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  • MC-ICPMS
  • Neptune
  • Cu, Zn, Fe isotopes
  • Human blooad

Isotopic analysis of the metabolically relevant transition metals Cu, Fe and Zn in human blood from vegetarians and omnivores using multi-collector ICP-mass spectrometry

Lana Van Heghe (1), Emma Engstrom (2), Ilia Rodushkin (2), Christophe Cloquet (3) and Frank Vanhaecke (1)

1) Department of Analytical Chemistry, Ghent University, Krijgslaan 281–S12, BE-9000 Ghent, Belgium, 2) ALS Scandinavia AB, Aurorum 10, SE-977 75 Lulea, Swede, 3) CRPG/CNRS, BP 20, 54501, Vandoeuvre-Nancy, France

Journal of Analytical Atomic Spectrometry (2012), V27, pp1327-1334, 10.1039/c2ja30070b

Goal: Multi-collector ICP-mass spectrometry (MC-ICP-MS) was used for the isotopic analysis of Cu, Fe and Zn, isolated from human whole blood. For Fe, the by now well-known difference in isotopic composition between blood from male and female individuals was confirmed. The isotopic composition of Zn in whole blood was assessed to be governed by the diet as a significant difference could be established between blood from vegetarians and from omnivores, respectively. For the isotopic composition of Cu, interpretation of the results is more challenging, as neither gender, nor diet seems to have a significant influence, but the combined influence of both factors may show an effect.

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  • MC-ICPMS
  • Neptune
  • Cu-Zn isotopes
  • Protein

Re-partitioning of Cu and Zn isotopes by modified protein expression

Anette Büchl (1), Chris J Hawkesworth (1), K Vala Ragnarsdottir (1,3) and David R Brown (2)

1) Department of Earth Sciences, University of Bristol, Wills Memorial Building, Bristol, BS8 4EU, UK, 2) Department of Biology and Biochemistry, University of Bath, Bath, BA2 7AY, UK, 3) School of Engineering and Natural Sciences, University of Iceland, Hjarðarhagi 6, 107 Reykjavík, Iceland

Geochemical Transactions (2008), V9, doi: 10.1186/1467-4866-9-11

Goal: Cu and Zn have naturally occurring non radioactive isotopes, and their isotopic systematics in a biological context are poorly understood. In this study we used double focussing mass spectroscopy to determine the ratios for these isotopes for the first time in mouse brain. The Cu and Zn isotope ratios for four strains of wild-type mice showed no significant difference (δ65Cu -0.12 to -0.78 permil; δ66Zn -0.23 to -0.48 permil). We also looked at how altering the expression of a single copper binding protein, the prion protein (PrP), alters the isotope ratios.

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  • MC-ICPMS
  • Neptune
  • Cu-Zn isotopes
  • Soil

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

O.S. Pokrovsky (1), J. Viers (1), E.E. Emnova (2), E.I. Kompantseva (3), R. Freydier (1)

1) Laboratoire de Me´canismes et Transfert en Ge´ologie (LMTG), Universite´ de Toulouse, CNRS, IRD, OMP, 14 Avenue Edouard Belin, 31400 Toulouse, France, 2) Institute of Genetics and Plant Physiology, Moldavian Academy of Science, Kishinev, Moldavia, 3) Institute of Microbiology, Russian Academy of Science, Moscow, Russia

Geochimica et Cosmochimica Acta (2008), V72, pp1742–1757, doi: 10.1016/j.gca.2008.01.018

Goal: This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS.

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  • MC-ICPMS
  • Neptune
  • Cu-Zn isotopes
  • Seawater

The determination of the isotopic composition of Cu and Zn in seawater

J. Bermin (1), D. Vance (2), C. Archer (2), P.J. Statham (3)

1) Department of Geology, Royal Holloway, University of London, Egham, Surrey TW20 0EX, UK, 2) Department of Earth Sciences, University of Bristol, Wills Memorial Building, Bristol BS8 1RJ, UK, 3) School of Ocean and Earth Sciences, Southampton Oceanography Centre, University of Southampton, European Way, Southampton, SO14 3ZH, UK

Chemical Geology (2006), V226, pp280– 297, doi: 10.1016/j.chemgeo.2005.09.025

Goal: The stable isotope compositions of Zn and Cu in natural materials are newly available for measurement with the advent of multiple-collector inductively coupled mass spectrometry (MC–ICPMS). Although the oceans are prime scientific targets, no progress has been made as yet because of considerable analytical challenges involving the low concentrations of these elements in seawater. We present a procedure which allows isotopic analysis of Zn and Cu isotope compositions of seawater samples at least 1 L in size by MC ICPMS.

