dilution inductively coupled plasma-mass spectrometry  

SciTech Connect

An isotope dilution/inductively coupled plasma mass spectrometric method (ID/ICP-MS) for measuring the concentration of technetium-99 in aqueous samples was developed at the Savannah River Technology Center (SRTC). The procedure is faster than radiometric techniques, is also less subject to interferences, and has equal or better detection limits. It is currently being used to measure the concentration of {sup 99}Tc in samples of Savannah River water collected in the vicinity of the Savannah River Site. In this method, one liter samples of water are spiked with {sup 97}Tc. After equilibration, the technetium is extracted from the sample with a chromatographic resin. Interfering elements, molybdenum and ruthenium, are either not retained by the resin or are washed off with dilute nitric acid. The technetium is then eluted with more concentrated nitric acid, and the {sup 99}Tc/{sup 97}Tc ratio in the eluant is measured with an ICP-MS. The {sup 99}Tc concentration in the original sample is calculated from the {sup 99}Tc/{sup 97}Tc ratio. The chemical recovery of the extraction procedure is greater than 90%. The detection limit of the instrument, taken as three times the background counts at m/z = 99, is 0.6 part per trillion (ppt). The detection limit of the procedure, taken as three times the standard deviation of several reagent blank analyses, is 0.33 pCi/L.

Beals, D.M.

1992-01-01

188

[Accurate determination of chloramphenicol in pork by isotope dilution liquid chromatography-electrospray ionization tandem mass spectrometry].  

PubMed

An accurate method was described for the determination of chloramphenicol (CAP) in pork. The analyte was quantified by isotope dilution liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) operating in negative ion multiple reaction monitoring (MRM) mode. The sample was treated by liquid-liquid extraction with ethyl acetate followed by a clean-up step on an HLB solid-phase extraction cartridge. Chloramphenicol-D5 (CAP-D5) was added as an isotope internal standard. Under the optimized conditions, the calibration curve showed a good linearity in ranging from 0.01 to 0.5 ng/g CAP. The correlation coefficient r2 was 0.9998. The limit of detection and the limit of quantification were 0.004 and 0.02 ng/g, respectively. The average recoveries of CAP at 0.02 ng/g and 1.0 ng/g spiked levels ranged from 95.2%-109.1%, 99.7%-102.5%, respectively. The relative standard deviations (RSDs) of intra-day and inter-day were less than 2%. Meanwhile, matrix effect factors k of CAP and CAP-D5 were determined under different mobile phases and the sample solvent composition, the k was in the range of 0.950-1.015. The method can be used as a confirmed method for the determination of CAP in pork. PMID:22233085

Yang, Zong; Li, Xiuqin; Wang, Juan; Zhang, Qinghe

2011-09-01

189

Mass spectrometry of long-lived radionuclides  

Microsoft Academic Search

The capability of determining element concentrations at the trace and ultratrace level and isotope ratios is a main feature of inorganic mass spectrometry. The precise and accurate determination of isotope ratios of long-lived natural and artificial radionuclides is required, e.g. for their environmental monitoring and health control, for studying radionuclide migration, for age dating, for determining isotope ratios of radiogenic

Johanna Sabine Becker

2003-01-01

190

Osmium isotope ratio measurements by negative thermal ionization mass spectrometry (NTI-MS)  

Microsoft Academic Search

A negative thermal ionization technique using a Faraday cup as detector is presented, which allows precise isotope ratio measurements of osmium. For the major isotopes the relative standard deviation is in the range of 0.004% to 0.07%. Sample amounts down to 1 ng were loaded as hexachloroosmic acid. From the results it is concluded that also sample amounts in the

Thomas Walczyk; Erhard H. Hebeda; Klaus G. Heumann

1991-01-01

191

Determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell.  

PubMed

A method is described for determination of selenium in sediment by isotope-dilution inductively coupled plasma mass spectrometry with an octapole reaction cell (ID-ICP-ORCMS). Sediment samples were digested with HNO3, HClO4, and HF, and the digestion included an elaborate evaporation process to remove bromine from the digested solution. Simple strong cation-exchange disk filtration was used to remove rare earth elements (REE) from the digested solution, because REE2+ seriously interfere with Se isotopes (i.e. 156Gd2+ with 78Se+, 160Gd2+ with 80Se+). Addition of acetic acid to the filtrate was examined to improve the sensitivity of ICP-ORCMS measurement of Se+ by means of a carbon-enhancement effect. The interfering Ar2+ for selenium isotopes were almost eliminated by use of H2 as reaction gas. Interference from BrH+ formed in the reaction cell was negligible because the Br was removed in the evaporation process. Approximately 99.5% of REE were removed by cation-exchange disk filtration yet more than 99% of Se remained in the filtrate solution. The intensity for Se+ was enhanced approximately fourfold by addition of 5% (v/v) of acetic acid whereas that for Ar2+ was barely enhanced. Measured 80Se/78Se ratios in unspiked digested solutions of the sample were in good agreement with that for an Se standard solution. The analytical results for Se in the certified reference materials MESS-3 and PACS-1 were in good agreement with their certified values, with small uncertainties. PMID:16557408

Inagaki, Kazumi; Takatsu, Akiko; Nakama, Atsuko; Eyama, Sakae; Yarita, Takashi; Okamoto, Kensaku; Chiba, Koichi

2006-03-24

192

Analysis of Atmospheric Nitrogen Inputs to the Forest Through Isotope Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Understanding the fate of atmospheric nitrogen is essential to understanding the forest nitrogen cycle. Recent studies have indicated that atmospheric nitrogen deposition has an important role in the nitrogen cycle for nitrogen-limited forests. Since most of the forests of the northern hemisphere are nitrogen-limited, wet and dry deposition of atmospheric nitrogen may have a significant impact on carbon sequestration. The current study hypothesizes that a significant fraction of nitrogen that is in the soil is deposited from the atmosphere. In this study, we sampled soil, rainfall, and cloud water in the vicinity of the University of Michigan Biological Station, and determined the value for ?17O in NO3- from those samples. The average tropospheric ?17O value for NO3-atm (nitrate aerosol and gaseous HNO3) for the U. S. Midwest region is approximately 23‰ based on recent measurements and modeling considerations. In contrast, nitrate from microbial nitrification of fertilizer or plant matter has ?17O of zero. This makes ?17O signals in soil and water nitrate a positive indicator of un-cycled atmospherically-derived nitrate. For this work, the nitrate was extracted, purified, and converted to N2O, which was then separated by GC and detected using a Thermo Delta V continuous flow isotope ratio mass spectrometer. Here we will present and discuss the results of ?17O measurements for NO3- in these samples, to accurately quantify the proportion of atmospheric nitrate in soils. The dissolved nitrate ?17O values give both the atmospheric component and the biological component through a two source mixing model. This quantification contributes to the long term effort on improving our understanding of the nature, chemistry, and impact of atmospheric nitrogen on the carbon cycle.

Wright, A. J.; Alexander, B.; Michalski, G. M.; Shepson, P. B.

2010-12-01

193

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

Microsoft Academic Search

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

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

2006-01-01

194

Revisiting type-A uncertainties relating to the measurement of mass fraction of lead using isotope-dilution inductively coupled plasma mass spectrometry: a way of improving measurement precision and expanded uncertainty  

Microsoft Academic Search

A quadrupole inductively coupled plasma mass spectrometer (Q-ICP-MS) has been used for determination of lead in plant materials\\u000a using isotope-dilution inductively coupled plasma mass spectrometry. The accuracy of the method was demonstrated by analysis\\u000a of a matrix certified reference material, NIST SRM 1547 Peach Leaves. Specific instrumental parameters of Q-ICP-MS, including\\u000a isotope analysis mode, integration time per point, number of

James Chung Wah Lam; Yiu Chung Yip; Wai Fong Tong

2008-01-01

195

Assessing the stable carbon isotopic composition of intercellular CO2 in a CAM plant using gas chromatography-combustion-isotope ratio mass spectrometry.  

PubMed

Most of the literature focused on internal CO(2) (Ci) determinations in plants has used indirect methods based on gas-exchange estimations. We have developed a new method based on the capture of internal air gas samples and their analysis by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). This method provided a direct measure of intercellular CO(2) concentrations combined with stable carbon isotopic composition in O. ficus-indica plants. Plants were grown at both ambient and elevated CO(2) concentration. During the day period, when the stomata are closed, the Ci was high and was very (13)C-enriched in both ambient and elevated CO(2)-grown plants, reflecting Rubisco's fractionation (this plant enzyme has been shown to discriminate by 29 per thousand, in vitro, against (13)CO(2)). Other enzyme fractionations involved in C metabolism in plants, such as carbonic anhydrase, could also be playing an important role in the diurnal delta(13)C enrichment of the Ci. During the night, when stomata are open, Ci concentrations were higher in elevated (and the corresponding delta(13)C values were more (13)C-depleted) than in ambient CO(2)-grown plants. PMID:18320540

Nogués, Salvador; Aranjuelo, Iker; Pardo, Antoni; Azcón-Bieto, Joaquim

2008-04-01

196

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

197

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

PubMed

Gas chromatography coupled to isotope ratio mass spectrometry after on-line combustion (GC-C-IRMS) and high temperature conversion (GC-HTC-IRMS) is used for compound specific isotope ratio determination. This determination can only be performed successfully if the target solutes are fully resolved from other compounds. A new instrumental set-up consisting of heart-cutting two-dimensional GC based on capillary flow technology and a low thermal mass GC oven in combination with an isotope ratio mass spectrometer is presented. Capillary flow technology was also used in all column and interface connections for robust and leak-free operation. The new configuration was applied to the characterization of wax compounds in tobacco leaf and corresponding smoke samples. It is demonstrated that high accuracy is obtained, both in the determination of ?(13)C and ?(2)H values, allowing the study of biosynthesis and delivery mechanisms of naturally occurring compounds in tobacco. PMID:23721809

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

2013-04-30

198

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

199

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

200

Determination of 5-methyltetrahydrofolic acid and folic acid in citrus juices using stable isotope dilution-mass spectrometry.  

PubMed

A stable isotope liquid chromatography-mass spectrometry (LC-MS) method was developed for the quantitative determination of 5-methyltetrahydrofolic acid (5-MTHFA) and folic acid in a variety of commercial citrus juices. Folates were extracted from juices, and the polyglutamyl side chain of 5-MTHFA was cleaved to the monoglutamate form using rat plasma conjugase. The folates were purified on a Bond-Elut column and analyzed by LC-MS with electrospray ionization. The analytes were quantified using the (13)C(5) analogues of 5-MTHFA and folic acid as internal standards. The relative standard error of the method was 3.35% based on replicate analyses (n = 4). This method was then applied to the determination of 5-MTHFA and folic acid in a variety of citrus juices obtained from local supermarkets. It was observed that although both "store" brands and "national" brands of fresh (nonfrozen) juices contained similar concentrations of 5-MTHFA, the "store" brands of fresh juices had on average >5-fold the amount of folic acid compared to the "national" brands. In addition, the "total" folate concentrations were generally below values listed on the food label. PMID:12590471

Thomas, Paul M; Flanagan, Vincent P; Pawlosky, Robert J

2003-02-26

201

Evaluation of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) for the quality assessment of citrus liqueurs.  

PubMed

Citrus liqueurs are alcoholic beverages obtained by maceration. The European Parliament protects these alcoholic beverages, forbidding the addition of nature-identical flavoring substances. However, for economical and technological reasons, producers often add natural and/or synthetic flavors to the alcoholic syrup, obtaining artificial spirit drinks. The aim of this study is to investigate the authenticity of Italian liqueurs, of lemon, bergamot, and mandarin (locally known as "limoncello", "bargamino", and "mandarinetto"), comparing the carbon isotope ratios with values determined in genuine cold-pressed peel oils. Authenticity assessment was performed using headspace-solid phase microextraction coupled to gas chromatography-combustion-isotope ratio mass spectrometry. Additional analyses were performed by direct enantioselective gas chromatography to determine the enantiomeric distribution of selected chiral volatiles and by gas chromatography-mass spectrometry for the qualitative analyses of the samples. The method allowed confirmation of genuineness. Enantioselective gas chromatography analyses confirmed the results, demonstrating the reliability of the method. PMID:23101544

Schipilliti, Luisa; Bonaccorsi, Ivana; Cotroneo, Antonella; Dugo, Paola; Mondello, Luigi

2012-11-05

202

Simultaneous determination of amphetamine and methamphetamine enantiomers in urine by simultaneous liquid–liquid extraction and diastereomeric derivatization followed by gas chromatographic–isotope dilution mass spectrometry  

Microsoft Academic Search

A simple, rapid, reliable, and economic analytical scheme starting with in situ liquid–liquid extraction and asymmetric (or diastereomeric) chemical derivatization (ChD) followed by gas chromatography (GC)-isotope dilution mass spectrometry (MS) is described for the simultaneous determination of d- and l-amphetamine (AP) and methamphetamine (MA) in urine which could have resulted from the administration of various forms of questioned amphetamines or

Sheng-Meng Wang; Ting-Cheng Wang; Yun-Seng Giang

2005-01-01

203

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.

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

2011-01-01

204

Assay of tyrosol and hydroxytyrosol in olive oil by tandem mass spectrometry and isotope dilution method.  

PubMed

Hydroxytyrosol and tyrosol, the strong antioxidant present in large amount in virgin olive oil have been assayed by LC-MS/MS under MRM condition and isotope dilution method, using d(2)-labelled internal standards obtained by simple synthetic procedures. The assay has been performed under MRM condition monitoring two transitions for each analyte to improve the specificity. This paper deals with a modern approach for assaying the content of this polyphenols in virgin olive oil down to a limit of a few hundreds of parts per billion. Tyrosol and hydroxytyrosol ranged from 10 to 47ppm and from 5 to 25ppm in commercial olive oil, respectively. The accuracy (98-107%) and analytical parameters values confirm the reliability of the proposed approach. The method can be extended to any natural matrices, including mill wastes, after a simple step of sample preparation. PMID:22953817

Mazzotti, Fabio; Benabdelkamel, Hicham; Di Donna, Leonardo; Maiuolo, Loredana; Napoli, Anna; Sindona, Giovanni

2012-05-31

205

Automated cryogenic collection of carbon dioxide for stable isotope analysis and carbon-14 accelerator mass spectrometry dating  

Microsoft Academic Search

A vacuum-powered high-vacuum glass valve has been used to develop gas sample bottles with automated taps. The automated, cryogenic systems have performed well for COâ collection to perform mass spectrometric analysis of ¹³C and tandem accelerator mass spectrometry of ¹⁴C.

C. A. M. Brenninkmeijer

1988-01-01

206

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

207

Sequencing of Isotope-Labeled Small RNA Using Femtosecond Laser Ablation Time-of-Flight Mass Spectrometry  

NASA Astrophysics Data System (ADS)

A novel method for the analysis of sequences of small RNAs using nucleotide triphosphates labeled with stable isotopes has been developed using time-of-flight mass spectroscopy combined with femtosecond laser ablation (fsLA-TOF-MS). Small RNAs synthesized with nucleotides enriched in 13C and 15N were efficiently atomized and ionized by single-shot fsLA and the isotope ratios 13C/12C and 15N/14N were evaluated using the TOF-MS method. By comparing the isotope ratios among four different configurations, the number of nucleotide contents of the control RNA sample were successfully reproduced.

Kurata-Nishimura, Mizuki; Ando, Yoshinari; Kobayashi, Tohru; Matsuo, Yukari; Suzuki, Harukazu; Hayashizaki, Yoshihide; Kawai, Jun

2010-04-01

208

Comprehensive and highly sensitive urinary steroid hormone profiling method based on stable isotope-labeling liquid chromatography-mass spectrometry.  

PubMed

Steroid hormones are crucial substances that mediate a wide range of vital physiological functions of the body. Determination of the levels of steroid hormones plays an important role in understanding the mechanism of the steroid hormone-related diseases. In this study, we present a novel targeted metabolic profiling method based on the introduction of an easily protonated stable isotope tag to a hydroxyl-containing steroid hormone with a synthesized derivatization reagent, deuterium 4-(dimethylamino)-benzoic acid (d(4)-DMBA), and liquid chromatography-mass spectrometry (LC-MS). Different from other reported derivatization reagents that have been used to enhance the sensitivities for estrogens or androgens, our method is comprehensive with the capability of covering hydroxyl-containing androgens, estrogens, corticoids, and progestogens. Furthermore, the nonderivatized steroid hormones (e.g., 17?-hydroxyprogesterone, progesterone, and androstenedione) were not destroyed during the derivatization process, and their levels could still be obtained in one LC-MS run. We were able to detect 24 steroid hormones at subng/mL levels (the lower limit of detection could reach 5 pg/mL for estrone and 16?-hydroxy estrone, which is equivalent to 0.1 pg on column) with maximum sensitivity enhancement factors of more than 10(3)- to 10(4)-fold after derivatization. The method was successfully applied to the measurement of free (unconjugated) steroid hormones in urine samples of males, females, and pregnant women. Because the significant role the steroid hormone pathway plays in humans, a comprehensive, sensitive, specific, and accurate method for profiling the steroid hormone metabolome shall offer new insights into hormone-related diseases. PMID:23110480

Dai, Weidong; Huang, Qiang; Yin, Peiyuan; Li, Jia; Zhou, Jia; Kong, Hongwei; Zhao, Chunxia; Lu, Xin; Xu, Guowang

2012-11-13

209

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

210

Precise determinations of the isotopic compositions and atomic weights of molybdenum, tellurium, tin and tungsten using ICP source magnetic sector multiple collector mass spectrometry  

SciTech Connect

Precise determinations of the isotopic compositions of molybdenum, tellurium, tin and tungsten were obtained utilizing an inductively coupled plasma source (ICP) magnetic sector mass spectrometer equipped with multiple collectors. The results of this study are comparable to those measured by conventional and negative thermal ionization mass spectrometry (TIMS and NTIMS) and the values recommended by the International Union of Pure and Applied Chemistry (IUPAC), but with improvement in precision by up to two orders of magnitude. The isotopic abundances and atomic weight for each element calculated from the data obtained in this study are also in excellent agreement with previously published values. The only disagreement between this study and IUPAC recommended values is for tellurium. However, with the exception of {sup 130}Te, the Te data are in good agreement with those reported in a recent study by De Laeter. The results of this study demonstrate the capability of this new instrument to produce precise and reproducible isotopic data for elements that are difficult to ionize and measure with TIMS. Furthermore, the greater precision of isotopic measurements possible with the ICP source multiple collector magnet sector mass spectrometer greatly enhances the prospects for research on the distribution and isotopic compositions of these elements in terrestrial and meteoritic materials.

Lee, Der-Chuen; Halliday, A.N.

1994-11-01

211

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

212

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

213

Improvement in Thermal-Ionization Mass Spectrometry (TIMS) using Total Flash Evaporation (TFE) method for lanthanides isotope ratio measurements in transmutation targets  

SciTech Connect

The experiments involved in the PHENIX french nuclear reactor to obtain precise and accurate data on the total capture cross sections of the heavy isotopes and fission products require isotopic ratios measurements with uncertainty of a few per mil. These accurate isotopic ratio measurements are performed with mass spectrometer equipped with multi-collector system. The major difficulty for the analyses of these actinides and fission products is the low quantity of the initial powder enclosed in steel container (3 to 5 mg) and the very low quantities of products formed (several {mu}g) after irradiation. Specific analytical developments are performed by Thermal Ionization Mass Spectrometry (TIMS) to be able to analyse several nanograms of elements with this technique. A specific method of acquisition named Total Flash Evaporation was adapted in this study in the case of lanthanide measurements for quantity deposited on the filament in the order of 2 ng and applied on irradiated fuel. To validate the analytical approach and discuss about the accuracy of the data, the isotopic ratios obtained by TIMS are compared with other mass spectrometric techniques such as Multiple-Collector Inductively Coupled Plasma Mass Spectrometer (MC-ICPMS). (authors)

Mialle, S.; Gourgiotis, A.; Aubert, M.; Stadelmann, G.; Gautier, C.; Isnard, H. [Commissariat a l'Energie Atomique, CEA Saclay, DEN/DPC/SECR/LANIE, 91191 Gif sur Yvette (France); Chartier, F. [Commissariat a l'Energie Atomique, CEA Saclay, DEN/DPC, 91191 Gif sur Yvette (France)

2011-07-01

214

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

Microsoft Academic Search

A gas chromatograph\\/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and

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

1993-01-01

215

Determination of depleted uranium in urine via isotope ratio measurements using large-bore direct injection high efficiency nebulizer-inductively coupled plasma mass spectrometry.  

