Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Qafoku, Odeta; Kovarik, Libor; Bowden, Mark E.; Nakouzi, Elias; Sheng, Anxu; Liu, Juan; Pearce, Carolyn I.; Rosso, Kevin M.

doi:10.1039/d0en00730g

Title: Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Journal Article · Thu Aug 20 00:00:00 EDT 2020 · Environmental Science: Nano

DOI:https://doi.org/10.1039/d0en00730g· OSTI ID:1699508

^[1];

^[1]; Sheng, Anxu ^[2];

^[2];

^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Peking Univ., Beijing (China)

Because of its sorption properties, transformation of the nanomineral ferrihydrite (Fh) into more stable lepidocrocite (Lp) or goethite (Gt) has important impacts on the fate of metals, nutrients, and contaminants in soils/sediments. Although it is well known that the transformation rate is greatly accelerated under suboxic conditions by aqueous Fe(II), the enabling mass transfer process remains an ongoing debate among various mechanisms including dissolution/reprecipitation, solid-state recrystallization, and particle-mediated growth. In this paper, using electron microscopy, we examine the mineralogical evolution of 2-line Fh to Lp/Gt catalyzed by Fe(II) under strict anoxic conditions, including evaluation of Cl–SO₄–HCO₃ anion effects. Emergence of Lp/Gt crystallites at the nanoscale was observed at ~20 min of reaction, earlier than previously reported. Lp is the first phase to nucleate in Cl-rich solutions without HCO₃^–; whereas Lp and Gt concomitantly nucleate in SO₄^2–-rich solutions, and also when co-solute HCO₃^– is added. Lp crystallites nucleate as quasi-2D nanosheets one-unit-cell thick that contour the Fh surface; in contrast, rod-shaped (in Cl/SO₄) or acicular needle-shaped (in HCO₃) Gt crystals nucleate and grow radially outward from the Fh aggregates. Stages of transformation monitored by in situ μ-XRD coupled with aqueous Fe(II) uptake/release measurements are correlated with a short initial sorption stage followed by the onset of Lp/Gt growth that then progresses to Lp loss in favor of Gt. Microscopy data overwhelmingly support dissolution/reprecipitation as the underlying mechanism, including direct evidence for classical ion-by-ion Lp/Gt growth and Lp dissolution. The collective findings imply that the iron mass transfer through solution to distal Lp/Gt growth fronts is a critical enabling process facilitating rapid transformation.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1699508

Report Number(s):: PNNL-SA-155340

Journal Information:: Environmental Science: Nano, Vol. 7, Issue 10; ISSN 2051-8153

