S. G. John, E. A. Boyle, B. R. Cunningham, F.-X. Fu, S. Greene, C. Hodierne, D. A. Hutchins, A. Kavner, A. L. King, A. D. Rosenberg, M. A. Saito, A. Wasson
{"title":"将铁(III)还原为铁(II)过程中的动力学同位素效应:非生物还原过程中的巨大正负同位素效应和浮游植物培养过程中的较小分馏效应","authors":"S. G. John, E. A. Boyle, B. R. Cunningham, F.-X. Fu, S. Greene, C. Hodierne, D. A. Hutchins, A. Kavner, A. L. King, A. D. Rosenberg, M. A. Saito, A. Wasson","doi":"10.1029/2023GC010952","DOIUrl":null,"url":null,"abstract":"<p>Iron stable isotopes (δ<sup>56</sup>Fe) 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 δ<sup>56</sup>Fe, and the use of Fe isotopes as a tracer Fe source and biological processes in the ocean and other natural systems.</p>","PeriodicalId":50422,"journal":{"name":"Geochemistry Geophysics Geosystems","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1029/2023GC010952","citationCount":"0","resultStr":"{\"title\":\"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\",\"authors\":\"S. G. John, E. A. Boyle, B. R. Cunningham, F.-X. Fu, S. Greene, C. Hodierne, D. A. Hutchins, A. Kavner, A. L. King, A. D. Rosenberg, M. A. Saito, A. Wasson\",\"doi\":\"10.1029/2023GC010952\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Iron stable isotopes (δ<sup>56</sup>Fe) 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. 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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
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.
期刊介绍:
Geochemistry, Geophysics, Geosystems (G3) publishes research papers on Earth and planetary processes with a focus on understanding the Earth as a system. Observational, experimental, and theoretical investigations of the solid Earth, hydrosphere, atmosphere, biosphere, and solar system at all spatial and temporal scales are welcome. Articles should be of broad interest, and interdisciplinary approaches are encouraged.
Areas of interest for this peer-reviewed journal include, but are not limited to:
The physics and chemistry of the Earth, including its structure, composition, physical properties, dynamics, and evolution
Principles and applications of geochemical proxies to studies of Earth history
The physical properties, composition, and temporal evolution of the Earth''s major reservoirs and the coupling between them
The dynamics of geochemical and biogeochemical cycles at all spatial and temporal scales
Physical and cosmochemical constraints on the composition, origin, and evolution of the Earth and other terrestrial planets
The chemistry and physics of solar system materials that are relevant to the formation, evolution, and current state of the Earth and the planets
Advances in modeling, observation, and experimentation that are of widespread interest in the geosciences.