PubMed

Inductively coupled plasma mass spectrometry (ICP-MS), coupled with a large-bore direct injection high efficiency nebulizer (LB-DIHEN), was utilized to determine the concentration and isotopic ratio of uranium in 11 samples of synthetic urine spiked with varying concentrations and ratios of uranium isotopes. Total U concentrations and (235)U/(238)U isotopic ratios ranged from 0.1 to 10 microg/L and 0.0011 and 0.00725, respectively. The results are compared with data from other laboratories that used either alpha-spectrometry or quadrupole-based ICP-MS with a conventional nebulizer-spray chamber arrangement. Severe matrix effects due to the high total dissolved solid content of the samples resulted in a 60 to 80% loss of signal intensity, but were compensated for by using (233)U as an internal standard. Accurate results were obtained with LB-DIHEN-ICP-MS, allowing for the positive identification of depleted uranium based on the (235)U/(238)U ratio. Precision for the (235)U/(238)U ratio is typically better than 5% and 15% for ICP-MS and alpha-spectrometry, respectively, determined over the concentrations and ratios investigated in this study, with the LB-DIHEN-ICP-MS system providing the most accurate results. Short-term precision (6 min) for the individual (235)U and (238)U isotopes in synthetic urine is better than 2% (N = 7), compared to approximately 5% for conventional nebulizer-spray chamber arrangements and >10% for alpha-spectrometry. The significance of these measurements is discussed for uranium exposure assessment of Persian Gulf War veterans affected by depleted uranium ammunitions. PMID:15479520

Westphal, Craig S; McLean, John A; Hakspiel, Shelly J; Jackson, William E; McClain, David E; Montaser, Akbar

2004-09-01

216

Comparison of water isotope-ratio determinations using two cavity ring-down instruments and classical mass spectrometry in continuous ice-core analysis.  

PubMed

We present a detailed comparison between subsequent versions of commercially available wavelength-scanned cavity ring-down water isotope analysers (L2120-i and L2130-i, Picarro Inc.). The analysers are used in parallel in a continuous mode by adaption of a low-volume flash evaporation module. Application of the analysers to ice-core analysis is assessed by comparison between continuous water isotope measurements of a glacial ice-core from Severnaya Zemlya with discrete isotope-ratio mass spectrometry measurements performed on parallel samples from the same ice-core. The great advances between instrument versions, particularly in the measurement of ?(2)H, allow the continuous technique to achieve the same high level of accuracy and precision obtained using traditional isotope spectrometry techniques in a fraction of the experiment time. However, when applied to continuous ice-core measurements, increased integration times result in a compromise of the achievable depth resolution of the ice-core records. PMID:23713832

Maselli, Olivia J; Fritzsche, Diedrich; Layman, Lawrence; McConnell, Joseph R; Meyer, Hanno

2013-05-29

217

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

218

Selected ion flow tube mass spectrometry analyses of stable isotopes in water: Isotopic composition of H3O+ and H3O+(H2O)(3) ions in exchange reactions with water vapor  

Microsoft Academic Search

A new method has been developed for the determination of the isotope abundance ratios of deuterium, D, and oxygen-18, O-18, in water vapor (and water) using selected ion flow tube mass spectrometry (SIFT-MS). H3O+ ions are injected into the helium carrier gas where they associate with the H2O and HDO molecules in a sample of water introduced into the carrier

Patrik Špan?l; David Smith

2000-01-01

219

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

2013-05-27

220

Further development of IDGS: Isotope dilution gamma-ray spectrometry  

SciTech Connect

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

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

1991-01-01

221

Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction.  

PubMed

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl. PMID:16504353

Boulyga, Sergei F; Heumann, Klaus G

2006-02-28

222

Non-linear signal response functions and their effects on the statistical and noise cancellation properties of isotope ratio measurements by multi-collector plasma mass spectrometry  

NASA Astrophysics Data System (ADS)

A nebulizer-centric response function model of the analytical inductively coupled argon plasma ion source was used to investigate the statistical frequency distributions and noise reduction factors of simultaneously measured flicker noise limited isotope ion signals and their ratios. The response function model was extended by assuming i) a single gaussian distributed random noise source (nebulizer gas pressure fluctuations) and ii) the isotope ion signal response is a parabolic function of the nebulizer gas pressure. Model calculations of ion signal and signal ratio histograms were obtained by applying the statistical method of translation to the non-linear response function model of the plasma. Histograms of Ni, Cu, Pr, Tl and Pb isotope ion signals measured using a multi-collector plasma mass spectrometer were, without exception, negative skew. Histograms of the corresponding isotope ratios of Ni, Cu, Tl and Pb were either positive or negative skew. There was a complete agreement between the measured and model calculated histogram skew properties. The nebulizer-centric response function model was also used to investigate the effect of non-linear response functions on the effectiveness of noise cancellation by signal division. An alternative noise correction procedure suitable for parabolic signal response functions was derived and applied to measurements of isotope ratios of Cu, Ni, Pb and Tl. The largest noise reduction factors were always obtained when the non-linearity of the response functions was taken into account by the isotope ratio calculation. Possible applications of the nebulizer-centric response function model to other types of analytical instrumentation, large amplitude signal noise sources (e.g., lasers, pumped nebulizers) and analytical error in isotope ratio measurements by multi-collector plasma mass spectrometry are discussed.

Doherty, W.

2013-07-01

223

Simultaneous determination of androstenediol 3-sulfate and dehydroepiandrosterone sulfate in human serum using isotope diluted liquid chromatography–electrospray ionization-mass spectrometry  

Microsoft Academic Search

A simple method for simultaneous determination of androstenediol 3-sulfate (Adiol-3S) and dehydroepiandrosterone sulfate (DHEA-S) in human serum using isotope diluted liquid chromatography–electrospray ionization-ion trap-mass spectrometry (LC–ESI-ion trap-MS) was developed. After addition of deuterated internal standards ([2H5]Adiol-3S and [2H4]DHEA-S), human serum (100?l) was deproteinized with acetonitrile and then applied to a solid-phase extraction cartridge, Oasis HLB. The obtained steroid sulfates fraction

Kuniko Mitamura; Yoko Nagaoka; Kazutake Shimada; Seijiro Honma; Mikio Namiki; Eitetsu Koh; Atsushi Mizokami

2003-01-01

224

Probing the in vivo biosynthesis of scytonemin, a cyanobacterial ultraviolet radiation sunscreen, through small scale stable isotope incubation studies and MALDI-TOF mass spectrometry  

PubMed Central

Scytonemin is a dimeric indole phenolic pigment found in the sheath of many cyanobacteria. This pigment absorbs UV radiation protecting subtending cyanobacterial cells from harmful effects. Based on scytonemin’s unique chemical structure, the pathway to its biosynthesis is uncertain, thus motivating the current investigation. Herein, we report the incorporation of both tyrosine and tryptophan into scytonemin, and provide in vivo data supporting the tryptophan origin of the ketone carbon involved in the condensation of the two biosynthetic precursors. This study also reports on the new use of a small-scale, MALDI-TOF mass spectrometry technique to monitor the incorporation of isotopically labeled tyrosine during scytonemin biosynthesis.

Jones, Carla S.; Esquenazi, Eduardo; Dorrestein, Pieter C.; Gerwick, William H.

2011-01-01

225

Mass spectrometry and proteomics  

Microsoft Academic Search

Proteomics is the systematic analysis of the proteins expressed by a cell or tissue, and mass spectrometry is its essential analytical tool. In the past two years, incremental advances in standard proteome technology have increased the speed of protein identification with higher levels of automation and sensitivity. Furthermore, new approaches have provided landmark advances in determining functionally relevant properties of

Steven P Gygi; Ruedi Aebersold; J YATESIII

2000-01-01

226

Analytical mass spectrometry  

SciTech Connect

This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

Not Available

1990-01-01

227

Analytical mass spectrometry. Abstracts  

SciTech Connect

This 43rd Annual Summer Symposium on Analytical Chemistry was held July 24--27, 1990 at Oak Ridge, TN and contained sessions on the following topics: Fundamentals of Analytical Mass Spectrometry (MS), MS in the National Laboratories, Lasers and Fourier Transform Methods, Future of MS, New Ionization and LC/MS Methods, and an extra session. (WET)

Not Available

1990-12-31

228

Method for the Determination of Total Homocysteine in Plasma and Urine by Stable Isotope Dilution and Electrospray Tandem Mass Spectrometry  

Microsoft Academic Search

Background: Total homocysteine (tHcy) has emerged as an important independent risk factor for cardiovascular disease. Analytical methods are needed to accommodate the high testing volumes for tHcy and provide rapid turnaround. Methods: We developed liquid chromatography electro- spray tandem mass spectrometry (LC-MS\\/MS) method based on the analysis of 100 mL of either plasma or urine with homocystine-d8 (2 nmol) added

Mark J. Magera; Jean M. Lacey; Bruno Casetta; Piero Rinaldo

229

Multielement Determination and Lead Isotope Ratio Measurement in Alcoholic Beverages by High–Resolution Inductively Coupled Plasma Mass Spectrometry  

Microsoft Academic Search

The analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the inorganic analysis of alcoholic beverages was evaluated using double-focusing sector field ICP-MS (ICP-SMS). No sample pre-treatment other than acidification and dilution was carried out. Though aspiration of ethanol-containing solutions into the ICP caused significant matrix effects, accurate results could be obtained by using matrix-matched blanks and standards. Method

Ilia Rodushkin; Fredrik Ödman; Petra K. Appelblad

1999-01-01

230

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

Microsoft Academic Search

A gas chromatographic (GC) method with mass spectrometry detection (MS) for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in olive pomace oil has been developed. The oil was diluted with n-pentane and extracted by liquid–liquid partition with dimethyl sulphoxide (DMSO). After water addition and back-extraction with cyclohexane, a thin-layer chromatography on silica gel was performed as a further purification

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

2005-01-01

231

Stable Isotope Ratiometer-Multiple Ion Detector (Sirmid) Unit for Quantitative and Qualitative Stable Isotope Studies by Gas Chromatography-Mass Spectrometry.  

National Technical Information Service (NTIS)

A stable isotope ratiometer-multiple ion detector (SIRMID) unit which can drive existing gas chromatograph-quadrupole or magnetic sector mass spectrometers to monitor up to six ions in turn is described. Each of the three pairs of ions can be selected for...

P. D. Klein J. R. Haumann D. L. Hachey

1975-01-01

232

Determination of uranium isotopic composition and 236U content of soil samples and hot particles using inductively coupled plasma mass spectrometry.  

PubMed

As a result of the accident at the Chernobyl nuclear power plant (NPP) the environment was contaminated with spent nuclear fuel. The 236U isotope was used in this study to monitor the spent uranium from nuclear fallout in soil samples collected in the vicinity of the Chernobyl NPP. Nuclear track radiography was applied for the identification and extraction of hot radioactive particles from soil samples. A rapid and sensitive analytical procedure was developed for uranium isotopic ratio measurement in environmental samples based on double-focusing inductively coupled plasma mass spectrometry (DF-ICP-MS) with a MicroMist nebulizer and a direct injection high-efficiency nebulizer (DIHEN). The performance of the DF-ICP-MS with a quartz DIHEN and plasma shielded torch was studied. Overall detection efficiencies of 4 x 10(-4) and 10(-3) counts per atom were achieved for 238U in DF-ICP-QMS with the MicroMist nebulizer and DIHEN, respectively. The rate of formation of uranium hydride ions UH+/U+ was 1.2 x 10(-4) and 1.4 x 10(-4), respectively. The precision of short-term measurements of uranium isotopic ratios (n = 5) in 1 microg L(-1) NBS U-020 standard solution was 0.11% (238U/235U) and 1.4% (236U/238U) using a MicroMist nebulizer and 0.25% (235U/238U) and 1.9% (236U/P38U) using a DIHEN. The isotopic composition of all investigated Chernobyl soil samples differed from those of natural uranium; i.e. in these samples the 236U/238U ratio ranged from 10(-5) to 10(-3). Results obtained with ICP-MS, alpha- and gamma-spectrometry showed differences in the migration properties of spent uranium, plutonium, and americium. The isotopic ratio of uranium was also measured in hot particles extracted from soil samples. PMID:11496994

Boulyga, S F; Becker, J S

2001-07-01

233

Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS for isotope analysis of long-lived radionuclides  

NASA Astrophysics Data System (ADS)

For a few years now inductively coupled plasma mass spectrometry has been increasingly used for precise and accurate determination of isotope ratios of long-lived radionuclides at the trace and ultratrace level due to its excellent sensitivity, good precision and accuracy. At present, ICP-MS and also laser ablation ICP-MS are applied as powerful analytical techniques in different fields such as the characterization of nuclear materials, recycled and by-products (e.g., spent nuclear fuel or depleted uranium ammunitions), radioactive waste control, in environmental monitoring and in bioassay measurements, in health control, in geochemistry and geochronology. Especially double-focusing sector field ICP mass spectrometers with single ion detector or with multiple ion collector device have been used for the precise determination of long-lived radionuclides isotope ratios at very low concentration levels. Progress has been achieved by the combination of ultrasensitive mass spectrometric techniques with effective separation and enrichment procedures in order to improve detection limits or by the introduction of the collision cell in ICP-MS for reducing disturbing interfering ions (e.g., of 129Xe+ for the determination of 129I). This review describes the state of the art and the progress of ICP-MS and laser ablation ICP-MS for isotope ratio measurements of long-lived radionuclides in different sample types, especially in the main application fields of characterization of nuclear and radioactive waste material, environmental research and health controls.

Becker, J. Sabine

2005-04-01

234

Secondary Ion Mass Spectrometry (SIMS): A tool for elemental and isotopic analysis of small objects, small volumes and small samples  

NASA Astrophysics Data System (ADS)

SIMS utilizes a beam of primary ions to dynamically sputter solid material, producing secondary ions derived from that material. These secondary ions are extracted very directly in to a mass spectrometer. As a consequence, a very high collection efficiency and high mass spectrometric transmission of these ionized species can be achieved. Ion microscopy (lateral mass imaging) can also be accomplished, using either direct imaging ion optics, or by Scanning Ion Imaging utilizing rastered primary beams. Focused ion beams can be used to remove extremely small samples of sputtered material (< 1 ng), or to perform ion imaging with lateral spatial resolutions as low as 50 nm. In SIMS, the greatest limit on useful yield is not secondary ion collection or transmission, but the relative ionization efficiency of a given element (X) to analyte secondary ions, most commonly ^mX^+ or ^mX^-. Further, the relative complexity of the sputtered ion mass spectrum requires sophisticated mass spectrometers (e.g., SHRIMP, IMS 1270 or NanoSIMS50) capable of either energy filtering or high mass resolution to eliminate isobaric interferences - and often incorporating multicollector arrays. SIMS has been used with increasing utility in the microanalytical determination of ?18O (and ?17O) and other light stable isotopes in a variety of natural materials. For example, in minerals such as quartz or calcite, ?18O can routinely be determined with a < 10 ?m lateral resolution (˜1 ng of sample), and reproducibilities of better than ±0.5 per mil. As the total size of the object, or volume sampled, decreases substantially below this level, limits of precision, and stability of charge compensation, cause overall uncertainty to increase. Nevertheless, for many applications, such as cosmochemistry, ?18O can usefully be measured in sub-?m size particles. Other applications where SIMS is particularly advantageous include melt inclusion analysis (B, Cl and Pb isotopes), trace element analysis of marine biomineralization, and carbon isotopes in graphite and carbonate microparticles (early life and biogeochemical studies). New techniques have also been developed for the direct determination of Cl isotopes in dried submarine vent fluid samples (<1 ?l fluid), and 232Th/230Th in Th chemically separated from young volcanic rocks (<10 ng total Th).

Layne, G.

2003-04-01

235

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

236

When other separation techniques fail: compound-specific carbon isotope ratio analysis of sulfonamide containing pharmaceuticals by high-temperature-liquid chromatography-isotope ratio mass spectrometry.  

PubMed

Compound-specific isotope analysis (CISA) of nonvolatile analytes has been enabled by the introduction of the first commercial interface to hyphenate liquid chromatography with an isotope ratio mass spectrometer (LC-IRMS) in 2004, yet carbon isotope analysis of unpolar and moderately polar compounds is still a challenging task since only water as the eluent and no organic modifiers can be used to drive the separation in LC. The only way to increase the elution strength of aqueous eluents in reversed phase LC is the application of high temperatures to the mobile and stationary phases (HT-LC-IRMS). In this context we present the first method to determine carbon isotope ratios of pharmaceuticals that cannot be separated by already existing separation techniques for LC-IRMS, such as reversed phase chromatography at normal temperatures, ion-chromatography, and mixed mode chomatography. The pharmaceutical group of sulfonamides, which is generally mixed with trimethoprim in pharmaceutical products, has been chosen as probe compounds. Substance amounts as low as 0.3 ?g are sufficient to perform a precise analysis. The successful applicability and reproducibility of this method is shown by the analysis of real pharmaceutical samples. The method provides the first tool to study the pharmaceutical authenticity as well as degradation and mobility of such substances in the environment by using the stable isotopic signature of these compounds. PMID:22880688

Kujawinski, Dorothea M; Zhang, Lijun; Schmidt, Torsten C; Jochmann, Maik A

2012-08-27

237

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.

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

2010-01-01

238

Multiple spiking species-specific isotope dilution analysis by molecular mass spectrometry: simultaneous determination of inorganic mercury and methylmercury in fish tissues.  

PubMed

This work demonstrates, for the first time, the applicability of multiple spiking isotope dilution analysis to molecular mass spectrometry exemplified by the speciation analysis of mercury using GC(EI)MS instrumentation. A double spike isotope dilution approach using isotopically enriched mercury isotopes has been applied for the determination of inorganic mercury Hg(II) and methylmercury (MeHg) in fish reference materials. The method is based on the application of isotope pattern deconvolution for the simultaneous determination of degradation-corrected concentrations of methylmercury and inorganic mercury. Mass isotopomer distributions are employed instead of isotope ratios to calculate the corrected concentrations of the Hg species as well as the extent of species degradation reactions. The isotope pattern deconvolution equations developed here allow the calculation of the different molar fractions directly from the GC(EI)MS mass isotopomer distribution pattern and take into account possible impurities present in the spike solutions employed. The procedure has been successfully validated with the analysis of two different certified reference materials (BCR-464 and DOLT-4) and with the comparison of the results obtained by GC(ICP)MS. For the tuna fish matrix (BCR-464), no interconversion reactions were observed at the optimized conditions of open focused microwave extraction at 70 degrees C during 8 min. However, significant demethylation was found under the same conditions in the case of the certified dogfish liver DOLT-4. Methylation and demethylation factors were confirmed by GC(ICP)MS. Transformation reactions have been found to depend on the sample matrix and on the derivatization reagent employed. Thus, it is not possible to recommend optimum extraction conditions suitable for all types of matrices demonstrating the need to apply multiple spiking methodologies for the determination of MeHg and Hg(II) in biological samples. Double spike isotope dilution analysis methodologies using widespread GC(EI)MS instrumentation are proposed here for the routine analysis of inorganic mercury and methylmercury in fish samples. The estimated method detection limits were below 10 ng g(-1) for both mercury species. Precision was evaluated for the concentrations present in the certified reference materials (CRMs) which vary from 0.1 to 5 microg g(-1), achieving values of coefficients of variation ranging from 7% to 2%. The concentrations obtained in both CRMs analyzed were in excellent agreement with the certified values, demonstrating the accuracy of the method at these concentration levels. PMID:20192179

Castillo, Angel; Rodríguez-González, Pablo; Centineo, Giuseppe; Roig-Navarro, Antoni Francesc; García Alonso, J Ignacio

2010-04-01

239

[Photon burst mass spectrometry technique.] Final report  

SciTech Connect

The basic tools have been developed and demonstrated for selective detection of Kr isotopes in the Photon Burst Mass Spectrometry technique. The effort is divided into: photon burst measurements on Mg{sup +} demonstrating high isotopic selectivity, charge exchange of Kr{sup +} with Cs and Rb to produce metastable Kr atoms, development of a diode laser system for photon burst detection of Kr{sup +}, and measurements of photon bursts detection of Kr.

