Electrochemical Analysis of Changes in Iron Oxide Reducibility during Abiotic Ferrihydrite Transformation into Goethite and Magnetite

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Date
2019-04-02Type
- Journal Article
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Cited 37 times in
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Cited 39 times in
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Abstract
Electron transfer to ferric iron in (oxyhydr-)oxides (hereafter iron oxides) is a critical step in many processes that are central to the biogeochemical cycling of elements and to pollutant dynamics. Understanding these processes requires analytical approaches that allow for characterizing the reactivity of iron oxides toward reduction under controlled thermodynamic boundary conditions. Here, we used mediated electrochemical reduction (MER) to follow changes in iron oxide reduction extents and rates during abiotic ferrous iron-induced transformation of six-line ferrihydrite. Transformation experiments (10 mM ferrihydrite-FeIII) were conducted over a range of solution conditions (pHtrans = 6.50 to 7.50 at 5 mM Fe2+ and for pHtrans = 7.00 also at 1 mM Fe2+) that resulted in the transformation of ferrihydrite into thermodynamically more stable goethite or magnetite. The changes in iron oxide mineralogy during the transformations were quantified using X-ray diffraction analysis. MER measurements on iron oxide suspension aliquots collected during the transformations were performed over a range of pHMER at constant applied reduction potential. The extents and rates of iron oxide reduction in MER decreased with decreasing reaction driving force resulting from both increasing pHMER and increasing transformation of ferrihydrite into thermodynamically more stable iron oxides. We show that the decreases in iron oxide reduction extents and rates during ferrihydrite transformations can be linked to the concurrent changes in iron oxide mineralogy. Show more
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https://doi.org/10.3929/ethz-b-000338554Publication status
publishedExternal links
Journal / series
Environmental Science & TechnologyVolume
Pages / Article No.
Publisher
American Chemical Society (ACS)Organisational unit
00012 - Lehre und Forschung03541 - Kretzschmar, Ruben / Kretzschmar, Ruben
03850 - McNeill, Kristopher / McNeill, Kristopher
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Citations
Cited 37 times in
Web of Science
Cited 39 times in
Scopus
ETH Bibliography
yes
Altmetrics