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Biogeochemical processes controlling the speciation and transport of arsenic within iron coated sands Herbel, Mitchell; Fendorf, Scott Chemical Geology, Vol. 228, Issue 1-3 https://doi.org/10.1016/j.chemgeo.2005.11.016	journal	April 2006
Ferrozine---a new spectrophotometric reagent for iron Stookey, Lawrence L. Analytical Chemistry, Vol. 42, Issue 7, p. 779-781 https://doi.org/10.1021/ac60289a016	journal	June 1970
Labile Fe(III) from sorbed Fe(II) oxidation is the key intermediate in Fe(II)-catalyzed ferrihydrite transformation Sheng, Anxu; Liu, Juan; Li, Xiaoxu Geochimica et Cosmochimica Acta, Vol. 272 https://doi.org/10.1016/j.gca.2019.12.028	journal	March 2020
Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow Hansel, Colleen M.; Benner, Shawn G.; Neiss, Jim Geochimica et Cosmochimica Acta, Vol. 67, Issue 16 https://doi.org/10.1016/S0016-7037(03)00276-X	journal	August 2003
Adsorption of carbon dioxide on goethite (α-FeOOH) surfaces, and its implications for anion adsorption Russell, J. D.; Paterson, E.; Fraser, A. R. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 71, Issue 0 https://doi.org/10.1039/f19757101623	journal	January 1975
The rate of ferrihydrite transformation to goethite via the Fe(II) pathway Yee, Nathan; Shaw, Samuel; Benning, Liane G. American Mineralogist, Vol. 91, Issue 1 https://doi.org/10.2138/am.2006.1860	journal	January 2006
Electrochemical Analysis of Changes in Iron Oxide Reducibility during Abiotic Ferrihydrite Transformation into Goethite and Magnetite Aeppli, Meret; Kaegi, Ralf; Kretzschmar, Ruben Environmental Science & Technology, Vol. 53, Issue 7 https://doi.org/10.1021/acs.est.8b07190	journal	February 2019
Iron-oxide crystallinity increases during soil redox oscillations Thompson, Aaron; Chadwick, Oliver A.; Rancourt, Denis G. Geochimica et Cosmochimica Acta, Vol. 70, Issue 7 https://doi.org/10.1016/j.gca.2005.12.005	journal	April 2006
Phase transformations in the ferrihydrite/cysteine system Cornell, R. M.; Schneider, W.; Giovanoli, R. Polyhedron, Vol. 8, Issue 23 https://doi.org/10.1016/S0277-5387(00)80544-6	journal	January 1989
Carbonate adsorption on goethite under closed and open CO2 conditions Villalobos, Mario; Leckie, James O. Geochimica et Cosmochimica Acta, Vol. 64, Issue 22 https://doi.org/10.1016/S0016-7037(00)00465-8	journal	November 2000
Aqueous formation and manipulation of the iron-oxo Keggin ion Sadeghi, O.; Zakharov, L. N.; Nyman, M. Science, Vol. 347, Issue 6228 https://doi.org/10.1126/science.aaa4620	journal	February 2015
Citrate Controls Fe(II)-Catalyzed Transformation of Ferrihydrite by Complexation of the Labile Fe(III) Intermediate Sheng, Anxu; Li, Xiaoxu; Arai, Yuji Environmental Science & Technology, Vol. 54, Issue 12 https://doi.org/10.1021/acs.est.0c00996	journal	May 2020
The Ostwald Rule of Stages Nývlt, Jaroslav Crystal Research and Technology, Vol. 30, Issue 4 https://doi.org/10.1002/crat.2170300402	journal	January 1995
Electron Small Polarons and Their Mobility in Iron (Oxyhydr)oxide Nanoparticles Katz, J. E.; Zhang, X.; Attenkofer, K. Science, Vol. 337, Issue 6099 https://doi.org/10.1126/science.1223598	journal	September 2012
New Data and a Revised Structural Model for Ferrihydrite Eggleton, Richard A. Clays and Clay Minerals, Vol. 36, Issue 2 https://doi.org/10.1346/CCMN.1988.0360203	journal	January 1988
Impact of Organic Matter on Iron(II)-Catalyzed Mineral Transformations in Ferrihydrite–Organic Matter Coprecipitates ThomasArrigo, Laurel K.; Byrne, James M.; Kappler, Andreas Environmental Science & Technology, Vol. 52, Issue 21 https://doi.org/10.1021/acs.est.8b03206	journal	October 2018
Use of fourier transform infrared spectroscopy to examine the Fe(II)-Catalyzed transformation of ferrihydrite Xiao, Wei; Jones, Adele M.; Collins, Richard N. Talanta, Vol. 175 https://doi.org/10.1016/j.talanta.2017.07.018	journal	December 2017
Effect of Silicate Species on the Transformation of Ferrihydrite into Goethite and Hematite in Alkaline Media Cornell, R. M. Clays and Clay Minerals, Vol. 35, Issue 1 https://doi.org/10.1346/CCMN.1987.0350103	journal	January 1987