Fairbank, W.M. Jr [Colorado State Univ., Fort Collins, CO (United States). Dept. of Physics

1996-04-01

240

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

241

Identification of honokiol metabolites in rats by the method of stable isotope cluster technique and ultra-high performance liquid chromatography/quadrupole-time-of-flight mass spectrometry.  

PubMed

Honokiol, a natural molecule isolated from Magnolia officinalis Rehd. et Wils., is widely known as an antitumor agent. In present work, an analysis of in vivo biotransformation and metabolites of honokiol has been performed by a combined method based on stable isotope cluster technique with honokiol-[(13)C6]-labeled and ultra-high performance liquid chromatography/quadrupole-time-of-flight-mass spectrometry (UHPLC/Q-TOF-MS). The metabolites could be easily identified by the determination of a chromatographically co-eluted pair of isotopomers (MS doublet peaks) with similar peak intensities and mass difference corresponding to that between isotope-labeled and non-isotope-labeled honokiol. A total of eighteen metabolites were detected and tentatively identified, fourteen of which were reported for the first time. The results indicated that the main metabolic pathways of honokiol in rats were hydroxylation, methylation, sulfation and glucuronidation. This study provided the first essential information on biotransformation and metabolites of honokiol in rats, which was very useful for further pharmacological and clinical studies of honokiol as a potent drug candidate. PMID:23792368

Lai, Huijun; Tang, Minghai; Liu, Juan; Dong, Yinfeng; Qiu, Neng; Li, Shucai; Ma, Liang; Yang, Jianhong; Song, Hang; Zhang, Yongkui; Peng, Aihua; Chen, Lijuan

2013-05-28

242

High-resolution direct infusion-based mass spectrometry in combination with whole 13C metabolome isotope labeling allows unambiguous assignment of chemical sum formulas.  

PubMed

A new strategy for direct infusion-based metabolite analysis employing a combination of high-resolution mass spectrometry and (13)C-isotope labeling of entire metabolomes is described. Differentially isotope labeled metabolite extracts from otherwise identically grown reference plants were prepared and infused into a Fourier transform ion cyclotron resonance mass spectrometer. The derived accurate mass lists from each extract were searched, using an in-house-developed database search tool, against a number of comprehensive metabolite databases. Comparison of the retrieved chemical formulas from both, the (12)C and (13)C samples, leads to two major advantages compared to nonisotope-based metabolite fingerprinting: first, removal of background contaminations from the result list, due to the (12)C/(13)C peak pairing principle and therefore positive identification of compounds of true biological origin; second, elimination of ambiguity in chemical formula assignment due to the same principle, leading to the clear association of one measured mass to only one chemical formula. Applying this combination of strategies to metabolite extracts of the model plant Arabidopsis thaliana therefore resulted in the reproducible identification of more than 1000 unambiguous chemical sum formulas of biological origin of which more than 80% have not been associated to Arabidopsis before. PMID:19072260

Giavalisco, Patrick; Hummel, Jan; Lisec, Jan; Inostroza, Alvaro Cuadros; Catchpole, Gareth; Willmitzer, Lothar

2008-12-15

243

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

PubMed

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

Hattori, M; Hirata, T

2001-06-01

244

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

245

Can we use the CO2 concentrations determined by continuous-flow isotope ratio mass spectrometry from small samples for the Keeling plot approach?  

PubMed

A common method to estimate the carbon isotopic composition of soil-respired air is to use Keeling plots (delta(13)C versus 1/CO2 concentration). This approach requires the precise determination of both CO2 concentration ([CO2]), usually measured with an infrared gas analyser (IRGA) in the field, and the analysis of delta(13)C by isotope ratio mass spectrometry (IRMS) in the laboratory. We measured [CO2] with an IRGA in the field (n = 637) and simultaneously collected air samples in 12 mL vials for analysis of the 13C values and the [CO2] using a continuous-flow isotope ratio mass spectrometer. In this study we tested if measurements by the IRGA and IRMS yielded the same results for [CO2], and also investigated the effects of different sample vial preparation methods on the [CO2] measurement and the thereby obtained Keeling plot results. Our results show that IRMS measurements of the [CO2] (during the isotope analysis) were lower than when the [CO2] was measured in the field with the IRGA. This is especially evident when the sample vials were not treated in the same way as the standard vials. From the three different vial preparation methods, the one using N2-filled and overpressurised vials resulted in the best agreement between the IRGA and IRMS [CO2] values. There was no effect on the (13)C-values from the different methods. The Keeling plot results confirmed that the overpressurised vials performed best. We conclude that in the cases where the ranges of [CO2] are large (>300 ppm; in our case it ranged between 70 and 1500 ppm) reliable estimation of the [CO2] with small samples using IRMS is possible for Keeling plot application. We also suggest some guidelines for sample handling in order to achieve proper results. PMID:19009520

Joos, Ottmar; Saurer, Matthias; Heim, Alexander; Hagedorn, Frank; Schmidt, Michael W I; Siegwolf, Rolf T W

2008-12-01

246

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.

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

2010-01-01

247

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

2010-03-06

248

Effective elimination of organic matter interference in boron isotopic analysis by thermal ionization mass spectrometry of coral/foraminifera: micro-sublimation technology combined with ion exchange.  

PubMed

In order to better estimate the effectiveness of micro-sublimation technology on the elimination of organic matter interference during boron isotopic analysis, a series of improved experiments was carried out using simple apparatus. Recovery rates after micro-sublimation were measured for boric acid solutions with different B contents or different B/organic matter ratios. The improved micro-sublimation procedure combined with ion-exchange technology was then used to test natural samples (coral and foraminifera) for the separation of boron. Our results show that the time taken for 100% recovery of different amounts of B differed and that the proportions of B/organic matter within the natural organic matter have little effect on the relationship between the recovery rates of B and the micro-sublimation times. The experiments further confirm that the organic matter does indeed have an effect on boron isotope analyses by positive thermal ionization mass spectrometry and that the use of micro-sublimation can effectively remove interferences from the organic matter during boron isotopic analysis. PMID:21337635

He, Maoyong; Xiao, Yingkai; Ma, Yunqi; Jin, Zhangdong; Xiao, Jun

2011-03-30

249

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

SciTech Connect

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

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

1985-12-01

250

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

SciTech Connect

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

Bandy, A.R.; Thornton, D.C.; Driedger, A.R. III [Drexel Univ., Philadelphia, PA (United States)

1993-12-01

251

The assay of pterostilbene in spiked matrices by liquid chromatography tandem mass spectrometry and isotope dilution method.  

PubMed

Pterostilbene (trans-3,5-dimethoxy-4-hydroxystilbene) is an active component found in several plant species, exhibiting important pharmacological properties. A new and reliable method of assaying this phyto compound in various matrices is presented; the assay is based on (1) the selectivity of liquid chromatography (LC) hyphenated with electrospray ionisation (ESI), (2) the specificity of a two-step mass spectrometric analysis (MS/MS) and (3) the accuracy of the isotope dilution method. The labelled analogue may be conveniently synthesised in a few steps. The sensitivity of the method is confirmed by the very low limit of detection (LOD) and limit of quantitation (LOQ) values achieved in the assay of pterostilbene in two distinct fortified matrices, and is further supported by the observed accuracy values. PMID:20198601

Mazzotti, Fabio; Di Donna, Leonardo; Benabdelkamel, Hicham; Gabriele, Bartolo; Napoli, Anna; Sindona, Giovanni

2010-04-01

252

MALDI Imaging Mass Spectrometry  

PubMed Central

A decade after its inception, MALDI imaging mass spectrometry has become a unique technique in the proteomics arsenal for biomarker hunting in a variety of diseases. At this stage of development, it is important to ask whether we can consider this technique to be sufficiently developed for routine use in a clinical setting or an indispensable technology used in translational research. In this report, we consider the contributions of MALDI imaging mass spectrometry and profiling technologies to clinical studies. In addition, we outline new directions that are required to align these technologies with the objectives of clinical proteomics, including: 1) diagnosis based on profile signatures that complement histopathology, 2) early detection of disease, 3) selection of therapeutic combinations based on the individual patient's entire disease-specific protein network, 4) real time assessment of therapeutic efficacy and toxicity, 5) rational redirection of therapy based on changes in the diseased protein network that are associated with drug resistance, and 6) combinatorial therapy in which the signaling pathway itself is viewed as the target rather than any single “node” in the pathway.

Franck, Julien; Arafah, Karim; Elayed, Mohamed; Bonnel, David; Vergara, Daniele; Jacquet, Amelie; Vinatier, Denis; Wisztorski, Maxence; Day, Robert; Fournier, Isabelle; Salzet, Michel

2009-01-01

253

Deuterium\\/hydrogen ratio analysis of thymol, carvacrol, ?-terpinene and p-cymene in thyme, savory and oregano essential oils by gas chromatography–pyrolysis–isotope ratio mass spectrometry  

Microsoft Academic Search

Isotope ratio mass spectrometry online coupled with capillary gas chromatography (GC–Py–IRMS) on column INNOWAX is used in the origin specific analysis and the authenticity control of the phenolic essential oils (EOs). Isotopic data ?2HV-SMOW of thymol and carvacrol in natural essential oils were evidently more depleted than synthetic products (from ?49 to 7‰ for thymol and ?61‰ for carvacrol). ?2HV-SMOW

Tran-Thi Nhu-Trang; Hervé Casabianca; Marie-Florence Grenier-Loustalot

2006-01-01

254

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

255

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

NASA Astrophysics Data System (ADS)

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

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

2009-11-01

256

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

2006-07-26

257

A rapid, sensitive method for the quantitation of specific metabolites of sulfur mustard in human urine using isotope-dilution gas chromatography-tandem mass spectrometry.  

PubMed

Sulfur mustard agent (HD) (2,2'-dichloroethyl sulfide), a Schedule I compound on the Chemical Weapons Convention Schedule of Chemicals, remains a public health concern because it is simple to synthesize and it is in the chemical weapon stockpiles of several countries. A sensitive, rapid, accurate, and precise method was developed to quantitate trace levels of 1,1'-sulfonylbis [2-(methylthio) ethane] (SBMTE) in human urine as a means of assessing exposure to HD. The method used immobilized liquid-liquid extraction with diatomaceous earth, followed by the analysis of the urine extract using isotope-dilution gas chromatography-tandem mass spectrometry. Relative standard deviations were less than 8.6% at 1 ng/mL and 3.6% at 20 ng/mL. The limit of detection for SBMTE was 0.038 ng/mL in 0.5 mL of urine. PMID:15239853

Young, Carrie L; Ash, Doris; Driskell, W J; Boyer, Anne E; Martinez, Rodolfo A; Silks, L A; Barr, John R

258

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

PubMed

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

Wang, Jian-Hua; Guo, Cui

2010-07-01

259

Mass Spectrometry and Protein Analysis  

NSDL National Science Digital Library

Mass spectrometry is a central analytical technique for protein research and for the study of biomolecules in general. Driven by the need to identify, characterize, and quantify proteins at ever increasing sensitivity and in ever more complex samples, a wide range of new mass spectrometryâÂÂbased analytical platforms and experimental strategies have emerged. Here we review recent advances in mass spectrometry instrumentation in the context of current and emerging research strategies in protein science.

Bruno Domon (ETH Zurich;Institute of Molecular Systems Biology); Ruedi Aebersold (University of Zurich;Faculty of Sciences/Institute of Molecular Systems Biology)

2006-04-14

260

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

PubMed Central

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

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

2012-01-01

261

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.

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

2011-01-01

262

The Absolute Isotopic Composition of Zn in Terrestrial Materials Determined Using Double Spike Thermal Ionization Mass Spectrometry  

Microsoft Academic Search

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

O. Y. Ghidan; R. D. Loss

2008-01-01

263

Separating Autotrophic and Heterotrophic Contributions to Soil Respiration in Maize-Based Agroecosystems Using Stable Carbon Isotope Ratio Mass Spectrometry.  

NASA Astrophysics Data System (ADS)

Any effort to establish a carbon budget for a growing crop by means of a thorough accounting of all C sources and sinks will require the ability to discriminate between autotrophic and heterotrophic contributions to soil surface CO2 flux. Autotrophic soil respiration (Ra) is defined as combined root respiration and the respiration of soil microorganisms residing in the rhizosphere and using root-derived carbohydrates as an energy source, while heterotrophic respiration (Rh) is defined as the respiration of soil microorganisms and macroorganisms not directly under the influence of the live root system and using SOM as an energy source. We partition soil surface CO2 flux into its autotrophic and heterotrophic components by combining root exclusion with stable carbon isotope techniques in production scale (~65 ha) maize-based agroecosystems. After flux measurements, small chambers are placed on collars in both root excluded shields and in non-root excluded soil, ambient headspace CO2 is removed using a soda lime trap, and soil-respired C is allowed to collect in the chambers. Soil respiration samples are then collected in 12mL evacuated exetainers and analyzed for ?13C by means of a Finnigan Delta-S isotope ratio mass spectrometer interfaced with a Thermo Finnigan GasBench II and a cryogenic trap to increase CO2 concentration. These ?13C measurements were made throughout the 2005 growing season in maize fields representing three agroecosystems: irrigated continuous maize, irrigated maize-soybean rotation, and rainfed maize soybean rotation. Estimates of autotrophic and heterotrophic soil respiration along with other results of this study will be presented.

Amos, B.; Walters, D. T.; Madhavan, S.; Arkebauer, T. J.; Scoby, D. L.

2005-12-01

264

Glycomics and Mass Spectrometry  

NASA Astrophysics Data System (ADS)

There is an increasing body of evidence indicating that glycans are implicated in numerous biological processes such as cell-cell interactions, intracellular signaling, and immune response. Glycomics emerges from the necessity to understand the mechanisms underlying the interactions responsible for these activities. The term glycomics is used to describe experimental approaches to studying the structure and function of the glycomes of fluids, cells, tissues, organs etc. Glycomics embraces a variety of technologies amongst which mass spectrometry (MS) plays a pivotal role because it is the method of choice for defining the primary structures of glycopolymers. This chapter provides an insight into MS -based structural strategies that are best suited to studying complex glycomes.

Dell, Anne; Jang-Lee, Jihye; Pang, Poh-Choo; Parry, Simon; Sutton-Smith, Mark; Tissot, Berangere; Morris, Howard R.; Panico, Maria; Haslam, Stuart M.

265

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

SciTech Connect

A ThermoFisher 'Triton' multi-collector thermal ionization mass spectrometer (MC-TIMS) was evaluated for trace and ultra-trace level isotoperatioanalysis 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 (10{sup 4} atoms to 10{sup 5} atoms) for {sup 239-242+244}Pu, {sup 233+236}U, {sup 241-243}Am, {sup 89,90}Sr, and {sup 134,135,137}Cs, and {le} 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 x 10{sup 6} or better using a SEM are reported here. Precisions of RSD {approx} 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, Stefan [New Brunswick Laboratory, Argonne, IL; Riciputi, Lee R [Los Alamos National Laboratory (LANL); Bostick, Debra A [ORNL; Turgeon, Steven [University of Alberta, Edmondton, Canada; McBay, Eddie H [ORNL; Lavelle, Mark [ORNL

2009-01-01

266

Measurement of testosterone and its 5-alfa-reduced metabolites in human prostatic tissue using isotope dilution mass spectrometry.  

PubMed

5 alpha-Dihydrotestosterone (DHT) has been widely measured in human prostatic tissue using RIA since it is found to be involved in pathogenesis of human prostatic hyperplasia (BHP) and to be the best index for the follow-up of patients affected by prostatic cancer under endocrine treatment. A GC/MS method for the simultaneous determination of testosterone (T), dihydrotestosterone (DHT), 5 alpha-androstan-3 alpha,17 beta-diol (3 alpha-diol) and 5 alpha-androstan-3 beta-17 beta-diol (3 beta-diol) in prostatic tissue was developed based on the isotopic dilution technique. Trideuterated internal standards of each compound were previously synthesized in our laboratory. After previous extraction and purification on Sep-Pak C-18 cartridges and Lipidex DEAP columns, T and its metabolites were measured as heptafluorobutyric esters (HFB). Quantitative analysis was performed on a VG 7070 EQ mass spectrometer equipped with a fused silica capillary column using the Selected Ion Monitoring technique. Steroid values (means +/- SD; ng/g tissue) found in 9 human hypertrophic prostates were: T, 0.71 +/- 0.43; DHT, 4.46 +/- 1.41; 3 alpha-diol, 0.34 +/- 0.23; 3 beta-diol, 0.14 +/- 0.32. PMID:3807362

Moneti, G; Costantini, A; Guarna, A; Salerno, R; Pazzagli, M; Natali, A; Goti, A; Serio, M

1986-11-01

267

13C-Isotope ratio mass spectrometry as a potential tool for the forensic analysis of white architectural paint: a preliminary study.  

PubMed

Paints have a dual role in society, to protect materials from environmental agents such as ultraviolet light, moisture and oxygen, and to make painted materials look more attractive. Variability in paint samples is often due to binder and pigment type within the sample. The most common resin used in decorative paints is drying oil alkyd resin, which incorporates soybean oil and vinyl acrylic based latexes. Traditional analytical methods used by forensic scientists may be able to say whether two paint samples are indistinguishable but cannot conclusively say that they both originate from the same source. To find out if isotopic composition can provide an added dimension of information, 28 different white architectural paints were analysed for (13)C abundance using isotope ratio mass spectrometry. In addition, variations in application, drying time and thickness were also investigated to assess the discriminatory power of (13)C data from white paints with an unknown history. Preliminary results indicate that this method could aid screening of paint samples. PMID:15945023

Reidy, L J; Meier-Augenstein, W; Kalin, R M

2005-01-01

268

Analysis of estrogenic compounds in environmental and biological samples by liquid chromatography-tandem mass spectrometry with stable isotope-coded ionization-enhancing reagent.  

PubMed

A sensitive and reliable stable isotope labeling technology was developed for the determination of estrogenic compounds in environmental and biological samples based on the derivatization of estrogenic compounds with 10-methyl-acridone-2-sulfonyl chloride (d(0)-MASC) and its deuterated counterpart d(3)-MASC. The labeling reaction of MASC with estrogenic compounds is simple and robust and can be carried out under mild conditions within 5 min. Internal standard-based quantification was achieved by this labeling strategy without the need of using expensive internal standard analogy to every analyte of interest. Meanwhile, the sensitivity obtained by liquid chromatography-tandem mass spectrometry (LC-MS/MS) was enhanced by 2-3 orders of magnitude compared to the underivatized counterparts. Application of the stable isotope labeling technology in relative and absolute quantification of estrogenic compounds in complicated samples indicated that the labeling strategy was effective in overcoming matrix effects. The proposed method was successfully applied to the analysis estrogenic compounds in different environmental and biological samples with high sensitivity and accuracy. PMID:23374368

Zhang, Shijuan; You, Jinmao; Ning, Shujing; Song, Cuihua; Suo, You-Rui

2013-01-16

269

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

2012-04-30

270

Structural Analysis of Guanylyl Cyclase-Activating Protein-2 (GCAP-2) Homodimer by Stable Isotope-Labeling, Chemical Cross-Linking, and Mass Spectrometry  

NASA Astrophysics Data System (ADS)

The topology of the GCAP-2 homodimer was investigated by chemical cross-linking and high resolution mass spectrometry. Complementary conducted size-exclusion chromatography and analytical ultracentrifugation studies indicated that GCAP-2 forms a homodimer both in the absence and in the presence of Ca2+. In-depth MS and MS/MS analysis of the cross-linked products was aided by 15 N-labeled GCAP-2. The use of isotope-labeled protein delivered reliable structural information on the GCAP-2 homodimer, enabling an unambiguous discrimination between cross-links within one monomer (intramolecular) or between two subunits (intermolecular). The limited number of cross-links obtained in the Ca2+-bound state allowed us to deduce a defined homodimeric GCAP-2 structure by a docking and molecular dynamics approach. In the Ca2+-free state, GCAP-2 is more flexible as indicated by the higher number of cross-links. We consider stable isotope-labeling to be indispensable for deriving reliable structural information from chemical cross-linking data of multi-subunit protein assemblies.