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  • MC-ICPMS
  • Neptune
  • Cu-Zn isotopes
  • Human blood

Measurement of iron and zinc isotopes in human whole blood: Preliminary application to the study of HFE genotypes

Anna Stenberg (1), Dmitry Malinovsky (1), Björn Öhlander (1), Henrik Andrén (2), Willis Forsling (2), Lena-Maria Engström (3), Anders Wahlin (3), Emma Engström (4), Ilia Rodushkin (4), Douglas C. Baxter (4)

1) Division of Applied Geology, Lulea University of Technology, S-971 87 Lulea, Sweden, 2) Division of Chemistry, Lulea University of Technology, S-971 87 Lulea, Sweden, 3) Department of Medicine, Section of Hematology, Umea University, S-901 85 Umea, Sweden, 4) Analytica AB, Aurorum 10, S-977 75 Lulea, Sweden

Journal of Trace Elements in Medicine and Biology (2005), V19, pp55–60

Goal: Multi-collector inductively coupled plasma – sector field mass spectrometry was applied to the measurement of Fe and Zn isotopes in human whole blood samples. For the Fe present in the blood of healthy adults, enrichment of the lighter isotopes relative to a standard material was observed, in agreement with earlier studies. The level of fractionation was found to be lower in hemochromatosis patients exhibiting homozygous (C282Y/C282Y) mutation of the HFE gene.

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  • MC-ICPMS
  • Neptune
  • Compound Specific Sulpur isotopes
  • Gas Chromatography

Origin and quantitative source assessment of deep oils in the Tazhong Uplift, Tarim Basin

Sumei Li (1), Alon Amrani (2), Xiongqi Pang (1), Haijun Yang (3), Ward Said-Ahmad (2), Baoshou Zhang (3), Qiuju Pang (1)

1) State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum, Beijing 102249, China, 2) Institute of Earth Sciences, The Hebrew University, Jerusalem 91904, Israel, 3) Tarim Oilfield Company, PetroChina, Korla, Xinjiang 841000, China

Organic Geochemistry (2015), V78, pp1–22, doi: 10.1016/j.orggeochem.2014.10.004

Goal: A large amount of deep oil has been discovered in the Tazhong Uplift, Tarim Basin whereas the oil source is still controversial. An integrated geochemical approach was utilized to unravel the characteristics, origin and alteration of the deep oils. This study showed that the Lower Cambrian oil from well ZS1C (1x) was featured by small or trace amounts of biomarkers, unusually high concentration of dibenzothiophenes (DBTs), high d34S of DBTs and high d13C value of n-alkanes. These suggest a close genetic relationship with the Cambrian source rocks and TSR alteration.

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  • MC-ICPMS
  • Neptune
  • S isotopes
  • Gas Chromatography
  • Oil

Compound-specific sulfur isotope analysis of thiadiamondoids of oils from the Smackover Formation, USA

Zvi Gvirtzman (1), Ward Said-Ahmad (1), Geoffrey S. Ellis (2), Ronald J. Hill (3), J. Michael Moldowan (4), Zhibin Wei (5), Alon Amrani (1)

1) Institute of Earth Sciences, Hebrew University, Jerusalem 91904, Israel, 2) US Geological Survey, Denver, CO 80225, USA, 3) EOG Resources, Denver, CO 80202, USA, 4) Biomarker Technologies, Rohnert Park, CA 94928, USA, 5) ExxonMobil Upstream Research Company, Houston, TX 77389, USA

Geochimica et Cosmochimica Acta (2015), V167, pp144–161, doi: 10.1016/j.gca.2015.07.008

Goal: In this study, we analyzed a suite of 12 Upper Jurassic oil and condensate samples generated from source rocks in the Smackover Formation to perform a systematic study of the sulfur isotope distribution in thiadiamondoids (TD) (one and two cages). For comparison we measured the δ34S composition of benzothiophenes (BTs) and dibenzothiophenes (DBTs). We also conducted pyrolysis experiments with petroleum and model compounds to have an insight into the formation mechanisms of TDs. The δ34S of the TDs varied significantly (ca 30‰) between the different oils depending on the degree of thermochemical sulfate reduction alteration. The results showed that within the same oil, the one-cage TDs were relatively uniform, with 34S enriched values similar to those of the coexisting BTs.