Two-Step Growth of Goethite from Ferrihydrite Burleson, David J.; Penn, R. Lee Langmuir, Vol. 22, Issue 1 https://doi.org/10.1021/la051883g	journal	January 2006
Ferrihydrite Growth and Transformation in the Presence of Ferrous Iron and Model Organic Ligands ThomasArrigo, Laurel K.; Kaegi, Ralf; Kretzschmar, Ruben Environmental Science & Technology, Vol. 53, Issue 23 https://doi.org/10.1021/acs.est.9b03952	journal	November 2019
ATR-FTIR spectroscopic characterization of coexisting carbonate surface complexes on hematite Bargar, John R.; Kubicki, James D.; Reitmeyer, Rebecca Geochimica et Cosmochimica Acta, Vol. 69, Issue 6 https://doi.org/10.1016/j.gca.2004.08.002	journal	March 2005
In Situ Infrared Speciation of Adsorbed Carbonate on Aluminum and Iron Oxides Su, Chunming Clays and Clay Minerals, Vol. 45, Issue 6 https://doi.org/10.1346/CCMN.1997.0450605	journal	January 1997
A generalized geometric approach to anisotropic peak broadening due to domain morphology Ectors, D.; Goetz-Neunhoeffer, F.; Neubauer, J. Journal of Applied Crystallography, Vol. 48, Issue 1 https://doi.org/10.1107/S1600576714026557	journal	January 2015
Fe(II)-Catalyzed Transformation of Organic Matter–Ferrihydrite Coprecipitates: A Closer Look Using Fe Isotopes Zhou, Zhe; Latta, Drew E.; Noor, Nadia Environmental Science & Technology, Vol. 52, Issue 19 https://doi.org/10.1021/acs.est.8b03407	journal	September 2018
Decreases in Iron Oxide Reducibility during Microbial Reductive Dissolution and Transformation of Ferrihydrite Aeppli, Meret; Vranic, Sanja; Kaegi, Ralf Environmental Science & Technology, Vol. 53, Issue 15 https://doi.org/10.1021/acs.est.9b01299	journal	June 2019
The effect of CO ₂ and oxidation rate on the formation of goethite versus lepidocrocite from an Fe(II) system at pH 6 and 7 Carlson, L.; Schwertmann, U. Clay Minerals, Vol. 25, Issue 1 https://doi.org/10.1180/claymin.1990.025.1.07	journal	March 1990
Schwertmannite transformation to goethite via the Fe(II) pathway: Reaction rates and implications for iron–sulfide formation Burton, E. D.; Bush, R. T.; Sullivan, L. A. Geochimica et Cosmochimica Acta, Vol. 72, Issue 18 https://doi.org/10.1016/j.gca.2008.06.019	journal	September 2008
X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces Gu, Chunhao; Wang, Zimeng; Kubicki, James D. Environmental Science & Technology, Vol. 50, Issue 15 https://doi.org/10.1021/acs.est.6b00753	journal	July 2016
Fe(II)-Induced Mineral Transformation of Ferrihydrite–Organic Matter Adsorption and Co-precipitation Complexes in the Absence and Presence of As(III) Chen, Chunmei; Sparks, Donald L. ACS Earth and Space Chemistry, Vol. 2, Issue 11 https://doi.org/10.1021/acsearthspacechem.8b00041	journal	September 2018
Fast transformation of iron oxyhydroxides by the catalytic action of aqueous Fe(II) Pedersen, Hanne D.; Postma, Dieke; Jakobsen, Rasmus Geochimica et Cosmochimica Acta, Vol. 69, Issue 16 https://doi.org/10.1016/j.gca.2005.03.016	journal	August 2005
Surface Charge Effects on Fe(II) Sorption and Oxidation at (110) Goethite Surfaces Zarzycki, Piotr; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 122, Issue 18 https://doi.org/10.1021/acs.jpcc.8b02099	journal	April 2018
Surface Complexation Modeling and FTIR Study of Carbonate Adsorption to Goethite Villalobos, Mario; Leckie, James O. Journal of Colloid and Interface Science, Vol. 235, Issue 1 https://doi.org/10.1006/jcis.2000.7341	journal	March 2001
An in Situ ATR-FTIR Investigation of Sulfate Bonding Mechanisms on Goethite Peak, Derek; Ford, Robert G.; Sparks, Donald L. Journal of Colloid and Interface Science, Vol. 218, Issue 1 https://doi.org/10.1006/jcis.1999.6405	journal	October 1999
Behaviour of Fe-oxides relevant to contaminant uptake in the environment Stipp, S. L. S.; Hansen, M.; Kristensen, R. Chemical Geology, Vol. 190, Issue 1-4 https://doi.org/10.1016/S0009-2541(02)00123-7	journal	October 2002