Pettelkau, Jens; Thondorf, Iris; Theisgen, Stephan; Lilie, Hauke; Schröder, Thomas; Arlt, Christian; Ihling, Christian H.; Sinz, Andrea

2013-09-01

271

Tracing Cationic Nutrients from Xylem into Stem Tissue of French Bean by Stable Isotope Tracers and Cryo-Secondary Ion Mass Spectrometry[W][OA  

PubMed Central

Fluxes of mineral nutrients in the xylem are strongly influenced by interactions with the surrounding stem tissues and are probably regulated by them. Toward a mechanistic understanding of these interactions, we applied stable isotope tracers of magnesium, potassium, and calcium continuously to the transpiration stream of cut bean (Phaseolus vulgaris) shoots to study their radial exchange at the cell and tissue level with stem tissues between pith and phloem. For isotope localization, we combined sample preparation with secondary ion mass spectrometry in a completely cryogenic workflow. After 20 min of application, tracers were readily detectable to various degrees in all tissues. The xylem parenchyma near the vessels exchanged freely with the vessels, its nutrient elements reaching a steady state of strong exchange with elements in the vessels within 20 min, mainly via apoplastic pathways. A slow exchange between vessels and cambium and phloem suggested that they are separated from the xylem, parenchyma, and pith, possibly by an apoplastic barrier to diffusion for nutrients (as for carbohydrates). There was little difference in these distributions when tracers were applied directly to intact xylem via a microcapillary, suggesting that xylem tension had little effect on radial exchange of these nutrients and that their movement was mainly diffusive.

Metzner, Ralf; Schneider, Heike Ursula; Breuer, Uwe; Thorpe, Michael Robert; Schurr, Ulrich; Schroeder, Walter Heinz

2010-01-01

272

Determination of the alkylpyrazine composition of coffee using stable isotope dilution-gas chromatography-mass spectrometry (SIDA-GC-MS).  

PubMed

A stable isotope dilution analysis based on gas chromatography-mass spectrometry analysis (SIDA-GC-MS) was developed for the quantitative analysis of 12 alkylpyrazines found in commercially available coffee samples. These compounds contribute to coffee flavor. The accuracy of this method was tested by analyzing model mixtures of alkylpyrazines. Comparisons of alkylpyrazine-concentrations suggested that water as extraction solvent was superior to dichloromethane. The distribution patterns of alkylpyrazines in different roasted coffees were quite similar. The most abundant alkylpyrazine in each coffee sample was 2-methylpyrazine, followed by 2,6-dimethylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, and 2,3,5-trimethylpyrazine, respectively. Among the alkylpyrazines tested, 2,3-dimethylpyrazine, 2-ethyl-3-methylpyrazine, 2-ethyl-3,6-dimethylpyrazine, and 2-ethyl-3,5-dimethylpyrazine revealed the lowest concentrations in roasted coffee. By the use of isotope dilution analysis, the total concentrations of alkylpyrazines in commercially available ground coffee ranged between 82.1 and 211.6 mg/kg, respectively. Decaffeinated coffee samples were found to contain lower amounts of alkylpyrazines than regular coffee samples by a factor of 0.3-0.7, which might be a result of the decaffeination procedure. PMID:23745606

Pickard, Stephanie; Becker, Irina; Merz, Karl-Heinz; Richling, Elke

2013-06-20

273

Determination of very low stable isotope enrichments of [(2)H(5)]-phenylalanine in chicken liver using liquid chromatography-tandem mass spectrometry (LC-MS/MS).  

PubMed

Stable isotope labeled amino acids are frequently used to examine nutritive effects on protein synthesis. This technique is characterized by tracing the incorporation of the label into newly synthesized proteins. In the present investigation, a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for the determination of very low enrichment of protein-bound l-[(2)H(5)]-phenylalanine ([(2)H(5)]-phe) in chicken liver. The LC-MS/MS measurements were carried out in positive atmospheric pressure chemical ionization (APCI) mode. Two mass transitions each for [(2)H(5)]-phe (171.1/125.1 and 171.1/106.1) and l-phenylalanine (phe) (166.1/91.1 and 166.1/93.1) were chosen for quantification and qualification. Due to the high excesses of phe, less sensitive transitions were chosen in the case of phe. The separation was carried out on a phenyl-hexyl column using 0.1% formic acid as eluent A and methanol as eluent B. The method was calibrated with calibration standard solutions in the range of 0.01-0.5 mole percent excess (MPE). Linear regression analysis led to coefficients of determination (r(2)) greater than 0.9995. The method was applied on liver samples from experiments investigating nutritive effects on tissue protein synthesis in broiler chickens. These samples were analyzed with a gas chromatography-mass spectrometry (GC-MS) method and reanalyzed with the developed LC-MS/MS method one year later. Compared to GC-MS, the main advantages of the LC-MS/MS method are its higher selectivity as well as the elimination of the need to convert and derivatize the samples prior to measuring. PMID:23217318

Wilkerling, Katrin; Valenta, Hana; Kersten, Susanne; Dänicke, Sven

2012-11-03

274

Nanopore Mass Spectrometry  

NASA Astrophysics Data System (ADS)

We report on the design, construction, and characterization of a nanopore-based ion source for mass spectrometry. Our goal is to field-extract ions directly from solution into the high vacuum to enable unit collection efficiency and temporal resolution of sequential ion emissions for DNA sequencing. The ion source features a capillary whose tip, measuring tens to hundreds of nanometers in inner diameter, is situated in the vacuum ˜ 1.5 cm away from an extractor electrode. The capillary was filled with conductive solution and voltage-biased relative to the extractor. Applied voltages of hundreds of volts extracted tens to hundreds of nA of current from the tip. A mass analysis of the extracted ions showed primarily singly charged clusters comprising the cation or anion solvated by several solvent molecules. Our interpretation of these results, based on the works of Taylor and of de la Mora, is that the applied electric stresses distort the fluid meniscus into a Taylor cone, where electric fields reach ˜ 1V/nm and induce significant ion evaporation. Accordingly, the abundances of extracted ionic clusters resemble a Boltzmann distribution.

Bush, Joseph; Mihovilovic, Mirna; Maulbetsch, William; Frenchette, Layne; Moon, Wooyoung; Pruitt, Cole; Bazemore-Walker, Carthene; Weber, Peter; Stein, Derek

2013-03-01

275

Ultratrace Uranium Fingerprinting with Isotope Selective Laser Ionization Spectrometry  

SciTech Connect

Uranium isotope ratios can provide source information for tracking uranium contamination in a variety of fields, ranging from occupational bioassay to monitoring aftereffects of nuclear accidents. We describe the development of Isotope Selective Laser Ionization Spectrometry (ISLIS) for ultratrace measurement of the minor isotopes 234U, 235U, and 236U with respect to 238U. Optical isotopic selectivity in three-step excitation with single-mode continuous wave lasers is capable of measuring the minor isotopes at relative abundances below 1 ppm, and is not limited by isobaric interferences such as 235UH+ during measurement of 236U. This relative abundance limit approaches the threshold for measurement of uranium minor isotopes with conventional mass spectrometry, typically 10-7, but without mass spectrometric analysis of the laser-created ions. Uranyl nitrate standards from an international blind comparison were used to test analytical performance for different isotopic compositions and with quantities ranging from 11 ng to 10 µg total uranium. Isotopic ratio determination was demonstrated over a linear dynamic range of 7 orders of magnitude with a few percent relative precision and detection limits below 500 fg for the minor isotopes.

Ziegler, Summer L.; Bushaw, Bruce A.

2008-08-01

276

Development of N-acetyl methyl ester derivatives for the determination of delta13C values of amino acids using gas chromatography-combustion- isotope ratio mass spectrometry.  

PubMed

A novel derivatization procedure, N-acetyl methyl (NACME) esterification, was developed to improve the accuracy and precision of amino acid delta13C value determination using gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS). Standard mixtures of 15 protein amino acids were converted to NACME and N-acetyl-isopropyl (NAIP) esters; the latter established derivative was employed for comparison purposes. Both procedures yielded baseline-resolved peaks for all 15 amino acids when GC columns coated with polar stationary phases were employed. For NACME esters, the methylation conditions governed reaction yields, with highest yields observed when a 1 h, 70 degrees C methylation procedure (anhydrous MeOH/acetyl chloride, 25:4, v/v) was performed. The mean derivatization yields expressed relative to an underivatized coinjected standard (n-nonadecane) for both NACME and NAIP esters were identical. Likewise, the mean kinetic isotope effects (KIEs) were not significantly different (KIE(NACME) = 1.036; KIE(NAIP) = 1.038) and were shown in both cases to be reproducible. The mean reproducibility obtained from 15 replicates (3 x batches of 5) of both derivatives was strong (mean STDV(NACME) = 0.3 per thousand and STDV(NAIP) = 0.4 per thousand). The isotopic robustness of both derivatization procedures was observed over a concentration range of 52,500 microg of amino acid. NACME esters displayed low errors (+/-0.6 per thousand for phenylalanine to +/-1.1 per thousand for serine) due to the higher sample-to-derivative carbon ratio of this derivative. Finally, the integrity of the new NACME procedure was confirmed through analysis of diet and bone collagen amino acids of rats reared on C3 or C4 diets, which indicated the high degree of both accuracy and precision of the delta13C values obtained for individual amino acids. PMID:17973497

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

2007-11-01

277

Selective ultra trace isotope determination in environmental and biomedical studies by high-resolution resonance ionization mass spectrometry  

Microsoft Academic Search

The precise determination of relative abundances of ultra trace isotopes in the range below 10-9 is of importance for a wide spectrum of applications in fields like environmental protection, cosmo-chemistry, bio-medical tracer studies or geological and geo-chronological investigations. The necessary high isotopic selectivity, rather complete isobaric suppression and good overall efficiency for these investigations is provided by high-resolution resonance ionization

Klaus Wendt; K. Blaum; Ch. Geppert; P. Mueller; N. Trautmann

2002-01-01

278

High precision Hf isotope measurements of MORB and OIB by thermal ionisation mass spectrometry: insights into the depleted mantle  

Microsoft Academic Search

The existing Hf isotope database for mid-ocean ridge basalts (MORB) is limited in both quantity and precision. Nevertheless, in Hf–Nd isotope space, MORBs show a wide variation in 176Hf\\/177Hf over a relatively restricted range in 143Nd\\/144Nd. The highest 176Hf\\/177Hf ratios (?0.283355) within the MORB range are restricted to just four samples (<6.5% of total). Of these high 176Hf\\/177Hf MORBs, three

G. M. Nowell; P. D. Kempton; S. R. Noble; J. G. Fitton; A. D. Saunders; J. J. Mahoney; R. N. Taylor

1998-01-01

279

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)  

Microsoft Academic Search

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources

Christopher F. Brown; P. Evan Dresel; Keith N. Geiszler; Orville T. Farmer

2006-01-01

280

Accelerator mass spectrometry as a bioanalytical tool for nutritional research  

SciTech Connect

Accelerator Mass Spectrometry is a mass spectrometric method of detecting long-lived radioisotopes without regard to their decay products or half-life. The technique is normally applied to geochronology, but recently has been developed for bioanalytical tracing. AMS detects isotope concentrations to parts per quadrillion, quantifying labeled biochemicals to attomole levels in milligram- sized samples. Its advantages over non-isotopeic and stable isotope labeling methods are reviewed and examples of analytical integrity, sensitivity, specificity, and applicability are provided.

Vogel, J.S.; Turteltaub, K.W.

1997-09-01

281

Stable-Isotope Labeled Hydrophobic Hydrazide Reagents for the Relative Quantification of N-linked Glycans by Electrospray Ionization Mass Spectrometry  

PubMed Central

This study presents the development of stable-isotope labeled hydrophobic, hydrazide reagents for the relative quantification of N-linked glycans. The P2GPN ‘light’ (12C) and ‘heavy’ (13C6) pair are used to differentially label two N-linked glycan samples. The samples are combined 1:1, separated using HILIC, and then mass differentiated and quantified using mass spectrometry. These reagents have several benefits: 1) impart hydrophobic character to the glycans affording an increase in electrospray ionization efficiency and MS detection; 2) indistinguishable chromatographic, MS, and MS/MS performance of the ‘light’ and ‘heavy’ reagents affording relative quantification; and 3) analytical variability is significantly reduced due to the two samples being mixed together after sample preparation. Obtaining these analytical benefits only requires ~4 hours of sample preparation time. It is shown that these reagents are capable of quantifying changes in glycosylation in simple mixtures, and the analytical variability of the reagents in pooled plasma samples is shown to be less than ±30%. Additionally, the incorporation of an internal standard allows one to account for the difference in systematic error between the two samples due to the samples being processed in parallel and not mixed until after derivatization.

Walker, S. Hunter; Budhathoki-Uprety, Januka; Novak, Bruce M.; Muddiman, David C.

2011-01-01

282

Development of isotope dilution-liquid chromatography tandem mass spectrometry for the accurate determination of fluoroquinolones in animal meat products: optimization of chromatographic separation for eliminating matrix effects on isotope ratio measurements.  

PubMed

Isotope dilution-liquid chromatography/tandem mass spectrometry (ID-LC-MS/MS) has been established as a candidate reference method for the accurate determination of three representative fluoroquinolone antibiotics (enrofloxacin, ciprofloxacin, and norfloxacin) in meat products. Enrofloxacin-d?, ciprofloxacin-¹³C?¹?N, and norfloxacin-d? were used as internal standards. After extraction and SPE clean-up, samples were analyzed by using LC-MS/MS in positive ion mode. We observed that the deuterium-labeled internal standards have slightly different LC retention time from their native analogues, which reduces the benefits of using isotope dilution techniques as ion suppression/enhancement effects caused by co-eluting matrix interferences are not completely compensated. In this study, LC conditions were optimized to minimize matrix effects causing different ionization efficiency between the target analytes and their isotope analogues by separating them from significant matrix interferences. The analytical method was validated by measuring samples (chicken breast, bovine muscle, and porcine muscle) gravimetrically fortified in various levels with the target analytes. The method provided accurate analytical results of the target analytes in the range of 5-50 ?g/kg with the relative expanded uncertainty of 1-5%. PMID:23332302

Lee, Suyoung; Kim, Byungjoo; Kim, Jeongkwon

2012-12-29

283

Continuous Simultaneous Detection in Mass Spectrometry  

SciTech Connect

In mass spectrometry, several advantages can be derived when multiple mass-to-charge values are detected simultaneously. One such advantage is an improved duty cycle, which leads to superior limits of detection, better precision, shorter analysis times, and reduced sample sizes. A second advantage is the ability to reduce correlated noise by taking the ratio of two or more simultaneously collected signals, enabling greatly enhanced isotope ratio data. A final advantage is the elimination of spectral skew, leading to more accurate transient signal analysis. Here, these advantages are demonstrated by means of a novel Faraday-strip array detector coupled to a Mattauch-Herzog mass spectrograph. The same system is used to monitor elemental fractionation phenomena in laser ablation inductively coupled plasma mass spectrometry.

Schilling, G. D.; Andrade, Francisco J.; Barnes IV., James H.; Sperline, Roger P.; Denton, M. Bonner; Barinaga, Charles J.; Koppenaal, David W.; Hieftje, Gary M.

2007-10-15

284

Pitfalls encountered during quantitative determination of 3-alkyl-2-methoxypyrazines in grape must and wine using gas chromatography-mass spectrometry with stable isotope dilution analysis. Comprehensive two-dimensional gas chromatography-mass spectrometry and on-line liquid chromatography-multidimensional gas chromatography-mass spectrometry as potential loopholes.  

PubMed

The analysis of 3-alkyl-2-methoxypyrazines in Vitis vinifera grape must or wine at the low nanogram per liter level failed in several situations when applying a one-dimensional gas chromatographic analysis with mass spectrometric detection (GC-MS). Sample preparation methods such as headspace solid phase microextraction or solid phase extraction were convenient procedures, however lacking extraction selectivity for complex matrices. Analysis by comprehensive two-dimensional gas chromatography with mass spectrometric detection clearly demonstrated the potential for co-elution in such matrices and the risk for erroneous results when applying one-dimensional GC-MS. In one example, matrix problems would have been a challenge even for a comprehensive two-dimensional chromatographic approach with MS detection (GC×GC-MS). A solution to matrix problems was found by protonating the 3-alkyl-2-methoxypyrazines in acidic pH and sample clean-up using solid phase extraction with a mixed-mode polymeric cation-exchange sorbent. Quantification was performed by a stable isotope dilution assay, following analysis by on-line coupled high performance liquid chromatography with multidimensional gas chromatography and detection with mass spectrometry (on-line LC-MDGC-MS). This new approach allowed trace-level analysis of 3-alkyl-2-methoxypyrazines in grape musts and wines and is described for V. vinifera Sauvignon blanc, following 3-alkyl-2-methoxypyrazines concentrations during ripening and in the processed wines. PMID:20637469

Schmarr, Hans-Georg; Ganss, Sebastian; Koschinski, Stefan; Fischer, Ulrich; Riehle, Carmen; Kinnart, Julian; Potouridis, Theodoros; Kutyrev, Maria

2010-06-25

285

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

Microsoft Academic Search

Plastic bags are frequently used to package drugs, explosives and other contraband. There exists, therefore, a requirement in forensic casework to compare bags found at different locations. This is currently achieved almost exclusively by the use of physical comparisons such as birefringence patterns. This paper discusses some of the advantages and shortcomings of this approach, and presents stable isotope ratio

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

2008-01-01

286

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

287

Mass spectrometry of fatty aldehydes  

Microsoft Academic Search

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

Evgeny V. Berdyshev

2011-01-01

288

Influence of relative abundance of isotopes on depth resolution for depth profiling of metal coatings by laser ablation inductively coupled plasma mass spectrometry.  

PubMed

A systematic study on the influence of relative abundance of isotopes of elements in the coating (A(c)) and in the substrate (A(s)) on both shape of time-resolved signals and depth resolution (Delta z) was performed for depth profile analysis of metal coatings on metal substrates by ultraviolet (266 nm) nanosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. Five coated samples with coating thicknesses of the same order of magnitude (20-30 microm) were tested: nickel coating on aluminium, chromium and copper, and steel coated with copper and zinc. A laser repetition rate of 1 Hz and a laser fluence of 21 J cm(-2) were used. Five different depth profile types were established, which showed a clear dependence on A(c)/A(s) ratio. In general, depth profiles obtained for ratios above 1-10 could not be used to determine Delta z. We found that Delta z increased non-linearly with A(c)/A(s) ratio. The best depth profile types, leading to highest depth resolution and reproducibility, were attained in all cases by using the isotopes with low/medium A(c) values and with the highest A(s) values. In these conditions, an improvement of up to 4 times in Delta z values was achieved. The average ablation rates were in the range from 0.55 microm pulse(-1) for copper coating on steel to 0.83 microm pulse(-1) for zinc coating on steel, and the Delta z values were between 2.74 microm for nickel coating on chromium and 5.91 microm for nickel coating on copper, with RSD values about 5-8%. PMID:20188923

Fariñas, Juan C; Coedo, Aurora G; Dorado, Teresa

2009-12-16

289

Biochemical fractionation and stable isotope dilution liquid chromatography-mass spectrometry for targeted and microdomain-specific protein quantification in human postmortem brain tissue.  

PubMed

Synaptic architecture and its adaptive changes require numerous molecular events that are both highly ordered and complex. A majority of neuropsychiatric illnesses are complex trait disorders, in which multiple etiologic factors converge at the synapse via many signaling pathways. Investigating the protein composition of synaptic microdomains from human patient brain tissues will yield valuable insights into the interactions of risk genes in many disorders. These types of studies in postmortem tissues have been limited by the lack of proper study paradigms. Thus, it is necessary not only to develop strategies to quantify protein and post-translational modifications at the synapse, but also to rigorously validate them for use in postmortem human brain tissues. In this study we describe the development of a liquid chromatography-selected reaction monitoring method, using a stable isotope-labeled neuronal proteome standard prepared from the brain tissue of a stable isotope-labeled mouse, for the multiplexed quantification of target synaptic proteins in mammalian samples. Additionally, we report the use of this method to validate a biochemical approach for the preparation of synaptic microdomain enrichments from human postmortem prefrontal cortex. Our data demonstrate that a targeted mass spectrometry approach with a true neuronal proteome standard facilitates accurate and precise quantification of over 100 synaptic proteins in mammalian samples, with the potential to quantify over 1000 proteins. Using this method, we found that protein enrichments in subcellular fractions prepared from human postmortem brain tissue were strikingly similar to those prepared from fresh mouse brain tissue. These findings demonstrate that biochemical fractionation methods paired with targeted proteomic strategies can be used in human brain tissues, with important implications for the study of neuropsychiatric disease. PMID:22942359

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

2012-08-31

290

High-precision D/H measurement from organic mixtures by gas chromatography continuous-flow isotope ratio mass spectrometry using a palladium filter.  

