Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Liu, Juan; Sheng, Anxu; Li, Xiaoxu; Arai, Yuji; Ding, Yuefei; Nie, Mingjun; Yan, Mingquan; Rosso, Kevin M.

doi:10.1021/acs.est.1c08044

Title: Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

Journal Article · 20 February 2022 · Environmental Science and Technology

DOI: https://doi.org/10.1021/acs.est.1c08044 · OSTI ID:2217529

^[1];

^[1]; Li, Xiaoxu ^[1];

^[2]; Ding, Yuefei ^[1]; Nie, Mingjun ^[1];

^[1];

^[3]

Peking Univ., Beijing (China)
Univ. of Illinois at Urbana-Champaign, IL (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Transformation of metastable Fe(III) oxyhydroxides is a prominent process in natural environments and can be significantly accelerated by the coexisting aqueous Fe(II) (Fe(II)_aq). Recent evidence points to the solution mass transfer of labile Fe(III) (Fe(III)_labile) as the primary intermediate species of general importance. However, a mechanistic aspect that remains unclear is the dependence of phase outcomes on the identity of the metastable Fe(III) oxyhydroxide precursor. Here, we compared the coupled evolution of Fe(II) species, solid phases, and Fe(III)_labile throughout the Fe(II)-catalyzed transformation of lepidocrocite (Lp) versus ferrihydrite (Fh) at equal Fe(III) mass loadings with 0.2–1.0 mM Fe(II)_aq at pH = 7.0. Similar to Fh, the conversion of Lp to product phases occurs by a dissolution–reprecipitation mechanism mediated by Fe(III)_labile that seeds the nucleation of products. Though for Fh we observed a transformation to goethite (Gt), accompanied by the transient emergence and decline of Lp, for initial Lp we observed magnetite (Mt) as the main product. Further, a linear correlation between the formation rate of Mt and the effective supersaturation in terms of Fe(III)_labile concentration shows that Fe(II)-induced transformation of Lp into Mt is governed by the classical nucleation theory. When Lp is replaced by equimolar Gt, Mt formation is suppressed by opening a lower barrier pathway to Gt by heterogeneous nucleation and growth on the added Gt seeds. The collective findings add to the mechanistic understanding of factors governing phase selections that impact iron bioavailability, system redox potential, and the fate and transport of coupled elements.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

OSTI ID:: 2217529

Report Number(s):: PNNL-SA--178846

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 6 Vol. 56; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
classical nucleation theory
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labile Fe(III)
lepidocrocite
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Title: Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides

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