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2004 Annual Science Report

University of California, Los Angeles Reporting  |  JUL 2003 – JUN 2004

Electrochemical Isotope Effects With Applications to Stable Isotope Fractionation in Transition Metals

4 Institutions
3 Teams
0 Publications
0 Field Sites
Field Sites

Project Progress

Our project to identify the underlying mechanisms of stable isotope fractionation in biological systems is moving forward. We have recently collected evidence that there is a charge-transfer contribution to kinetic stable isotope fractionation that should have significance for the biological fractionation of 56Fe, 57 Fe, and 54 Fe and other transition metal isotopes. We performed a series of electroplating experiments that demonstrated a voltage-dependent isotope fractionation during reduction of Fe +2 to Fe metal, with magnitudes covering the range observed in natural biotic and abiotic systems. We have developed a theory, based on the fundamental theory for electron transfer developed previously by Marcus, that accounts for the observed voltage dependent fractionation. The theory is general and makes a broad-based series of predictions concerning stable isotope fractionation in a wide variety of charge-transfer reactions. Our results demonstrate a specific mechanistic origin of stable isotope fractionations in Fe during redox phenomena.

Armed with this new tool, we are now in position to use observed stable isotope fractionations as markers for the specific driving forces in charge-transfer reactions, including biologically mediated electron exchange reactions. In particular, the theory makes testable predictions about the isotope fractionation to be observed based on the ligands that surround a given transition metal during the electron-transfer processes. We are presently expanding our experiments to test these predictions.

    Abby Kavner
    Unspecified Role
    Edward Young Edward Young
    Unspecified Role
    Objective 3.1
    Sources of prebiotic materials and catalysts

    Objective 4.1
    Earth's early biosphere

    Objective 4.2
    Foundations of complex life

    Objective 6.1
    Environmental changes and the cycling of elements by the biota, communities, and ecosystems

    Objective 7.1
    Biosignatures to be sought in Solar System materials