PubMed

Continuous-flow high-precision determination of D/H ratios from an organic mixture is described using gas chromatography coupled to a Pd filter system as an interface for isotope ratio mass spectrometry. A gas chromatograph and combustion and reduction furnaces are connected to a Pd filter via a postcolumn head pressure makeup gas to increase chromatographic sensitivity. This interface is evaluated using benzene as an internal standard in a mixture of ethylbenzene and cyclohexanone in hexane with analyte quantities of < 3 ng (< 300 pg of H). A calibration curve is constructed using four benzene samples over a range of -48 to 372/1000 (delta DSMOW), resulting in an average benzene D/H precision of SD < 5/1000 (delta DSMOW) and deviations of < 4/1000 from the calibration curve. Ethylbenzene and cyclohexanone of a single D enrichment are analyzed as unknowns in three sample mixtures with varying D-enriched benzene and result in precisions of SD < 5/1000. No apparent memory is observed between peaks of differently enriched analytes within the same chromatogram. All results are corrected for ion source nonlinearities characteristic of hydrogen analysis, using the internal peakwise correction algorithm, described previously. A small dependence of isotope ratio on palladium membrane temperature is demonstrated over a range of 4 degrees C; therefore, with tighter control of palladium temperature, precision can probably be improved. The data indicate that this system is useful for rapid continuous-flow IRMS analysis of D/H ratios from organics in complex mixtures characteristic of geological and biological samples. PMID:8794931

Tobias, H J; Brenna, J T

1996-09-01

291

Compound-specific delta18O analyses of neutral sugars in soils using gas chromatography-pyrolysis-isotope ratio mass spectrometry: problems, possible solutions and a first application.  

PubMed

Although gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-Py-IRMS) has allowed us to make online compound-specific delta18O measurements for about the last ten years, this technique has hardly been applied. We tested different pyrolysis reactor designs using standards (vanillin, ethylvanillin, a fatty acid methyl ester and alkanes) in order to optimize the GC-Py-IRMS delta18O measurements. The method was then applied to methylboronic acid (MBA) sugar derivatives (pentoses, 6-deoxyhexoses and hexoses). Plant- and microbial-derived monosaccharides were extracted hydrolytically from litter and topsoils before derivatization. The measured delta18O values of samples and co-analyzed reference material were first drift-corrected by use of regularly discharged pulses of CO reference gas. Secondly, they were corrected for the amount dependence of the delta18O values. Thirdly, the delta18O values were calibrated using the reference material (principle of 'Identical Treatment'), and, finally, a correction was applied by taking the hydrolytically introduced and water-exchangeable oxygen atoms into account. Our results suggest that the delta18O values of plant-derived monosaccharides in litter reflect the climatic conditions of the last year, whereas delta18O values of the respective topsoils reflect the averaged climate signal of the last decades or even centuries. This demonstrates the high potential of the method for palaeoclimate reconstructions. PMID:19844972

Zech, Michael; Glaser, Bruno

2009-11-01

292

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

NASA Astrophysics Data System (ADS)

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

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

2004-10-01

293

Trimester-specific reference intervals for thyroxine and triiodothyronine in pregnancy in iodine-sufficient women using isotope dilution tandem mass spectrometry and immunoassays  

PubMed Central

Background Accurate assessment of the pregnant woman’s thyroid status is critical, for both the initiation of thyroid hormone therapy and for the adjustment of thyroid hormone dose in those already receiving thyroid hormone. Trimester-specific intervals are especially important during pregnancy when thyroid insufficiency may be associated with adverse obstetric outcome and fetal neurodevelopmental deficits. We defined pregnancy-specific reference intervals for thyroxine (T4) and 3,5,3?-triiodothyronine (T3). We used a novel isotope dilution tandem mass spectrometry (LC/MS/MS) method, and compare these to reference intervals obtained by immunoassays (IAs) performed on the same samples. Methods Concentrations of circulating T4 and T3 were measured simultaneously during first, second and third trimesters and postpartum in iodine-sufficient, healthy, singleton pregnancies using API-3000 LC/MS/MS with deuterium-labeled internal standard (l-thyroxine-d2). Immunoassays were conducted on the same samples (T4 Dade Behring RxL, T3 DPC-Immunolite). Results Linear regression is reported for method comparisons; for T4, the slope decreased from r=0.900 in nonpregnant women to 0.802–0.820 during pregnancy. For T3, correlations between LC/MS/MS and immunoassays were weaker in all cases (r=0.407–0.574). Conclusion In this longitudinal study, we established trimester-specific reference intervals for T4 and T3 by LC/MS/MS and compare these to intervals obtained by immunoassays.

Soldin, O.P.; Hilakivi-Clarke, L.; Weiderpass, E.; Soldin, S.J.

2013-01-01

294

An optimised method for the accurate determination of zeranol and diethylstilbestrol in animal tissues using isotope dilution-liquid chromatography/mass spectrometry.  

PubMed

Isotope dilution-liquid chromatography/mass spectrometry (ID-LC/MS) has been established as a candidate reference method for the accurate determination of growth promoters (zeranol, taleranol, and diethylstilbesterol) in raw meat samples. Sample preparation processes including an enzymatic hydrolysis, extraction, and SPE clean-up were optimised. The sensitivity difference of trans- and cis-diethylstilbestrol (isomerizing in sample preparation processes) by the LC/MS was measured by running a trans/cis mixture (ratio measured by a quantitative NMR) with and without sample matrices, and applied for the determination of total diethylstilbestrol. Validity, repeatability, and reproducibility of the analytical method were tested by measuring gravimetrically fortified samples (chicken breast, bovine muscles, and porcine muscle) in a number of different time periods. Measurement results agreed with the fortified values within their uncertainties. The method provided accurate results of the target analytes in the range of 0.05-15 ?g/kg with the relative expanded uncertainty of 2-15%. PMID:23578613

Han, Hyesun; Kim, Byungjoo; Lee, Sueg Geun; Kim, Jeongkwon

2013-02-27

295

Quantification of DNA damage products resulting from deamination, oxidation and reaction with products of lipid peroxidation by liquid chromatography isotope dilution tandem mass spectrometry  

PubMed Central

The analysis of damage products as biomarkers of inflammation has been hampered by a poor understanding of the chemical biology of inflammation, the lack of sensitive analytical methods, and a focus on single chemicals as surrogates for inflammation. To overcome these problems, we developed a general and sensitive liquid chromatographic tandem mass spectrometry (LC/MS-MS) method to quantify, in a single DNA sample, the nucleoside forms of seven DNA lesions reflecting the range of chemistries associated with inflammation: 2?-deoxyuridine, 2?-deoxyxanthosine, and 2?-deoxyinosine from nitrosative deamination; 8-oxo-2?-deoxyguanosine from oxidation; and 1,N2-etheno-2?-deoxyguanosine, 1,N6-etheno-2?-deoxyadenosine, and 3,N4-etheno-2?-deoxycytidine arising from reaction of DNA with lipid peroxidation products. Using DNA purified from cells or tissues under conditions that minimize artifacts, individual nucleosides are purified by HPLC and quantified by isotope-dilution, electrospray ionization LC/MS-MS. The method can be applied to other DNA damage products and requires 4-6 days to complete depending upon the number of samples.

Taghizadeh, Koli; McFaline, Jose L.; Pang, Bo; Sullivan, Matthew; Dong, Min; Plummer, Elaine; Dedon, Peter C.

2009-01-01

296

Analysis of permethrin isomers in composite diet samples by molecularly imprinted solid-phase extraction and isotope dilution gas chromatography-ion trap mass spectrometry.  

PubMed

Determination of an individual's aggregate dietary ingestion of pesticides entails analysis of a difficult sample matrix. Permethrin-specific molecularly imprinted polymer (MIP) solid-phase extraction cartridges were developed for use as a sample preparation technique for a composite food matrix. Vortexing with acetonitrile and centrifugation were found to provide optimal extraction of the permethrin isomers from the composite foods. The acetonitrile (with 1% acetic acid) was mostly evaporated and the analytes reconstituted in 90:10 water/acetonitrile in preparation for molecularly imprinted solid-phase extraction. Permethrin elution was accomplished with acetonitrile and sample extracts were analyzed by isotope dilution gas chromatography-ion trap mass spectrometry. Quantitation of product ions provided definitive identification of the pesticide isomers. The final method parameters were tested with fortified composite food samples of varying fat content (1%, 5%, and 10%) and recoveries ranged from 99.3% to 126%. Vegetable samples with incurred pesticide levels were also analyzed with the given method and recoveries were acceptable (81.0-95.7%). Method detection limits were demonstrated in the low ppb range. Finally, the applicability of the MIP stationary phase to extract other pyrethroids, specifically cyfluthrin and cypermethrin, was also investigated. PMID:19393156

Vonderheide, Anne P; Boyd, Brian; Ryberg, Anna; Yilmaz, Ecevit; Hieber, Thomas E; Kauffman, Peter E; Garris, Sherry T; Morgan, Jeffrey N

2009-04-01

297

Innovative method for carbon dioxide determination in human postmortem cardiac gas samples using headspace-gas chromatography-mass spectrometry and stable labeled isotope as internal standard.  

PubMed

A novel approach to measure carbon dioxide (CO2) in gaseous samples, based on a precise and accurate quantification by (13)CO2 internal standard generated in situ is presented. The main goal of this study was to provide an innovative headspace-gas chromatography-mass spectrometry (HS-GC-MS) method applicable in the routine determination of CO2. The main drawback of the GC methods discussed in the literature for CO2 measurement is the lack of a specific internal standard necessary to perform quantification. CO2 measurement is still quantified by external calibration without taking into account analytical problems which can often occur considering gaseous samples. To avoid the manipulation of a stable isotope-labeled gas, we have chosen to generate in situ an internal labeled standard gas ((13)CO2) on the basis of the stoichiometric formation of CO2 by the reaction of hydrochloric acid (HCl) with sodium hydrogen carbonate (NaH(13)CO3). This method allows a precise measurement of CO2 concentration and was validated on various human postmortem gas samples in order to study its efficiency. PMID:23746406

Varlet, V; Smith, F; de Froidmont, S; Dominguez, A; Rinaldi, A; Augsburger, M; Mangin, P; Grabherr, S

2013-05-01

298

Modified method for determination of sulfur metabolites in plant tissues by stable isotope dilution-based liquid chromatography-electrospray ionization-tandem mass spectrometry.  

PubMed

A wide variety of sulfur metabolites play important roles in plant functions. We have developed a precise and sensitive method for the simultaneous measurement of several sulfur metabolites based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) and (34)S metabolic labeling of sulfur-containing metabolites in Arabidopsis thaliana seedlings. However, some sulfur metabolites were unstable during the extraction procedure. Our proposed method does not allow for the detection of the important sulfur metabolite homocysteine because of its instability during sample extraction. Stable isotope-labeled sulfur metabolites of A. thaliana shoot were extracted and utilized as internal standards for quantification of sulfur metabolites with LC-MS/MS using S-adenosylmethionine (SAM), S-adenosylhomocysteine (SAH), methionine (Met), glutathione (GSH), and glutathione disulfide (GSSG) as example metabolites. These metabolites were detected using electrospray ionization in positive mode. Standard curves were linear (r(2)>0.99) over a range of concentrations (SAM 0.01-2.0?M, SAH 0.002-0.10?M, Met 0.05-4.0?M, GSH 0.17-20.0?M, GSSG 0.07-20.0?M), with limits of detection for SAM, SAH, Met, GSH, and GSSG of 0.83, 0.67, 10, 0.56, and 1.1nM, respectively; and the within-run and between-run coefficients of variation based on quality control samples were less than 8%. PMID:23911527

Chang, Ya-Lan; Hsieh, Chin-Lin; Huang, Yao-Moan; Chiou, Wen-Liang; Kuo, Yueh-Hsiung; Tseng, Mei-Hwei

2013-07-31

299

Isotope dilution high-resolution gas chromatography/high-resolution mass spectrometry method for analysis of selected acidic herbicides in surface water.  

PubMed

In this work, an isotope dilution method for determination of selected acidic herbicides by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS) was developed for surface water samples. Average percent recoveries of native analytes were observed to be between 70.8 and 93.5% and average recoveries of labeled quantification standards [(13)C(6)]2,4-D and [(13)C(6)]2,4,5-T were 85.5 and 101%, respectively. Using this method, detection limits of 0.05 ng/L for dicamba, MCPA, MCPP, and triclopyr, and 0.5 ng/L for 2,4-D were routinely achieved. The method was applied to measuring the concentration of these analytes in surface water samples collected from five sampling locations in the Lower Fraser Valley region of British Columbia, Canada. All of the herbicides monitored were detected at varying levels in the surface water samples collected. The highest concentrations detected for each analyte were 345 ng/L for 2,4-D, 317 ng/L for MCPA, 271 ng/L for MCPP, 15.7 ng/L for dicamba, and 2.18 ng/L for triclopyr. Average detection frequencies of the herbicides were 95% for MCPA, 80% for MCPP, 70% for dicamba, 65% for 2,4-D, and 46% for triclopyr. Seasonal variations of herbicide levels are also discussed. PMID:16956613

Woudneh, Million B; Sekela, Mark; Tuominen, Taina; Gledhill, Melissa

2006-09-07

300

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

301

High-precision direct determination of the 87Sr\\/ 86Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry  

Microsoft Academic Search

We describe a precise and accurate method for the direct determination of the 87Sr\\/86Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method is validated by the comparative analysis of the same water with and without cation-exchange resin purification. The work indicates that isobarically interfering elements can be corrected

Yue-Heng Yang; Fu-Yuan Wu; Lie-Wen Xie; Jin-Hui Yang; Yan-Bin Zhang

2011-01-01

302

Application of routine estimation of Pb isotopic ratios by inductively coupled plasma mass spectrometry for studying the Pb origin in hair of children living in polluted areas. A pilot study  

Microsoft Academic Search

The analysis of 204Pb, 206Pb, 207Pb and 208Pb isotope ratios for environmental Pb markers (leaded gasoline, air-borne particulate matter, house window dust) and hair of children was undertaken by the routine quadrupole inductively coupled argon plasma mass spectrometry (Q-ICP-MS). Hair samples collected from 10-year-old children living in Krakow in 1995 and 35 randomly selected children, aged 11, both sexes were

H. Barton; Z. Zachwieja; S. D'Ilio; S. Caroli

2000-01-01

303

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

304

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

Microsoft Academic Search

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

Pilar Montero; Fernando Bea

1998-01-01

305

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

PubMed Central

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

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

2011-01-01

306

Ion Suppression in Mass Spectrometry  

Microsoft Academic Search

Background: Mass spectrometry (MS) is being intro- duced into a large number of clinical laboratories. It provides specificity because of its ability to monitor selected mass ions, sensitivity because of the enhanced signal-to-noise ratio, and speed because it can help avoid the need for intensive sample cleanup and long analysis times. However, MS is not without problems related to interference,

Thomas M. Annesley

307

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

308

Vitamin A status assessment in rats with (13)C(4)-retinyl acetate and gas chromatography/combustion/isotope ratio mass spectrometry.  

PubMed

Vitamin A assessment methods that indirectly determine liver reserves are still in development. The deuterated vitamin A assay has been successfully applied in several population groups, but large doses of vitamin A must be used and the gas chromatography/mass spectrometry analysis is not very sensitive. Therefore, 10,11,14,15-(13)C(4)-retinyl acetate was synthesized using a modified Wittig-Horner procedure. Thereafter, female Sprague-Dawley rats (n = 47) were fed a vitamin A-deficient diet and divided into three groups: low (L), moderate (M) and high (H) vitamin A. Groups L, M and H were supplemented with 35, 70 and 350 nmol of unlabeled retinyl acetate/d for 17 d. On d 18, three rats from each group were killed to determine baseline (13)C levels. Serum was prepared, and livers were collected and stored at -70 degrees C until analyzed with HPLC and gas chromatography/combustion/isotope ratio mass spectrometry. The remaining rats were supplemented with 52 nmol of (13)C(4)-retinyl acetate. Rats were killed on d 1, 2, 4 and 10. The calculated and measured values of total body reserves (TBR) of vitamin A were within 7% of each other overall, and the relationship was linear (r = 0.98, P < 0.0001). The calculated mean TBR were 0.49 +/- 0.03, 0.82 +/- 0.007 and 3.72 +/- 0.40 micromol, and the measured mean TBR were 0.50 +/- 0.045, 0.69 +/- 0.10 and 3.6 +/- 0.29 micromol for groups L, M and H, respectively. In contrast, serum retinol concentrations did not show a difference among the dietary groups: 1.32 +/- 0.14, 1.35 +/- 0.17 and 1.28 +/- 0.15 micromol/L for groups L, M and H, respectively (P = 0.25). In conclusion, this method offers more sensitivity than traditional methods and may be applicable to human vitamin A status assessment when TBR estimations are desired. PMID:11053530

Tanumihardjo, S A

2000-11-01

309

Digital Imaging Mass Spectrometry  

Microsoft Academic Search

Methods to visualize the two-dimensional (2D) distribution of molecules by mass spectrometric imaging evolve rapidly and yield\\u000a novel applications in biology, medicine, and material surface sciences. Most mass spectrometric imagers acquire high mass\\u000a resolution spectra spot-by-spot and thereby scan the object’s surface. Thus, imaging is slow and image reconstruction remains\\u000a cumbersome. Here we describe an imaging mass spectrometer that exploits

Casimir Bamberger; Uwe Renz; Andreas Bamberger

2011-01-01

310

Determination of 15N isotopic enrichment and concentrations of allantoin and uric acid in urine by gas chromatography/mass spectrometry.  

PubMed

A method for the determination of 15N enrichment and concentration of allantoin and uric acid simultaneously in urine using gas chromatography/mass spectrometry (GC/MS) is described. The urine samples contained [1,3-15N2] uric acid and its oxidation product allantoin. The uric acid and allantoin were isolated using an AG1-X8 (Cl-form) anion-exchange column and heated with a mixture containing 1:1 dimethylformamide and N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA). The tert-butyldimethylsilyl (TBDMS) derivatives of allantoin and uric acid formed were injected into a gas chromatograph interfaced with a mass spectrometer operated under electron impact ionization conditions. Isotope ratio measurements were made from the abundance of the M-57 ions at m/z 398, 399 and 400 for allantoin and at m/z 567 and 569 for uric acid. 15N2 allantoin (99 at.%) was produced from [1,3-15N2] uric acid by treatment with uricase and used as a standard. Quantitation of allantoin and uric acid was based on isotopic dilution by spiking the urine sample with known quantities of 99 at.% [15N] uric acid and allantoin internal standards. The observed isotope ratio measurements from the prepared standards matched the theoretical values. Coefficients of variation in measurements of isotope ratio and concentration were 0.2 and 0.5%, respectively. The method was applied in a study to measure the urinary recovery of [1,3-15N2] uric acid continuously infused for 8-10 h into the blood of four sheep each on two occasions. Within 24 h, 65.9 +/- 9.1% of the tracer was excreted in the urine unchanged. Little was converted into allantoin (approximately 7% of the dose). The total recovery (5 days) of the infused tracer averaged 69.5 +/- 7.6% as uric acid and 76.8 +/- 9.3% as the sum of uric acid and allantoin. Uricase activities in plasma, liver and kidney of sheep were also measured using [1,3-15N2] uric acid as a substrate. Uricase activity was estimated to be 0.6 mU g-1 wet tissue in the liver and there appeared to be none in plasma and kidney. The low uricase activities in sheep tissues appeared to explain the limited conversion of the intravenously administered [15N] uric acid to allantoin but did not explain the large quantities of allantoin excreted in urine (8.96 +/- 0.86 and 1.36 +/- 0.25 mmol d-1 for allantoin and uric acid, respectively). The GC/MS method for the determination of 15N enrichment and concentration of allantoin and uric acid in urine is accurate and precise and provides a useful tool for studies on uric acid and allantoin metabolism. PMID:9487687

Chen, X B; Calder, A G; Prasitkusol, P; Kyle, D J; Jayasuriya, M C

1998-02-01

311

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

Microsoft Academic Search

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. Permanent address: II. Physikalisches Institüt, 6300 Giessen Germany.

