Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides
Abstract
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 suppressedmore »
- Authors:
-
- Peking Univ., Beijing (China)
- Univ. of Illinois at Urbana-Champaign, IL (United States)
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); National Natural Science Foundation of China (NSFC)
- OSTI Identifier:
- 2217529
- Report Number(s):
- PNNL-SA-178846
Journal ID: ISSN 0013-936X
- Grant/Contract Number:
- AC05-76RL01830; AC02-06CH11357; 41820104003; 41972318
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Environmental Science and Technology
- Additional Journal Information:
- Journal Volume: 56; Journal Issue: 6; Journal ID: ISSN 0013-936X
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; iron; minerals; nanoparticles; nucleation; phase transitions; lepidocrocite; ferrihydrite; goethite; magnetite; labile Fe(III); dissolution−reprecipitation; classical nucleation theory; heterogeneous nucleation
Citation Formats
Liu, Juan, Sheng, Anxu, Li, Xiaoxu, Arai, Yuji, Ding, Yuefei, Nie, Mingjun, Yan, Mingquan, and Rosso, Kevin M. Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides. United States: N. p., 2022.
Web. doi:10.1021/acs.est.1c08044.
Liu, Juan, Sheng, Anxu, Li, Xiaoxu, Arai, Yuji, Ding, Yuefei, Nie, Mingjun, Yan, Mingquan, & Rosso, Kevin M. Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides. United States. https://doi.org/10.1021/acs.est.1c08044
Liu, Juan, Sheng, Anxu, Li, Xiaoxu, Arai, Yuji, Ding, Yuefei, Nie, Mingjun, Yan, Mingquan, and Rosso, Kevin M. Mon .
"Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides". United States. https://doi.org/10.1021/acs.est.1c08044. https://www.osti.gov/servlets/purl/2217529.
@article{osti_2217529,
title = {Understanding the Importance of Labile Fe(III) during Fe(II)-Catalyzed Transformation of Metastable Iron Oxyhydroxides},
author = {Liu, Juan and Sheng, Anxu and Li, Xiaoxu and Arai, Yuji and Ding, Yuefei and Nie, Mingjun and Yan, Mingquan and Rosso, Kevin M.},
abstractNote = {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.},
doi = {10.1021/acs.est.1c08044},
journal = {Environmental Science and Technology},
number = 6,
volume = 56,
place = {United States},
year = {Mon Feb 21 00:00:00 EST 2022},
month = {Mon Feb 21 00:00:00 EST 2022}
}
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