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  • MC-ICPMS
  • Neptune
  • Cl isotopes
  • Gas Chromatography

GC/Multiple Collector-ICPMS Method for Chlorine Stable Isotope Analysis of Chlorinated Aliphatic Hydrocarbons

Marc R. M. D. Van Acker (1), Anat Shahar (2), Edward D. Young (2) and Max L. Coleman (3)

1) School of Human and Environmental Sciences, University of Reading, Reading RG6 6AB, U.K., 2) Department of Earth and Space Sciences and Institute of Geophysics and Planetary Physics, University of California at Los Angeles, Los Angeles, California 90095, USA 3) Jet Propulsion Laboratory, California Institute of Technology, Pasadena, California 91109, USA

Analytical Chemistry (2006), V78(13), pp4663–4667, doi: 10.1021/ac0602120

Goal: Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of ≥10 000 to eliminate interference of mass 37 ArH with Cl.

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  • MC-ICPMS
  • Neptune
  • Br isotopes
  • Gas Chromatography

Compound-specific 81Br/79Br analysis by capillary gas chromatography/multicollector inductively coupled plasma mass spectrometry

Sean P. Sylva, Lary Ball, Robert K. Nelson and Christopher M. Reddy

Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, MA 02543, USA

Rapid Communications Mass Spectrometry (2007), V21, pp3301–3305, doi: 10.1002/rcm.3211

Goal: Brominated organic compounds (BOCs) are of great interest in atmospheric chemistry, natural products, geochemistry, and marine chemistry. The Br isotope ratios (81Br and 79Br; average 81Br/79Br = 0.97277) have significant potential for the study of the source, transport, and fate of these compounds. Currently, there is no published method for determining the Br isotopic content of BOCs in complex mixtures. To measure the ratios of stable Br in BOCs on a compound-specific basis, we assembled a gas chromatography/multicollector inductively coupled plasmamass spectrometry (GC/ MCICPMS) system.

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  • TIMS
  • MC-ICPMS
  • Cd isotopes
  • NIST SRM3108

A Common Reference Material for Cadmium Isotope Studies -- NIST SRM 3108

Wafa Abouchami (1, 2), Stephen J. G. Galer (2), Tristan J. Horner (3), Mark Rehkämper (4), Frank Wombacher (5, 9), Zichen Xue (4), Myriam Lambelet (4), Melanie Gault-Ringold (6), Claudine H. Stirling (6), Maria Schönbächler (7), Alyssa E. Shiel (8, 10), Dominique Weis (8) and Philip F. Holdship (3)

1) Westfälische Wilhelms Universität, Institut für Mineralogie, 48149 Münster, Germany, 2) Max Planck Institute for Chemistry, PO Box 3060, 55020 Mainz, Germany, 3) Department of Earth Sciences, University of Oxford, Oxford OX1 3AN, UK, 4) Department of Earth Science and Engineering, Imperial College, London SW7 2AZ, UK, 5) Institut für Geologie und Mineralogie, Universität zu Köln, 50674 Köln, Germany, 6) Department of Chemistry, University of Otago, Dunedin, New Zealand, 7) School of Earth, Atmospheric and Environmental Sciences, University of Manchester, Manchester M13 9PL, UK (8) Department of Earth and Ocean Sciences, University of British Columbia, British Columbia, Vancouver, Canada (9) Present address: Steinmann Institut, Universität Bonn, 53115 Bonn, Germany (10) Present address: Department of Geology, University of Illinois at Urbana–Champaign, Urbana, IL 61801, USA

Geostandards and Geoanalytical Research (2013), V37(1), pp5–17, doi: 10.1111/j.1751-908X.2012.00175.x

Goal: Research into natural mass-dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC-ICP-MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double-spike techniques, sample-calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in-house Cd solutions used as zero-delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round-robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in-house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero-delta’ in future studies.

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  • TIMS
  • Triton
  • Ca isotopes
  • Osteoporosis

A pilot study on the use of natural calcium isotope (44Ca/40Ca) fractionation in urine as a proxy for the human body calcium balance

Alexander Heuser (1,2), Anton Eisenhauer (2)

1) Leibniz-Institut für Meereswissenschaften, IFM-GEOMAR, Wischhofstr. 1-3, 24148 Kiel, Germany, 2) Steinmann Institut für Geologie, Mineralogie und Paläontologie, Universität Bonn, Poppelsdorfer Schloss, 53115 Bonn, Germany

Bone (2010), V46(4), pp889–896, doi: 10.1016/j.bone.2009.11.037

Goal: We explored the possibility of using natural calcium (Ca) isotope variations in the urine (δ44/40Ca urine) as a proxy for the Ca balance in the human body. We chose two test persons extremely different in their health status, gender and age (4-year-old healthy boy and a 60-year-old woman known to suffer from osteoporosis).