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

1980-01-01

312

Digital Imaging Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Methods to visualize the two-dimensional (2D) distribution of molecules by mass spectrometric imaging evolve rapidly and yield novel applications in biology, medicine, and material surface sciences. Most mass spectrometric imagers acquire high mass resolution spectra spot-by-spot and thereby scan the object's surface. Thus, imaging is slow and image reconstruction remains cumbersome. Here we describe an imaging mass spectrometer that exploits the true imaging capabilities by ion optical means for the time of flight mass separation. The mass spectrometer is equipped with the ASIC Timepix chip as an array detector to acquire the position, mass, and intensity of ions that are imaged by matrix-assisted laser desorption/ionization (MALDI) directly from the target sample onto the detector. This imaging mass spectrometer has a spatial resolving power at the specimen of (84 ± 35) ?m with a mass resolution of 45 and locates atoms or organic compounds on a surface area up to ~2 cm2. Extended laser spots of ~5 mm2 on structured specimens allows parallel imaging of selected masses. The digital imaging mass spectrometer proves high hit-multiplicity, straightforward image reconstruction, and potential for high-speed readout at 4 kHz or more. This device demonstrates a simple way of true image acquisition like a digital photographic camera. The technology may enable a fast analysis of biomolecular samples in near future.

Bamberger, Casimir; Renz, Uwe; Bamberger, Andreas

2011-06-01

313

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.

Watrous, Jeramie D.; Dorrestein, Pieter C.

2013-01-01

314

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

315

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

316

Simultaneous determination of amphetamine and methamphetamine enantiomers in urine by simultaneous liquid-liquid extraction and diastereomeric derivatization followed by gas chromatographic-isotope dilution mass spectrometry.  

PubMed

A simple, rapid, reliable, and economic analytical scheme starting with in situ liquid-liquid extraction and asymmetric (or diastereomeric) chemical derivatization (ChD) followed by gas chromatography (GC)-isotope dilution mass spectrometry (MS) is described for the simultaneous determination of D- and L-amphetamine (AP) and methamphetamine (MA) in urine which could have resulted from the administration of various forms of questioned amphetamines or amphetamines-generating drugs. By using L-N-trifluoroacetyl-1-prolyl chloride (L-TPC) as chiral derivatizing agent, resolutions of 2.2 and 2.0 were achieved for the separation of AP and MA enantiomeric pairs, respectively, on an ordinary HP-5MS capillary column. The GC-MS quantitation was carried out in the selected ion monitoring (SIM) mode using m/z 237 and 251 as the quantifier ions for the respective diastereomeric pairs of AP-L-TPC and MA-L-TPC. The calibration curves plotted for the two pairs of analytes stretch with good linearity down to 45 ng/mL, and the limits of detection and quantitation determined were as low as 40 and 45 ng/mL, respectively. Also, a comparative study using 10 real-case urine specimens previously screened as positive for MA administration showed mostly tolerable biases between the two sums (of concentration) of D- and L-MA obtained via an asymmetric L-TPC-ChD approach and via an ordinary pentafluoropropionylation (PFPA-ChD) approach, respectively, as well as between the two sums of D- and L-AP obtained thereupon, thus validating the proposed analytical scheme as a promising forensic protocol for the detailed analysis of enantiomeric amphetamines in urine. PMID:15664343

Wang, Sheng-Meng; Wang, Ting-Cheng; Giang, Yun-Seng

2005-02-25

317

Application of liquid chromatography-tandem mass spectrometry (LC-MS/MS) for the analysis of stable isotope enrichments of phenylalanine and tyrosine.  

PubMed

Whole-body protein synthesis and breakdown are measured by a combined tracer infusion protocol with the stable isotope amino acids L-[ring-(2)H(5)]-phenylalanine, L-[ring-(2)H(2)]-tyrosine and L-[ring-(2)H(4)]-tyrosine that enable the measurement of the phenylalanine to tyrosine conversion rate. We describe a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the measurement of very low tracer-tracee ratios (TTR) of the amino acids L-phenylalanine and L-tyrosine in human plasma. TTR calibration curves of the tracers L-[ring-(2)H(5)]-phenylalanine, L-[ring-(2)H(2)]-tyrosine and L-[ring-(2)H(4)]-tyrosine were linear (r(2)>0.99) in the range between 0.01% and 5.0% TTR and lowest measurable TTR for the tracers was 0.01% at a physiological concentration of 60 microM. The method was applied successfully to plasma samples from a clinical study reaching a steady state enrichment plateau (mean+/-SD) of 3.33+/-0.19% for L-[ring-(2)H(5)]-phenylalanine, 2.40+/-0.43% for L-[ring-(2)H(2)]-tyrosine and 0.29+/-0.07% for L-[ring-(2)H(4)]-tyrosine, respectively. The LC-MS/MS method can be applied for measurement of very low plasma enrichments of phenylalanine and tyrosine for the determination of whole-body protein synthesis and breakdown rates in humans. PMID:19036645

Meesters, Roland J W; Wolfe, Robert R; Deutz, Nicolaas E P

2008-11-14

318

Quantification of N-acetyl-seryl-aspartyl-lysyl-proline in hemodialysis patients administered angiotensin-converting enzyme inhibitors by stable isotope dilution liquid chromatography-tandem mass spectrometry.  

PubMed

We developed a sensitive, selective and accurate method based on liquid chromatography with tandem mass spectrometry (LC-MS/MS) to determine N-terminal thymosin-? peptides of Ac-SDKP and Ac-ADKP in human plasma samples. Quantification of Ac-SDKP and Ac-ADKP was performed using solid phase extraction (SPE) based on C(18), reversed phase LC separation, and stable isotope dilution electrospray ionization-MS/MS in multiple reaction-monitoring (MRM) mode. The Ac-SDKP-(13)C(6), (15)N(2) and Ac-ADKP-d(7) were synthesized for the internal standards. These MRM monitoring ions were m/z 488?129 (quantitative ion)/226 for Ac-SDKP, m/z 496?137 for Ac-SDKP-(13)C(6), (15)N(2), m/z 472?129 (quantitative ion)/226 for Ac-ADKP, and m/z 479?129 for Ac-ADKP-d(7), respectively. Lower limit of quantitation (LLOQ) of Ac-SDKP and Ac-ADKP was 0.1ng/mL in human plasma. Recovery values were ranged from 94.7% to 106.3% for inter- (RSD: 0.6-3.5%) and intra- (RSD: 0.4-4.9%) day assays. Plasma Ac-SDKP levels were significantly higher in hemodialyzed subjects treated with angiotensin-converting enzyme inhibitors of enalapril (27.3±24.6ng/mL, n=10) and trandolapril (12.3±16.9ng/mL, n=18) than healthy (0.4±0.2ng/mL, n=7) and hemodialyzed subjects (0.6±0.2ng/mL, n=34). This analytical method would be useful to measure N-terminal thymosin-? peptides in human plasma for the clinical study. PMID:21074346

Inoue, Koichi; Ikemura, Ayaka; Tsuruta, Yoshinari; Watanabe, Kazuki; Tsutsumiuchi, Kaname; Hino, Tomoaki; Oka, Hisao

2010-10-21

319

Determination of Hg Content in a Shallow Firn Core From Summit, Greenland Using Isotope Dilution Cold Vapor Inductively Coupled Plasma - Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Considerable attention has recently been focused on mercury (Hg) owing to its ability to bioaccumulate as highly toxic species in the biosphere. Hg in the environment is derived from both natural and anthropogenic sources and present day emissions for both are thought to be of similar magnitude. Once introduced into the atmosphere, Hgo can be transported long distances and as a result is considered to have global environmental influence. High levels of Hg have been found in Arctic food supplies and elevated levels have been observed in the native people of the circumpolar countries including Greenland. Mercury content was determined in surface snow and a 7 m shallow snow/firn core, recovered in May 2001 from Summit, Greenland (72.58oN, 38.53oW; elevation 3238 m), using a new method employing isotope dilution cold vapor inductively coupled plasma - mass spectrometry (ID-CV-ICPMS). The method, recently developed at the National Institute of Standards and Technology, uses a 201Hg spike that is equilibrated with the sample. Hg is measured by chemical reduction with tin (II) chloride and generation of a "cold vapor" (elemental Hg vapor) whereby the Hg vapor is separated from the matrix using a gas-liquid separator and is collected on gold guaze. Hg is then released by thermal desorption and the Hg isotope ratio (201Hg/202Hg) measured by quadrapole ICP-MS. There are considerable advantages to this new method in the analysis of very low concentration snow/firn/ice samples which include: 1) very high sensitivity (detection limit < 1 pg/mL, 3 sigma); 2) accuracy and precision of the order of one percent or better; and 3) complete freedom from spectral and matrix interferences. The concentrations determined ranged from 0.1 to 1.1 pg/g, which fall within the range of those previously determined by Boutron et al. (1998). Hg contributed from core processing, storage in LDPE bottles, and the analytical procedure yielded a blank value of 0.10 pg Hg/g equivalent. This was used to correct the measured Hg values. The uncertainty in the reported Hg concentrations was 0.1 to 0.2 pg Hg/g for a 10 mL aliquot. This new method may allow the examination of the high-resolution (sub-seasonal) snow/firn/ice record for better understanding of the short-term variability in Hg concentrations and their relationship to atmospheric mercury depletion events.

Mann, J. L.; Long, S. E.; Shuman, C. A.

2002-05-01

320

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

321

Simultaneous determination of tetrahydrocortisol and tetrahydrocortisone in human plasma and urine by stable isotope dilution mass spectrometry  

Microsoft Academic Search

A capillary gas chromatographic–mass spectrometric method for the simultaneous determination of tetrahydrocortisol (THF, 3?,11?,17?,21-tetrahydroxy-5?-pregnane-20-one), allo-tetrahydrocortisol (allo-THF, 3?,11?,17?,21-tetrahydroxy-5?-pregnane-20-one) and tetrahydrocortisone (THE, 3?,17?,21-trihydroxy-5?-pregnane-11,20-dione) in human plasma and urine is described. [1,2,3,4,5-2H5]THF (THF-d5), allo-[1,2,3,4,5-2H5]THF (allo-THF-d5) and [1,2,3,4,5-2H5]THE (THE-d5) were used as internal standards. A double derivatization (bismethylenedioxypentafluoropropionate, BMD-PFP) made possible the separation of the three tetrahydrocorticoids with good gas chromatographic behavior. Quantitation was

Takashi Furuta; Toshiyuki Namekawa; Hiromi Shibasaki; Yasuji Kasuya

1998-01-01

322

Halide compound mass spectrometry method and mass spectrometry apparatus  

US Patent & Trademark Office Database

A mass spectrometry apparatus is provided with an emitter for emitting metal ions, a reaction chamber where the detected gas is introduced and ionized by the metal ions, an aperture for guiding molecules of the ionized detected gas, and a mass spectrometer for measuring the guided molecules. The metal ions emitted from the emitter are caused to fly to the reaction chamber to ionize said detected gas. The detected gas is a halide compound. Further provision is made of a sample gas source for feeding a halide compound to the reaction chamber and an N.sub.2 gas source for feeding to the reaction chamber a gas (N.sub.2 etc.) to which the metal ions attach less easily than to the halide compound. It is therefore made possible to apply cation attachment of the Fujii system to mass spectrometry of a halide compound and enable precise measurement of fluoride compounds etc. having a large impact on global warming.

2003-01-14

323

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

324

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

325

Liquid chromatography\\/mass spectrometry  

Microsoft Academic Search

The combination of high-performance liquid chromatography (HPLC) and mass spectrometry (MS) offers the analytical chemist one of the most powerful analytical techniques of modern times. Both techniques have matured to the point that they represent two of the most important tools available for the characterization of organic compounds. Unfortunately, coupling these techniques (LC\\/MS) has been a more challenging task than

Thomas R. Covey; Edgar D. Lee; Andries P. Bruins; Jack D. Henion

1986-01-01

326

The use of Fluorinated Graphite Polymer in the Oxygen-Isotope Analysis of Silicates by Continuous Flow Isotope Ratio Mass Spectrometry (CF-IRMS)  

NASA Astrophysics Data System (ADS)

To date the majority of analytical procedures for ?18O analysis of silicates require relatively expensive apparatus involving the use of hazardous fluorine or halogen fluoride gases. Carbon reduction offers the potential to avoid the use of hazardous gases; however, it has been plagued by low yields and variable isotopic fractionation leading to significant differences in isotopic composition compared to conventional fluorination techniques (CFT). We adopt a carbon reduction method, which includes a fluorinated graphite polymer (F>60%) to help oxidize the silicate, thus increasing the percent yield as well as the precision of the analyses. Three silicate standards (NBS-28; UWG-2; GBW044190) were analyzed to compare this method against CFT. Silicate samples of 0.2mg are combined with 2mg of fluorinated graphite and sealed in a silver cup. The cups are then heated instantaneously to 1470°C in a high temperature conversion elemental analyzer (TC/EA). The evolved oxygen reacts with carbon in the furnace resulting in carbon monoxide which is transported via a helium carrier gas to a series of chemical and cold traps prior to introduction into the gas chromatograph. An Ascarite II and Mg(ClO4)2 chemical trap removes acids (e.g. HF) and water, followed by an LN2 cold trap to remove SiF4. The He carrier gas flow is kept low (0.7bar) to maximize reaction time, whereas He flow to the open split is increased (0.7bar) in order to reduce peak tailing in the IRMS. Using this method individual analysis can be completed in ~7 minutes. Oxygen yields range from 54-92%; however reproducibility better than 0.5‰ is normally achievable. Measured values are consistently enriched in 18O compared with accepted values; however, this offset is systematic and can be corrected for using a linear correction factor. Corrected values are: 9.11±0.3‰, 5.95±0.5‰, and -1.78±0.4‰ for NBS-28, UWG-2, and GBW044190 respectively. As the number of laboratories with CF-IRMS and TC/EA apparatus increases the development of this method has the potential to make ?18O analysis of silicates more widely available.

Kingston, A. W.; Weis, D.; Francois, R.

2008-12-01

327

Method for measurement of glucose enrichment in serum using isotope dilution mass spectrometry and its application for measurement of glucose kinetics  

SciTech Connect

An isotope dilution mass spectrometric method has been developed for kinetic studies of D-glucose in humans, using 6,6-dideuteroglucose as the internal standard. Glucose in plasma samples was purified by anion and cation exchange column chromatography after deproteinization and derivatized to ..cap alpha..-D-glucofuranose cyclic 1,2:3,5-bis (butylboronate)-6-acetate.

Dan, P.; Clemons, P.M.; Sperling, M.I.; Gelfand, M.J.; Chen, I.W.; Sperling, M.A.; Norman, E.J.

1983-01-01

328

Mass spectrometry and renal calculi.  

PubMed

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

Penescu, Mircea; Purcarea, Victor Lorin; Sisu, Ioana; Sisu, Eugen

329

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

330

Mass spectrometry and tandem mass spectrometry of citrus limonoids.  

PubMed

Methods for atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) of citrus limonoid aglycones and electrospray ionization tandem mass spectrometry (ESI-MS/MS) of limonoid glucosides are reported. The fragmentation patterns of four citrus limonoid aglycones (limonin, nomilin, obacunone, and deacetylnomilin) and six limonoid glucosides, that is, limonin 17-beta-D-glucopyranoside (LG), nomilin 17-beta-D-glucopyranoside (NG), nomilinic acid 17-beta-D-glucopyranoside (NAG), deacetyl nomilinic acid 17-beta-D-glucopyranoside (DNAG), obacunone 17-beta-D-glucopyranoside (OG), and obacunoic acid 17-beta-D-glucopyranoside (OAG) were investigated using a quadruple mass spectrometer in low-energy collisionally activated dissociation (CAD). The four limonoid aglycones and four limonoid glucosides (LG, OG, NAG, and DNAG) were purified from citrus seeds; the other two limonoid glucosides (NG and OAG) were tentatively identified in the crude extract of grapefruit seeds by ESI mass spectrometry in both positive and negative ion analysis. Ammonium hydroxide or acetic acid was added to the mobile phase to facilitate ionization. During positive ion APCI analysis of limonoid aglycones, protonated molecular ion, [M + H]+, or adduct ion, [M + NH3 + H]-, was formed as base peaks when ammonium hydroxide was added to the mobile phase. Molecular anions or adduct ions with acetic acid ([M + HOAc - H] and [M + HOAc]-) or a deprotonated molecular ion were produced during negative ion APCI analysis of limonoid aglycones, depending on the mobile-phase modifier used. Positive ion ESI-MS of limonoid glucosides produced adduct ions of [M + H + NH3]+, [M + Na]+, and [M + K]+ when ammonium hydroxide was added to the mobile phase. After collisionally activated dissociation (CAD) of the limonoid aglycone molecular ions in negative ion APCI analysis, fragment ions indicated structural information of the precursor ions, showing the presence of methyl, carboxyl, and oxygenated ring structure. CAD of the adduct ion [M + H + NH3]+ of limonoid glucosides produced the aglycone moiety corresponding to each glucoside. The combination of mass spectrometry and tandem mass spectrometry provides a powerful technique for identification and characterization of citrus limonoids. PMID:14710824

Tian, Qingguo; Schwartz, Steven J

2003-10-15

331

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

PubMed

A stable isotope dilution assay and liquid chromatography tandem mass spectrometry (LC-MS/MS) method was developed and validated for the determination of 12 mycotoxins, aflatoxins B1, B2, G1, G2, and M1, deoxynivalenol, fumonisins B1, B2, and B3, ochratoxin A, T-2 toxin, and zearalenone, in milk-based infant formula and foods. Samples were fortified with 12 (13)C uniformly labeled mycotoxins ([(13)C]-mycotoxins) that correspond to the 12 target mycotoxins and prepared by dilution and filtration, followed by LC-MS/MS analysis. Quantitation was achieved using the relative response factors of [(13)C]-mycotoxins and target mycotoxins. The average recoveries in fortified milk, milk-based infant formula, milk powder, and baby yogurt of aflatoxins B1, B2, G1, and G2 (2, 10, and 50 ?g/kg), aflatoxin M1 (0.5, 2.5, and 12.5 ?g/kg), deoxynivalenol, fumonisins B1, B2, and B3 (40, 200, and 1000 ?g/kg), ochratoxin A, T-2 toxin, and zearalenone (20, 100, and 500 ?g/kg), range from 89 to 126% with RSDs of <20%. The individual recoveries in the four fortified matrices range from 72% (fumonisin B3, 20 ?g/kg, milk-based infant formula) to 136% (T-2 toxin, 20 ?g/kg, milk powder), with RSDs ranging from 2 to 25%. The limits of quantitation (LOQs) were from 0.01 ?g/kg (aflatoxin M1) to 2 (fumonisin B1) ?g/kg. Aflatoxin M1 was detected in two European Reference materials at 0.127 ± 0.013 ?g/kg (certified value = 0.111 ± 0.018 ?g/kg) and 0.46 ± 0.04 ?g/kg (certified value = 0.44 ± 0.06 ?g/kg), respectively. In 60 local market samples, aflatoxins B1 (1.14 ± 0.10 ?g/kg) and B2 (0.20 ± 0.03 ?g/kg) were detected in one milk powder sample. Aflatoxin M1 was detected in three imported samples (condensed milk, milk-based infant formula, and table cream), ranging from 0.10 to 0.40 ?g/kg. The validated method provides sufficient selectivity, sensitivity, accuracy, and reproducibility to screen for aflatoxin M1 at nanograms per kilogram concentrations and other mycotoxins, without using standard addition or matrix-matched calibration to compensate for matrix effects. PMID:23746324

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

2013-06-24

332

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

333

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

PubMed Central

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

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

2013-01-01

334

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

2013-09-18

335

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.

Berdyshev, Evgeny V.

