1. Kinetic Isotope Effects During Reduction of Fe(III) to Fe(II): Large Normal and Inverse Isotope Effects for Abiotic Reduction and Smaller Fractionations by Phytoplankton in Culture.
- Author
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John, S. G., Boyle, E. A., Cunningham, B. R., Fu, F.‐X., Greene, S., Hodierne, C., Hutchins, D. A., Kavner, A., King, A. L., Rosenberg, A. D., Saito, M. A., and Wasson, A.
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KINETIC isotope effects ,IRON isotopes ,ETHYLENEDIAMINETETRAACETIC acid ,ISOTOPES ,ISOTOPIC fractionation ,CHEMICAL testing - Abstract
Iron stable isotopes (δ56Fe) are a useful tool for studying Earth processes, many of which involve redox transformations between Fe(III) and Fe(II). Here, we present two related experimental efforts, a study of the kinetic isotope effects (KIEs) associated with the reduction of Fe(III)‐ethylenediaminetetraacetic acid (EDTA) to Fe(II), and measurements of the biological fractionation of Fe isotopes by phytoplankton in culture. Reductants tested were ascorbate, hydroxylamine, Mn(II), dithionite, and photoreduction at pH between 5 and 9 and temperatures from 0 to 100°C. Isotope fractionations were very large, and included both normal and inverse KIEs, ranging from −4‰ to +5‰. Experiments were reproducible, yielding similar results for triplicate experiments run concurrently and for experiments run weeks apart. However, fractionations were not predictable, without a clear relationship to reaction rate, temperature, pH, or the reductant used. Acquisition of Fe by eukaryotic phytoplankton also often involves the reduction of Fe(III) to Fe(II). Several species of diatoms and a coccolithophore were tested for Fe isotope fractionation in culture using EDTA, NTA, and DFB as Fe(III) chelating ligands, yielding fractionations from −1.3‰ to +0.6‰. Biological isotope effects were also unpredictable, showing no clear relationship to species, growth rate, or Fe concentration. Variability in Fe isotope fractionation observed in culture may be explained in part by the sensitivity of KIEs. This work has implications for the industrial purification of isotopes, interpretation of natural δ56Fe, and the use of Fe isotopes as a tracer Fe source and biological processes in the ocean and other natural systems. Plain Language Summary: The stable isotopes of iron react at slightly different rates during natural processes, giving rise to variations in Fe stable isotope ratios (δ56Fe) on Earth's surface. We therefore designed two kinds of experiments with the goal of better understanding variations in δ56Fe on Earth. First, Fe(III) bound to the organic molecule ethylenediaminetetraacetic acid was reduced to Fe(II). It was found that under some conditions the lighter isotopes reacted more quickly and under some conditions heavier isotopes reacted more quickly, however there were no clear patterns which allowed us to predict these isotope fractionations. Second, phytoplankton were grown in the laboratory, and their Fe isotope ratios were measured and compared to the media in which they were grown. In these experiments too, a range of fractionations was observed but there were no clear patterns in the results. Though our experiments did not lead to easily predictable results, they contribute to our understanding of how Fe isotopes behave; for example, the large isotope fractionations observed here might have industrial applications for isotope purification, and our work suggests that determining the magnitude of biological Fe isotope fractionation might be better accomplished by in situ observation rather than additional laboratory experiments. Key Points: Iron isotope fractionation was tested during chemical reduction of Fe(III)‐ethylenediaminetetraacetic acid to Fe(II)‐(ferrozine)3Biological fractionation of Fe isotopes was tested for eukaryotic phytoplankton in cultureResults are not easily interpreted but have implications for understanding redox kinetic isotope effects in the laboratory and in nature [ABSTRACT FROM AUTHOR]
- Published
- 2024
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