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  • TIMS
  • Triton Plus
  • Ca isotopes
  • Static Collection

TIMS measurements of full range of natural Ca isotopes withinternally consistent fractionation correction

Maria O. Naumenko-Dèzes (1), Claudia Bouman (2), Thomas F. Nägler (1) Klaus Mezger (1) and Igor M. Villa (1,3)

1) Institute für Geologie, Universität Bern, Baltzerstrasse 1+3, 3012 Bern, Switzerland, 2) Thermo Fisher Scientific, Hanna-Kunath-Strasse 11, 28199 Bremen, Germany, 3) Università di Milano Bicocca, Piazza della Scienza 4, 20126 Milano, Italy

International Journal of Mass Spectrometry (2015), V387, pp60-68, doi: 10.1016/j.ijms.2015.07.012

Goal: This study presents static measurements of the Ca isotopic composition of standard reference materials SRM 915 a/b on a Triton Plus thermal ionization mass spectrometer with a specially developed Faradaycup array allowing simultaneous measurement of 40Ca and 48Ca. The total amount of Ca in all analyses was kept <1 g. With this setup the measurement uncertainties were 0.06‰ for 40Ca/44Ca and 0.12‰ for 48Ca/40Ca. Measuring all isotopes simultaneously better allows to test the internal consistency of different Ca isotope abundances reported in the literature.

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  • Mass Spectrometry
  • Ca Isotopes
  • Fractionation

Calcium Isotope Analysis by Mass Spectrometry

Sergei F. Boulyga

Safeguards Analytical Laboratory, Department of Nuclear Sciences and Applications, International Atomic Energy Agency, Wagramer Strasse 5, 1400 Vienna, Austria

Mass Spectrometry Reviews (2010), V29, pp685– 716, doi:

Goal: The variations in the isotopic composition of calcium caused by fractionation in heterogeneous systems and by nuclear reactions can provide insight into numerous biological, geological, and cosmic processes, and therefore isotopic analysis finds a wide spectrum of applications in cosmo- and geochemistry, paleoclimatic, nutritional, and biomedical studies. The measurement of calcium isotopic abundances in natural samples has challenged the analysts for more than three decades.

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  • TIMS
  • Triton: Ca isotopes
  • Meteorites

Calcium Isotope Composition of Meteorites, Earth, and Mars

Justin I. Simon (1), Donald J. DePaolo (1) and Frederic Moynier (2)

1) Center for Isotope Geochemistry, Earth and Planetary Science, University of California, Berkeley, CA 94720, USA, 2) Earth and Planetary Sciences and McDonnell Center for Space Sciences, Washington University in St Louis, MO 63130, USA

The Astrophysical Journal (2009), V702, pp707–715, doi: 10.1088/0004-637X/702/1/707

Goal: The relative abundances of calcium isotopes in the mass range 40–44 were measured in primitive and differentiated meteorites and igneous rocks from Earth and Mars in search of non-mass-dependent variations that could provide clues about early solar system processes. Most bulk samples of planetary materials have calcium isotopic compositions identical with Earth’s within the current resolution of about 0.01% in 40Ca/44Ca. Possible exceptions include carbonaceous chondrites, some ordinary chondrites, and two samples of calcium–aluminumrich inclusions, which have small excesses of 40Ca.

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  • MC-ICPMS
  • Neptune
  • Ca isotopes
  • Osteopenia

Rapidly assessing changes in bone mineral balance using natural stable calcium isotopes

Jennifer L. L. Morgan (1,3), Joseph L. Skulan (2), Gwyneth W. Gordon (2), Stephen J. Romaniello (2) Scott M. Smith (3) and Ariel D. Anbara (2)

1) Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ, 85287, USA; 2) School of Earth and Space Exploration, Arizona State University, Tempe, AZ, 85287, USA; 3) Human Adaptation and Countermeasures Division, National Aeronautics and Space Administration, Houston, TX, 77058, USA

Proceedings of the National Academy of Science of the United States of America (2012), V109(25), pp9989–9994, doi:10.1073/pnas.1119587109

Goal: The ability to rapidly detect changes in bone mineral balance (BMB) would be of great value in the early diagnosis and evaluation of therapies for metabolic bone diseases such as osteoporosis and some cancers. However, measurements of BMB are hampered by difficulties with using biochemical markers to quantify the relative rates of bone resorption and formation and the need to wait months to years for altered BMB to produce changes in bone mineral density large enough to resolve by X-ray densitometry. We show here that, in humans, the natural abundances of Ca isotopes in urine change rapidly in response to changes in BMB. In a bed rest experiment, use of high-precision isotope ratio MS allowed the onset of bone loss to be detected in Ca isotope data after about 1 wk, long before bone mineral density has changed enough to be detectable with densitometry.