2011-01-01

336

Calculation of Transactinide Homolog Isotope Production Reactions Possible with the Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory  

SciTech Connect

The LLNL heavy element group has been investigating the chemical properties of the heaviest elements over the past several years. The properties of the transactinides (elements with Z > 103) are often unknown due to their low production rates and short half-lives, which require lengthy cyclotron irradiations in order to make enough atoms for statistically significant evaluations of their chemistry. In addition, automated chemical methods are often required to perform consistent and rapid chemical separations on the order of minutes for the duration of the experiment, which can last from weeks to months. Separation methods can include extraction chromatography, liquid-liquid extraction, or gas-phase chromatography. Before a lengthy transactinide experiment can be performed at an accelerator, a large amount of preparatory work must be done both to ensure the successful application of the chosen chemical system to the transactinide chemistry problem being addressed, and to evaluate the behavior of the lighter elemental homologs in the same chemical system. Since transactinide chemistry is literally performed on one single atom, its chemical properties cannot be determined from bulk chemical matrices, but instead must be inferred from the behavior of the lighter elements that occur in its chemical group and in those of its neighboring elements. By first studying the lighter group homologs in a particular chemical system, when the same system is applied to the transactinide element under investigation, its decay properties can be directly compared to those of the homologues, thereby allowing an inference of its own chemistry. The Center for Accelerator Mass Spectrometry (CAMS) at Lawrence Livermore National Laboratory (LLNL) includes a 1 MV Tandem accelerator, capable of accelerating light ions such as protons to energies of roughly 15 MeV. By using the CAMS beamline, tracers of transactinide homolog elements can be produced both for development of chemical systems and for evaluation of homolog chemical properties. CAMS also offers an environment for testing these systems 'online' by incorporating automated chemical systems into the beamline so that tracers can be created, transported, and chemically separated all on the shorter timescales required for transactinide experiments. Even though CAMS is limited in the types and energies of ions they can accelerate, there are still a wide variety of reactions that can be performed there with commercially available target materials. The half-lives of these isotopes vary over a range that could be used for both online chemistry (where shorter half-lives are required) and benchtop tracers studies (where longer lived isotopes are preferred). In this document, they present a summary of tracer production reactions that could be performed at CAMS, specifically for online, automated chemical studies. They are from chemical groups four through seven, 13, and 14, which would be appropriate for studies of elements 104-107, 113, and 114. Reactions were selected that had (a) commercially available target material, (b) half-lives long enough for transport from a target chamber to an automated chemistry system, and (c) cross-sections at CAMS available projectile energies that were large enough to produce enough atoms to result in a statistically relevant signal after losses for transport and chemistry were considered. In addition, the resulting product atoms had to decay with an observable gamma-ray using standard Ge gamma-ray detectors. The table includes calculations performed for both metal targets and their corresponding oxides.

Moody, K J; Shaughnessy, D A; Gostic, J M

2011-11-29

337

Application of the isotope dilution technique for 93Zr determination in an irradiated cladding material by multiple collector-inductively coupled plasma mass spectrometry  

NASA Astrophysics Data System (ADS)

The determination of 93Zr concentration, a long-lived radionuclide present in spent nuclear fuel and in the structural components of nuclear reactors, is a major issue for nuclear waste disposal purpose and to validate neutronic calculation codes. To measure 93Zr concentration in irradiated cladding material with a high precision, an analytical method based on the use of multiple collector-inductively coupled plasma mass spectrometer (MC-ICPMS) combined to isotope dilution technique was developed. First a radiochemical separation of zirconium from a zircaloy sample (a zirconium alloy used as a cladding material for nuclear fuel elements), has allowed to obtain a very pure zirconium fraction with no potential isobaric interferences for mass spectrometric measurements. Then as the determination of all zirconium isotope ratios in the sample is necessary for the isotope dilution method, a MC-ICPMS procedure was developed to perform these precise measurements. Finally, the determination of 93Zr concentration in the same sample was performed, after preparation and calibration of a 96Zr spike solution. The uncertainties obtained on isotope ratios of zirconium by MC-ICPMS were in the order of 0.1%. The final uncertainty obtained on the 93Zr concentration in the nuclear material used and after chemical purification was lower than 0.6%.

Chartier, F.; Isnard, H.; Degros, J. P.; Faure, A. L.; Fréchou, C.

2008-03-01

338

Quantitative analysis of the microbial metabolome by isotope dilution mass spectrometry using uniformly 13C-labeled cell extracts as internal standards  

Microsoft Academic Search

A novel method was developed for the quantitative analysis of the microbial metabolome using a mixture of fully uniformly (U) 13C-labeled metabolites as internal standard (IS) in the metabolite extraction procedure the subsequent liquid chromatography–electrospray ionization-tandem mass spectrometry (LC–ESI-MS\\/MS) analysis. This mixture of fully U 13C-labeled metabolites was extracted from biomass of Saccharomyces cerevisiae cultivated in a fed-batch fermentation on

Liang Wu; Mlawule R. Mashego; Jan C. van Dam; Angela M. Proell; Jacobus L. Vinke; Cor Ras; Wouter A. van Winden; Walter M. van Gulik; Joseph J. Heijnen

2005-01-01

339

Development of chiral liquid chromatography–tandem mass spectrometry isotope dilution methods for the determination of unconjugated and total S-equol in human plasma and urine  

Microsoft Academic Search

Liquid chromatography–tandem mass spectrometry (LC–MS\\/MS) methods for the determination of unconjugated and total (conjugated plus unconjugated) S-equol in human plasma and urine were developed and validated. The separation of R and S enantiomers was achieved with a Chiracel OJ-H column operated in a normal phase mode using ethanol\\/hexane mobile phase components. Ionization of S-equol by negative ion electrospray generated the

Jeffry B. Plomley; Richard L. Jackson; Richard J. Schwen; Jeffrey S. Greiwe

2011-01-01

340

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

Microsoft Academic Search

This improved isotope-dilution gas chromatographic\\/mass spectrometric (GC\\/MS) method, in which (¹³C)glucose is the internal standard, meets the requirements of a Definitive Method. In a first study with five reconstituted lyophilized sera, a nested analysis of variance of GC\\/MS values indicated considerable among-vial variation. The CV for 32 measurements per serum ranged from 0.5 to 0.9%. However, concentration and uncertainty values

O. Pelletier; C. Arratoon

1987-01-01

341

Determination of Folate Vitamers in Human Serum by Stable-Isotope-Dilution Tandem Mass Spectrometry and Comparison with Radioassay and Microbiologic Assay  

Microsoft Academic Search

Background: Current clinical methods for folate give different results and cannot measure the various forms of folate. We developed an isotope-dilution tandem mass spectrometric method coupled to liquid chroma- tography (LC\\/MS\\/MS) as a candidate reference method for 5-methyltetrahydrofolic acid (5MeTHF), 5-formyltet- rahydrofolic acid (5FoTHF), and folic acid (FA) in hu- man serum. Methods: We quantitatively isolated folates from 275 L

Christine M. Pfeiffer; Zia Fazili; Ming Zhang; Elaine W. Gunter

342

Applications of diode lasers to resonance ionization mass spectrometry  

Microsoft Academic Search

Diode lasers have been utilized in resonance ionization mass spectrometry (RIMS). These devices have been used to excite the first transition of several 1 + 1 + 1 multiple photon processes for both lanthanum 138 and 139. Enhanced isotopic selectivity resulted. Very-high resolution spectra were also obtained with the diode laser step to yield new atomic hyperfine structure constants for

J. P. Young; R. W. Shaw; D. H. Smith

1990-01-01

343

Radiocarbon dating of sediments by accelerator mass spectrometry  

Microsoft Academic Search

Accelerator mass spectrometry allows the measurement of the abundance of carbon isotopes in much smaller samples (1 mg of carbon in the form of graphite) than conventional methods of radiocarbon dating. The small sample requirement widens the potential for sediment dating. In this study, fractions of the sedimentary organic matter, for example, humic acid, lipid, macrofossils, were isolated and each

A. J. Fowler; R. Gillespie; R. E. M. Hedges

1986-01-01

344

Probing phospholipid dynamics by electrospray ionisation mass spectrometry  

Microsoft Academic Search

Recent advances in electrospray ionisation mass spectrometry (ESI-MS) have greatly facilitated the analysis of phospholipid molecular species in a growing diversity of biological and clinical settings. The combination of ESI-MS and metabolic labelling employing substrates labelled with stable isotopes is especially exciting, permitting studies of phospholipid synthesis and turnover in vivo. This review will first describe the methodology involved and

Anthony D. Postle; David C. Wilton; Alan N. Hunt; George S. Attard

2007-01-01

345

Multiple ion Counting for Noble gas Mass Spectrometry  

Microsoft Academic Search

In geo- and cosmochemistry noble gases are analyzed for their abundance and isotopic composition by mass spectrometry in the static mode (no pumping). This results in that they are among the elements with the highest detection efficiency. This is especially so for xenon, where during the course of a normal measurement almost all atoms will have been ionized. Not all

U. Ott

2008-01-01

346

High-precision direct determination of the 87Sr/ 86Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry  

NASA Astrophysics Data System (ADS)

We describe a precise and accurate method for the direct determination of the 87Sr/ 86Sr isotope ratio of bottled Sr-rich natural mineral drinking water using multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS). The method is validated by the comparative analysis of the same water with and without cation-exchange resin purification. The work indicates that isobarically interfering elements can be corrected for when 87Rb/ 86Sr < 0.05 (Rb/Sr < 0.015), and that the matrix elements (Ca, Mg, K and Na) have no significant effect on the accuracy of the Sr isotope data. The method is simple, rapid, eliminates sample preparation time, and avoids potential contamination during complicated sample-preparation procedures. Therefore, the high sample throughput inherent to the MC-ICP-MS can be fully exploited.

Yang, Yue-Heng; Wu, Fu-Yuan; Xie, Lie-Wen; Yang, Jin-Hui; Zhang, Yan-Bin

2011-08-01

347

Accurate determination of Curium and Californium isotopic ratios by inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) in 248Cm samples for transmutation studies  

SciTech Connect

The French Atomic Energy Commission has carried out several experiments including the mini-INCA (INcineration of Actinides) project for the study of minor-actinide transmutation processes in high intensity thermal neutron fluxes, in view of proposing solutions to reduce the radiotoxicity of long-lived nuclear wastes. In this context, a Cm sample enriched in {sup 248}Cm ({approx}97 %) was irradiated in thermal neutron flux at the High Flux Reactor (HFR) of the Laue-Langevin Institute (ILL). This work describes a quadrupole ICP-MS (ICP-QMS) analytical procedure for precise and accurate isotopic composition determination of Cm before sample irradiation and of Cm and Cf after sample irradiation. The factors that affect the accuracy and reproducibility of isotopic ratio measurements by ICP-QMS, such as peak centre correction, detector dead time, mass bias, abundance sensitivity and hydrides formation, instrumental background, and memory blank were carefully evaluated and corrected. Uncertainties of the isotopic ratios, taking into account internal precision of isotope ratio measurements, peak tailing, and hydrides formations ranged from 0.3% to 1.3%. This uncertainties range is quite acceptable for the nuclear data to be used in transmutation studies.

Gourgiotis, A.; Isnard, H.; Aubert, M.; Dupont, E.; AlMahamid, I.; Cassette, P.; Panebianco, S.; Letourneau, A.; Chartier, F.; Tian, G.; Rao, L.; Lukens, W.

2011-02-01

348

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

Microsoft Academic Search

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

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

2006-01-01

349

Mass spectrometry with cryogenic detectors  

NASA Astrophysics Data System (ADS)

Cryogenic detectors have recently been applied for the first time as ion detectors in time-of-flight mass spectrometry (TOF-MS). Because of their energy sensitivity cryogenic detectors are expected to have near 100% efficiency even for very large, slow-moving molecules, in contrast to microchannel plates whose efficiency drops considerably at large mass. Thus, cryogenic detectors could contribute to extending the mass range accessible by TOF-MS and help improving detection limits. In addition, the energy resolution provided by cryogenic detectors can be used for charge discrimination and studies of ion fragmentation, ion-detector interaction, and internal energies of large molecular ions. Cryogenic detectors could therefore prove to be a valuable diagnostic tool in TOF-MS. Here I summarize the results of recent demonstration experiments.

Frank, M.

2000-04-01

350

Fast Atom Bombardment Mass Spectrometry  

NASA Astrophysics Data System (ADS)

Fast atom bombardment mass spectrometry has become a powerful structural tool since the first reports of its use in 1981. Samples are ionized in the condensed state, usually in a glycerol matrix, by bombarding the matrix with xenon or argon atoms with energies of 5000 to 10,000 electron volts. This yields both positive and negative secondary ions, which are sputtered from the surface. The technique has been used to detect inorganic ion clusters to mass 25,800 and biologically active peptides to mass 5700, and it gives molecular ions of such highly polar or labile organic compounds as glycosphingolipids and polyene antibiotics. It can be especially valuable in determining the sequences of amino acids in polypeptides.

Rinehart, Kenneth L.

1982-10-01

351

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

2006-07-14

352

IsoQuant: a software tool for stable isotope labeling by amino acids in cell culture-based mass spectrometry quantitation.  

PubMed

Accurate protein identification and quantitation are critical when interpreting the biological relevance of large-scale shotgun proteomics data sets. Although significant technical advances in peptide and protein identification have been made, accurate quantitation of high-throughput data sets remains a key challenge in mass spectrometry data analysis and is a labor intensive process for many proteomics laboratories. Here, we report a new SILAC-based proteomics quantitation software tool, named IsoQuant, which is used to process high mass accuracy mass spectrometry data. IsoQuant offers a convenient quantitation framework to calculate peptide/protein relative abundance ratios. At the same time, it also includes a visualization platform that permits users to validate the quality of SILAC peptide and protein ratios. The program is written in the C# programming language under the Microsoft .NET framework version 4.0 and has been tested to be compatible with both 32-bit and 64-bit Windows 7. It is freely available to noncommercial users at http://www.proteomeumb.org/MZw.html . PMID:22519468

Liao, Zhongping; Wan, Yunhu; Thomas, Stefani N; Yang, Austin J

2012-05-03

353

Quantitation of metabolites of the nerve agents sarin, soman, cyclohexylsarin, VX, and Russian VX in human urine using isotope-dilution gas chromatography-tandem mass spectrometry.  

PubMed

Organophosphorus nerve agents are among the most toxic organic compounds known and continue to be a threat for both military and terrorist use. We have developed an isotope-dilution gas chromatography-tandem mass spectrometric (GC-MS-MS) method for quantitating the urinary metabolites of the organophosphorus nerve agents sarin (GB), soman (GD), VX, Russian VX (RVX), and cyclohexylsarin (GF). Urine samples were acidified, extracted into ether-acetonitrile, derivatized by methylation with diazomethane, and analyzed by GC-MS-MS. The limits of detection were less than 1 micro g/L for all analytes. PMID:15239858

Barr, John R; Driskell, W J; Aston, Linda S; Martinez, Rodolfo A

354

Mass spectrometry of fatty aldehydes.  

PubMed

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

2011-09-09

355

Liquid chromatography/mass spectrometry  

SciTech Connect

The combination of high-performance liquid chromatography (HPLC) and mass spectrometry (MS) offers the analytical chemist one of the most powerful analytical techniques of modern times. Both techniques have matured to the point that they represent two of the most important tools available for the characterization of organic compounds. Unfortunately, coupling these techniques (LC/MS) has been a more challenging task than it was for gas chromatography/mass spectrometry (GC/MS). The potential benefits derived from on-line coupling of LC to MS have been known for about 12 years. The problems associated with interfacing these two techniques in a practical way are considerable, but recently there has been significant progress toward this end. An excellent review covering the status of this subject through 1978 appeared in this journal, and this article will attempt to cover the state of the art through early 1986. As with any rapidly developing area, the details of all aspects of LC/MS cannot be covered in a short overview. The reader may refer to the references and recent reviews more information on other aspects of this subject.

Covey, T.R.; Lee, E.D.; Bruins, A.P.; Henion, J.D.

1986-12-01

356

Determination of boron isotope ratios by Zeeman effect background correction-graphite furnace atomic absorption spectrometry  

NASA Astrophysics Data System (ADS)

A new method for the determination of isotopic ratio of boron using Zeeman effect background correction-graphite furnace atomic absorption spectrometry with conventional atomizer and natural-boron hollow cathode source is described. The isotope-shift Zeeman effect at 208.9 nm is utilized for isotopic ratio determination. At a given concentration of total boron, the net absorbance decreases linearly with increasing 10B/11B ratio. The absorbances are recorded at the field strength of 1.0 T. The isotope ratios measured by the proposed method were in good agreement with the results obtained by inductively coupled plasma-quadruple mass spectrometry or thermal ionization mass spectrometry. The present method is fairly fast and less expensive compared to the above techniques and is quite suitable for plant environments.

Thangavel, S.; Rao, S. V.; Dash, K.; Arunachalam, J.

2006-03-01

357

Quantification of steroid conjugates using fast atom bombardment mass spectrometry  

SciTech Connect

Fast atom bombardment/mass spectrometry or liquid secondary ion mass spectrometry provides the capability for direct analysis of steroid conjugates (sulfates, glucuronides) without prior hydrolysis or derivatization. During the analysis of biologic extracts, limitations on the sensitivity of detection arise from the presence of co-extracted material which may suppress or obscure the analyte signal. A procedure is described for the quantitative determination of dehydroepiandrosterone sulfate in serum which achieved selective isolation of the analyte using immunoadsorption extraction and highly specific detection using tandem mass spectrometry. A stable isotope-labeled analog (( 2H2)dehydroepiandrosterone sulfate) was used as internal standard. Fast atom bombardment of dehydroepiandrosterone sulfate yielded abundant (M-H)- ions that fragmented following collisional activation to give HSO4-; m/z 97. During fast atom bombardment/tandem mass spectrometry of serum extracts, a scan of precursor ions fragmenting to give m/z 97 detected dehydroepiandrosterone sulfate and the (2H2)-labeled analog with a selectivity markedly superior to that observed using conventional mass spectrometry detection. Satisfactory agreement was observed between quantitative data obtained in this way and data obtained by gas chromatography/mass spectrometry of the heptafluorobutyrates of dehydroepiandrosterone sulfate and (2H2)dehydroepiandrosterone sulfate obtained by direct derivatization. 21 refs.

Gaskell, S.J. (Baylor College of Medicine, Houston, TX (USA))

1990-10-01

358

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

359

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

360

Accelerator mass spectrometry in the biomedical sciences: Applications in low-exposure biomedical and environmental dosimetry.  

National Technical Information Service (NTIS)

We are utilizing Accelerator Mass Spectrometry (AMS) as a sensitive detector for tracking the disposition of radio-isotope labeled molecules in the biomedical sciences. These applications have shown the effectiveness of AMS as a tool to quantify biologica...

J. S. Felton K. W. Turteltaub J. S. Vogel R. Balhorn B. L. Gledhill

1990-01-01

361

Pushing the Limits of Accelerator Mass Spectrometry  

SciTech Connect

A renewed interest in Accelerator Mass Spectrometry (AMS) from nuclear physics laboratories is emerging in connection with Radioactive Ion Beams (RIBs). At the Holifield Radioactive Ion Beam Facility (HRIBF) at Oak Ridge National Laboratory (ORNL) we are exploring the AMS capabilities of the 25-MV Tandem acclerator. Behind this effort is the realization that two fields of research - AMS and RIBs - complement each other in techniques. Development of effective and efficient beam purification techniques is of common interest to both AMS and the RIB program. Two main characteristics of the 25-MV Tandem provide unique opportunities for performing the highest sensitivity measurements of AMS; namely i) the highest operating voltage in the world, and ii) a folded geometry which involves a 180 degree magnet in the terminal. For the RIB program, we have used AMS techniques to improve the sensitivity of detection of some radioactive species in the measurement of unknown massses of n-rich nuclei. For AMS, we have concentrated in exploring two important isotopes, 14C and 36Cl, for applications that require the highest sensitivity. We have successfully measured 36Cl/Cl ratios as low as a few times 10-16 in seawater samples demonstrating that our set has the highest sensitivity for this isotope and proving that 36Cl can be measured at the levels required for a tracer in oceanography.

