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    Isotope fractionation studies of molybdenum

    Access Status
    Fulltext not available
    Authors
    Wieser, M.
    De Laeter, John
    Varner, M.
    Date
    2007
    Type
    Journal Article
    
    Metadata
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    Citation
    Wieser, M. E. and De Laeter, J. R. and Varner, M. D. 2007. Isotope fractionation studies of molybdenum. International Journal of Mass Spectrometry 265: pp. 40-48.
    Source Title
    International Journal of Mass Spectrometry
    DOI
    10.1016/j.ijms.2007.05.010
    ISSN
    13873806
    Faculty
    School of Science and Computing
    Faculty of Science and Engineering
    Department of Imaging and Applied Physics
    Remarks

    Copyright © 2007 Elsevier B.V. All rights reserved

    The link to the journal’s home page is: http://www.elsevier.com/wps/find/journaldescription.cws_home/500847/description#description

    URI
    http://hdl.handle.net/20.500.11937/9501
    Collection
    • Curtin Research Publications
    Abstract

    Mass spectrometric studies of the isotopic composition of molybdenum have become an active area of research in stable isotope geochemistry, biogeochemistry and cosmochemistry. The redox chemistry of Mo, together with its proclivity for covalent bonding, indicates its importance in isotope fractionation studies such as palaeoceanography. The measurement of the magnitude of isotope fractionation of Mo in natural systems is a challenging task, in that natural fractionation has to be carefully distinguished from chemical and instrumental isotope fractionation. An ion exchange chemical separation procedure has been developed with high efficiency and low blank, to ensure that the isobaric elements Zr and Ru are removed from the samples before mass spectrometric analysis. The isotope fractionation resulting from this procedure is 0.14‰ per u. The isotopic composition of Mo of a Laboratory Standard has been measured by positive and negative thermal ionization mass spectrometry (P-TIMS and N-TIMS, respectively), to give an isotope fractionation of 6.4‰ and 0.5‰ per u, respectively, with respect to the absolute isotope abundances of Mo. In both cases the lighter isotopes are enhanced with respect to the heavier isotopes. An ascorbic acid activator has enabled the sensitivity of P-TIMS to be improved as compared to traditional methods. The same experiment was repeated using a multiple collector-inductively coupled plasma-mass spectrometer (MC-ICP-MS) to give an isotope fractionation of approximately 17.0‰ per u. In this case the heavier isotopes are enhanced with respect to the lighter isotopes. The strengths and weaknesses of these three mass spectrometric techniques are evaluated. We conclude that MC-ICP-MS is the optimum mass spectrometric method for accurately measuring the isotope fractionation of Mo in natural materials, provided chemical and instrumental isotope fractionation can be resolved from naturally induced isotope fractionation. There is an urgent need for an internationally accepted calibrated reference material to be developed. Our Laboratory Standard has recently been calibrated at Curtin University by measurements of gravimetric mixtures of two enriched isotopes of Mo, to obtain the absolute isotope abundances of Mo. This Laboratory Standard can be made available to those laboratories in which isotopic studies of Mo are executed, to enable meaningful inter-laboratory comparisons to be conducted.

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