Galindo-Uribarri, Alfredo {nmn} [ORNL; Beene, James R [ORNL; Danchev, M. [University of Tennessee, Knoxville (UTK); Doupe, J. [University of Toronto; Fuentes Madariaga, Beatriz E [ORNL; Gomez Del Campo, Jorge [ORNL; Hausladen, Paul [ORNL; Juras, Raymond C [ORNL; Liang, J Felix [ORNL; Litherland, Albert E [ORNL; Liu, Yuan [ORNL; Meigs, Martha J [ORNL; Mills, Gerald D [ORNL; Mueller, Paul Edward [ORNL; Padilla-Rodal, Elizabeth [ORNL; Pavan, John R [ORNL; Sinclair IV, John W [ORNL; Stracener, Daniel W [ORNL

2007-01-01

362

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

363

Injection optics for fast mass switching for accelerator mass spectrometry  

NASA Astrophysics Data System (ADS)

Accelerator Mass Spectrometry (AMS) measures the ratio of extremely small amounts of a radioactive isotope in the presence of ~ 1015 times more stable ones. The isotopes are injected sequentially over a repeated period and observed at the exit of the accelerator. so any fluctuations in ion source output or transmission through the accelerator over a time comparable to the measurement time, will reduce the accuracy of such measurements. This compromise in accuracy can be lessened by reducing the switching time between isotopes from several seconds to a few milli-seconds. New AMS systems accomplish fast switching by modifying the beam energy though the 90 injection magnet by pulsing the voltage by several kV on the flight tube in the magnet. That requires that the flight tube be electrically insulated which competes with having the flight tube as large as possible. At the ANU, insulating the magnet flight tube would not only have reduced the acceptance of the injection system, but conflicted with a beam chopper attached to the flight tube, that would also have had to be insulated from the ground. This was not practical so the novel alternative of pulsing the voltage on the high voltage ion source deck is being implemented. Beam optics calculations have been performed and beam tests conducted that demonstrated that, in addition to pulsing the voltage on the 150 kV ion source deck, a pulsed Einzel lens in front of the following electrostatic quadrupole triplet lens is required to maintain isotope-independent transmission through the 14UD Pelletron accelerator. The high voltage rise time performance of the components of the system has been shown to be satisfactory.

Weisser, D. C.; Fifield, L. K.; Tims, S. G.; Lobanov, N. R.; Crook, G. G.; Tsifakis, D.; Tunningley, T. B.

2013-02-01

364

Identification of unstable metabolites of Lonafarnib using liquid chromatography-quadrupole time-of-flight mass spectrometry, stable isotope incorporation and ion source temperature alteration.  

PubMed

Structural characterization of unstable metabolites and other drug-derived entities poses a serious challenge to the analytical chemist using instrumentation such as LC-MS and LC-MS/MS, and may lead to inaccurate identification of metabolite structures. The task of structural elucidation becomes even more difficult when an analyte is unstable in the ion source of the mass spectrometer. However, a judicious selection of the experimental conditions and the advanced features of new generation mass spectrometers can often overcome these difficulties. We describe here the identification of three drug-derived peaks (A, B and C) that were detected from a Schering-Plough developmental compound (Lonafarnib) following incubation with cDNA-expressed human CYP3A4. Definitive characterization was achieved using (1) accurate mass measurement, (2) stable isotope incorporation, (3) reduced ion source temperature, (4) alkali ion attachment and (5) MS/MS fragmentation studies. The protonated ions of compounds A and B fragmented almost completely in the source, yielding ions of the same mass-to-charge ratio (m/z) as that of protonated C (CH+). Fortunately, the presence of Na+ and K+ adducts of A and B provided information crucial to distinguishing AH+ and BH+ from their fragment ions. Metabolite A was shown to be an unstable hydroxylated metabolite of Lonafarnib. The metabolite C was shown to be a dehydrogenated metabolite of Lonafarnib (Lonafarnib-2H), unstable in the presence of protic solvents. Finally, B was artifactually formed most likely from C by the solvolytic addition of methanol during sample preparation. MS/MS fragmentation experiments assisted in identifying the site of metabolism in A and chemical modification in B. A and C readily interconvert through hydration/dehydration, and B and C through addition/elimination of methanol present in the sample-processing solvents. Finally, NMR experiments were performed to confirm the structures of A and C. PMID:17051523

Tong, Wei; Chowdhury, Swapan K; Su, Ai-Duen; Feng, Wenqing; Ghosal, Anima; Alton, Kevin B

2006-11-01

365

Determination of 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid in a urine-based standard reference material by isotope-dilution liquid chromatography-mass spectrometry with electrospray ionization.  

PubMed

A new method is presented for the determination of 11-nor-delta9-tetrahydrocannabinol-9-carboxylic acid (THC-9-COOH) in urine-based standard reference materials (SRMs) for marijuana metabolite. This method is based on isotope-dilution liquid chromatography-mass spectrometry (LC-MS) using electrospray for ionization (ESI). An isotopically labeled compound, 5',11-nor-delta9-THC-9-carboxylic acid-d3, was used as an internal standard. Solid-phase extraction (SPE) was used to prepare samples for LC-MS analyses. LC was performed on a C18 column with an isocratic mobile phase consisting of 0.05 M of ammonium acetate in methanol/water (75:25). Electrospray ionization in the negative ion mode was used to monitor the [M-H]- ions at m/z 343 and 346 for THC-9-COOH and its labeled internal standard, respectively. Samples of SRM 1507b (THC-9-COOH in freeze-dried urine) were prepared and measured on three separate sets. The within-set coefficients of variation ranged from 0.32% to 2.77%. The correlation coefficients of the regression lines were 0.999 to 1.000. The detection limit for THC-9-COOH with this method is estimated to be 5 pg/mL. This method compared well with the gas chromatography-mass spectrometry method used for certification, and results were within the certified values of THC-9-COOH for SRM 1507b. PMID:10999343

Tai, S S; Welch, M J

2000-09-01

366

Establishing drug resistance in microorganisms by mass spectrometry.  

PubMed

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 (13)C-labeled media, and analyzed by MALDI TOF MS. Algorithms for data analysis are presented as well. PMID:23568030

Demirev, Plamen A; Hagan, Nathan S; Antoine, Miquel D; Lin, Jeffrey S; Feldman, Andrew B

2013-04-09

367

Advanced Mass Spectrometers for Hydrogen Isotope Analyses  

SciTech Connect

This report is a summary of the results of a joint Savannah River Laboratory (SRL) - Savannah River Plant (SRP) ''Hydrogen Isotope Mass Spectrometer Evaluation Program''. The program was undertaken to evaluate two prototype hydrogen isotope mass spectrometers and obtain sufficient data to permit SRP personnel to specify the mass spectrometers to replace obsolete instruments.

Chastagner, P.

2001-08-01

368

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

369

Use of Differential Isotopic Labeling and Mass Spectrometry To Analyze Capacitation-Associated Changes in the Phosphorylation Status of Mouse Sperm Proteins  

PubMed Central

Mammalian sperm need to reside in the female reproductive tract for a finite period of time before acquiring fertilizing competence. The biochemical changes associated with this process are collectively known as “capacitation”. With the use of the mouse as an experimental model, we have previously demonstrated that capacitation is associated with a cAMP-dependent increase in protein tyrosine phosphorylation. However, little is known about the identity and function of the protein targets of this phosphorylation cascade. In the present work, we have used differential isotopic labeling coupled with immobilized metal affinity chromatography (IMAC)-based phosphopeptide enrichment and analysis on a hybrid linear ion trap/FT-ICR mass spectrometer to measure the changes in protein phosphorylation resulting from the capacitation process. As no kinase activators and/or phosphatase inhibitors were used in the preparation of the sperm samples, phosphorylated residues identified in this study represent in vivo sites of phosphorylation. Also, in contrast to other methods which rely on the incorporation of isotopically labeled amino acids at the protein level (e.g., SILAC), the present technique is based on the Fisher esterification of protein digests, allowing for the comparison of phosphorylation status in the absence of protein synthesis. This approach resulted in the identification of 55 unique, in vivo sites of phosphorylation and permitted the relative extent of phosphorylation, as a consequence of capacitation, to be calculated for 42 different phosphopeptides. This work represents the first effort to determine which specific protein phosphorylation sites change their phosphorylation status in vivo as a result of the mammalian capacitation process.

Platt, Mark D.; Salicioni, Ana M.; Hunt, Donald F.; Visconti, Pablo E.

2010-01-01

370

Gas chromatography-mass spectrometry (GC-MS) analysis of ...  

Treesearch

Title: Gas chromatography-mass spectrometry (GC-MS) analysis of ... trial using Gas Chromatography-Mass Spectrometry (GC-MS) detected differences in fatty acid ... methanol, chloroform, fatty acids, mass spectrometry, gas chromatography , ...

371

The Mass-Dependence of Cadmium Isotope Fractionation During Evaporation  

NASA Astrophysics Data System (ADS)

Isotope fractionation laws relate the isotope fractionation factor ?A of one isotope ratio to the fractionation factor ?B of a second isotope ratio of the same element with a fractionation exponent ?, such that ?A = ?B?. In a recent paper, Young et al. (GCA 66, 1095-1104 (2002)) inferred that kinetic and equilibrium isotope fractionations are characterized by different mass functions, such that ?kin is not equal to ?eq. As a consequence, kinetic isotope fractionation is expected to produce fractionation lines in three isotope space that are different from those generated by equilibrium fractionation processes. Young et al. furthermore stated that the variability in mass-dependent fractionation laws may be sufficient to account for the negative ?17O of tropospheric O2 and the ?17O anomalies of minerals in SNC meteorites. Such variations have otherwise been interpreted as evidence of non-mass dependant isotope fractionations (Luz et al., Nature 400, 547-550 (1999); Farquhar et al., Science 280, 1589-1582 (1998)). In the present study, we investigated the mass-dependence of isotope fractionation by evaluating the results of evaporation experiments that produced very large differences in Cd isotope compositions (up to about 100‰ ). In these experiments, liquid Cd was evaporated into a vacuum at a temperature of about 200°C. The metal residues remaining after evaporation were analyzed for their Cd isotope composition by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) relative to the unfractionated starting material. The precision of the measurements is sufficient to clearly distinguish between different fractionation mechanisms. In linearized three-isotope space, the residual Cd metals plot on fractionation lines (e.g., with a slope ? = 2.049 +/- 2 for 106}Cd/{114Cd vs. 110}Cd/{114Cd) that are intermediate between the kinetic (? = 2.036) and the equilibrium (? = 2.075) fractionation lines. This can be explained by an evaporation process that encompasses both "kinetic evaporation" into a vacuum and "equilibrium evaporation". Equilibrium evaporation requires that the Cd melt equilibrated with the vapor phase. This may have occurred within bubbles that formed in the liquid metal or by partial recondensation of vapor (back reaction). The data were further evaluated to extract the relative amount of isotope fractionation produced by kinetic and equilibrium evaporation, and to calculate the equilibrium isotope fractionation factor between liquid and molten Cd. In conclusion, the experimental results demonstrate that deviations from mass fractionation reference lines must be carefully evaluated before they are ascribed to non-mass dependent isotope effects.

Rehkamper, M.; Wombacher, F.; Mezger, K.; Wiechert, U.

2002-12-01

372

Application of diode lasers to resonance ionization mass spectrometry  

SciTech Connect

Detailed studies of the application of diode lasers to resonance ionization mass spectrometry (RIMS) have been made. These devices were used to excite the first transition of several 1+1+1 multiple photon processes for both lanthanum 138 and 139. Enhanced isotopic selectivity resulted; very-high resolution spectra were also obtained with the diode laser step to yield new atomic hyperfine structure constants. 4 refs., 3 figs.

Young, J.P.; Shaw, R.W.; Smith, D.H.

1990-01-01

373

Proposal on dynamic correction method for resonance ionization mass spectrometry  

NASA Astrophysics Data System (ADS)

For high precision and accuracy in isotopic ratio measurement of transuranic elements using laser ablation assisted resonance ionization mass spectrometry, a dynamic correction method based on correlation of ion signals with energy and timing of each laser pulse was proposed. The feasibility of this dynamic correction method was investigated through the use of a programmable electronics device for fast acquisition of the energy and timing of each laser pulse.

Noto, Takuma; Tomita, Hideki; Richter, Sven; Schneider, Fabian; Wendt, Klaus; Iguchi, Tetsuo; Kawarabayashi, Jun

2013-04-01

374

Development of isotope dilution gamma-ray spectrometry for plutonium analysis  

SciTech Connect

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

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

1991-01-01

375

Kinetics of labelling of organic and amino acids in potato tubers by gas chromatography-mass spectrometry following incubation in (13)C labelled isotopes.  

PubMed

Metabolic pathways of primary metabolism of discs isolated from potato tubers were evaluated by the use of a gas chromatography-mass spectrometry (GC-MS) method generated specifically for this purpose. After testing several possible methods including chemical ionization, it was decided for reasons of sensitivity, reproducibility and speed to use electron impact ionization-based GC-MS analysis. The specific labelling and label accumulation of over 30 metabolites including a broad number of sugars, organic and amino acids was analysed following the incubation of tuber discs in [U-(13)C]glucose. The reproducibility of this method was similar to that found for other GC-MS-based analyses and comparison of flux estimates from this method with those obtained from parallel, yet less comprehensive, radiolabel experiments revealed close agreement. Therefore, the novel method allows quantitatively evaluation of a broad range of metabolic pathways without the need for laborious (and potentially inaccurate), chemical fractionation procedures commonly used in the estimation of fluxes following incubation in radiolabelled substrates. As a first experiment the GC-MS method has been applied to compare the metabolism of wild type and well-characterized transgenic potato tubers exhibiting an enhanced sucrose mobilization. The fact that this method is able to rapidly yield further comprehensive information into primary metabolism illustrates its power as a further phenotyping tool for the analysis of plant metabolism. PMID:15272882

Roessner-Tunali, Ute; Liu, JunLi; Leisse, Andrea; Balbo, Ilse; Perez-Melis, Alicia; Willmitzer, Lothar; Fernie, Alisdair R

2004-08-01

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

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

PubMed Central

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

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

2008-01-01

378

Measurement of plutonium and uranium isotopic abundances by gamma-ray spectrometry  

SciTech Connect

The isotopic composition of plutonium and uranium is needed for purposes of sample confirmation, or for interpreting results from calorimeters or neutron-coincidence measurement instruments to determine nuclear material mass. The authors have developed measurement methods and computer codes utilizing high-resolution gamma-ray spectrometry to measure the relative isotopic abundances of plutonium and uranium in various forms nondestructively. The computer codes, known as MGA and MGAU, have unique analysis methodologies that the authors briefly describe in this paper.

Ruhter, W.D. [Lawrence Livermore National Lab., CA (United States); Gunnink, R. [Gunnink (Ray), Fremont, CA (United States)

1996-02-01

379

Deconvolution of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry isotope patterns to determine ratios of A-type to B-type interflavan bonds in cranberry proanthocyanidins.  

PubMed

A method to deconvolute overlapping isotope patterns in positive mode matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was developed to determine ratios of A- to B-type interflavan bonds in proanthocyanidins that were isolated from cranberry (Vaccinium macrocarpon, Ait.) press cake (c-PAC). Precision and accuracy was validated for binary mixtures of procyanidins A2 and B2. Deconvolution of c-PAC spectra indicated that oligomers with one or more A-type interflavan bonds occur in a higher proportion than oligomers with all B-type interflavan bonds. c-PAC with at least one A-type bond accounted for more than 91% of the oligomers between trimers and undecamers. The c-PAC isotope patterns are highly repeatable, suggesting that the method can be applied to authentication, standardization and efficacy of cranberry products in relationship to urinary tract health. This is the first time MALDI-TOF MS has been used for estimating ratios of A- to B-type bonds in PAC. PMID:22953884

Feliciano, Rodrigo P; Krueger, Christian G; Shanmuganayagam, Dhanansayan; Vestling, Martha M; Reed, Jess D

2012-06-07

380

Practical recommendations for the reduction of memory effects in compound-specific 15N/14N-ratio analysis of enriched amino acids by gas chromatography/combustion/isotope ratio mass spectrometry.  

PubMed

Gas chromatography/combustion/isotope ratio mass spectrometry (GC-C-IRMS) is a highly sensitive approach which allows the analysis of the (13)C/(12)C and (15)N/(14)N isotope composition of amino acids in the range of natural abundance or in slightly (13)C- and (15)N-enriched samples. However, the accuracy of measurements remains a permanent challenge. Here we show the effect of the presence of slightly (15)N-enriched compounds in physiological samples on the accuracy and reproducibility of (15)N-abundances of amino acids within or between analytical runs. We spiked several individual amino acids with the respective (15)N-labelled isotopomer and measured the (15)N/(14)N ratios of other amino acids in the same sample or in the following analytical runs. Intra- and inter-run memory effects can be observed in (15)N/(14)N ratios of amino acids. Sample throughput is reduced when cleaning runs using standard mixtures are required to restore initial conditions after runs of samples with (15)N-enriched analytes. Possible reasons for the observed phenomenon and its implications for work in the lower (15)N-enrichment range (<0.5 APE) are discussed and include different aspects of gas chromatography, derivatisation, and hot catalytic metal surface effects. Results need to be interpreted with caution if complex physiological samples contain (15)N-enriched amino acids beyond 500‰ ?(15)N (~0.18 APE). PMID:22173808

Petzke, Klaus J; Metges, Cornelia C

2012-01-30

381

An evaluation of a single-step extraction chromatography separation method for Sm-Nd isotope analysis of micro-samples of silicate rocks by high-sensitivity thermal ionization mass spectrometry.  

PubMed

A single-step separation scheme is presented for Sm-Nd radiogenic isotope system on very small samples (1-3 mg) of silicate rock. This method is based on Eichrom(®) LN Spec chromatographic material and affords a straightforward separation of Sm-Nd from complex matrix with good purity and satisfactory blank levels, suitable for thermal ionization mass spectrometry (TIMS). This technique, characterized by high efficiency (single-step Sm-Nd separation) and high sensitivity (TIMS on NdO(+) ion beam), is able to process rapidly (3-4 h), with low procedure blanks (<10 pg) and very small sample (1-3 mg). Replicate measurements by TIMS on (143)Nd/(144)Nd ratios and Sm-Nd concentrations are presented for eleven international silicate rock reference materials, spanning a wide range of Sm-Nd contents and bulk compositions. The analytical results show a good agreement with recommended values within ±0.004% for the (143)Nd/(144)Nd isotopic ratio and ±2% for Sm-Nd quantification at the 95% confidence level. It is noted that the uncertainty of this method is about 3 times larger than typical precision achievable with two-stage full separation followed by state-of-the-art conventional TIMS using Nd(+) ion beams which require much larger amounts of Nd. Hence, our single-step separation followed by NdO(+) ion beam technique is preferred to the analysis for microsamples. PMID:22023865

Li, Chao-Feng; Li, Xian-Hua; Li, Qiu-Li; Guo, Jing-Hui; Li, Xiang-Hui; Liu, Tao

2011-09-01

382

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

2013-02-08

383

Methods for recalibration of mass spectrometry data  

DOEpatents

Disclosed are methods for recalibrating mass spectrometry data that provide improvement in both mass accuracy and precision by adjusting for experimental variance in parameters that have a substantial impact on mass measurement accuracy. Optimal coefficients are determined using correlated pairs of mass values compiled by matching sets of measured and putative mass values that minimize overall effective mass error and mass error spread. Coefficients are subsequently used to correct mass values for peaks detected in the measured dataset, providing recalibration thereof. Sub-ppm mass measurement accuracy has been demonstrated on a complex fungal proteome after recalibration, providing improved confidence for peptide identifications.

Tolmachev, Aleksey V. (Richland, WA); Smith, Richard D. (Richland, WA)

2009-03-03

384

MAPPING HUMAN MOVEMENT USING STABLE OXYGEN ISOTOPIC RATIO MASS SPECTROMETRY: POTENTIAL APPLICATION TO FORENSIC SCIENCE DEMONSTRATED BY A MODERN HORSE-HUMAN STUDY  

Microsoft Academic Search

The utility of stable oxygen isotope analysis for demonstrating human migration has been developed and demonstrated on archaeological human populations. The application of this approach to tracking human movement has seldom been applied within forensic science. This paper gives results from a stable oxygen isotope assessment of extant mo