Effect of Solution Conditions on the Proportion and Morphology of Goethite Formed from Ferrihydrite Cornell, R. M. Clays and Clay Minerals, Vol. 33, Issue 5 https://doi.org/10.1346/CCMN.1985.0330508	journal	January 1985
Kinetics of As(V) and carbon sequestration during Fe(II)-induced transformation of ferrihydrite-As(V)-fulvic acid coprecipitates Hu, Shiwen; Liang, Yuzhen; Liu, Tongxu Geochimica et Cosmochimica Acta, Vol. 272 https://doi.org/10.1016/j.gca.2020.01.002	journal	March 2020
Principles of Crystal Nucleation and Growth De Yoreo, J. J. Reviews in Mineralogy and Geochemistry, Vol. 54, Issue 1 https://doi.org/10.2113/0540057	journal	January 2003
Trace element cycling through iron oxide minerals during redox-driven dynamic recrystallization Frierdich, Andrew J.; Luo, Yun; Catalano, Jeffrey G. Geology, Vol. 39, Issue 11 https://doi.org/10.1130/G32330.1	journal	November 2011
An in situ quick-EXAFS and redox potential study of the Fe(II)-catalysed transformation of ferrihydrite Boland, Daniel D.; Collins, Richard N.; Glover, Chris J. Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 435 https://doi.org/10.1016/j.colsurfa.2013.02.009	journal	October 2013
Facile and Sustainable Synthesis of Shaped Iron Oxide Nanoparticles: Effect of Iron Precursor Salts on the Shapes of Iron Oxides Sayed, Farheen N.; Polshettiwar, Vivek Scientific Reports, Vol. 5, Issue 1 https://doi.org/10.1038/srep09733	journal	May 2015
Competing Fe(II)-Induced Mineralization Pathways of Ferrihydrite Hansel, Colleen M.; Benner, Shawn G.; Fendorf, Scott Environmental Science & Technology, Vol. 39, Issue 18 https://doi.org/10.1021/es050666z	journal	September 2005
The mechanism of reequilibration of solids in the presence of a fluid phase Putnis, Andrew; Putnis, Christine V. Journal of Solid State Chemistry, Vol. 180, Issue 5 https://doi.org/10.1016/j.jssc.2007.03.023	journal	May 2007
Biogeochemical Redox Processes and their Impact on Contaminant Dynamics Borch, Thomas; Kretzschmar, Ruben; Kappler, Andreas Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es9026248	journal	January 2010
Transformation of 2-line ferrihydrite to 6-line ferrihydrite under oxic and anoxic conditions Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, James K. American Mineralogist, Vol. 88, Issue 11-12 https://doi.org/10.2138/am-2003-11-1233	journal	November 2003
Surface and mineral structure of ferrihydrite Hiemstra, Tjisse Geochimica et Cosmochimica Acta, Vol. 105 https://doi.org/10.1016/j.gca.2012.12.002	journal	March 2013
Surface Complexation of Ferrous Iron and Carbonate on Ferrihydrite and the Mobilization of Arsenic Appelo, C. A. J.; Van Der Weiden, M. J. J.; Tournassat, C. Environmental Science & Technology, Vol. 36, Issue 14 https://doi.org/10.1021/es010130n	journal	July 2002
Carbonate adsorption on goethite in competition with phosphate Rahnemaie, Rasoul; Hiemstra, Tjisse; van Riemsdijk, Willem H. Journal of Colloid and Interface Science, Vol. 315, Issue 2 https://doi.org/10.1016/j.jcis.2007.07.017	journal	November 2007
Chromate adsorption on amorphous iron oxyhydroxide in the presence of major groundwater ions Zachara, John M.; Girvin, Donald C.; Schmidt, Ronald L. Environmental Science & Technology, Vol. 21, Issue 6 https://doi.org/10.1021/es00160a010	journal	June 1987
Surface complexation of carbonate on goethite: IR spectroscopy, structure and charge distribution Hiemstra, Tjisse; Rahnemaie, Rasoul; van Riemsdijk, Willem H. Journal of Colloid and Interface Science, Vol. 278, Issue 2 https://doi.org/10.1016/j.jcis.2004.06.014	journal	October 2004
The ostwald rule of stages in precipitation from highly supersaturated solutions: a model and its application to the formation of the nonstoichiometric amorphous calcium phosphate precursor phase Feenstra, T. P.; De Bruyn, P. L. Journal of Colloid and Interface Science, Vol. 84, Issue 1 https://doi.org/10.1016/0021-9797(81)90260-5	journal	November 1981
The Structure of Ferrihydrite, a Nanocrystalline Material Michel, F. M.; Ehm, L.; Antao, S. M. Science, Vol. 316, Issue 5832 https://doi.org/10.1126/science.1142525	journal	June 2007
Potentiometric and spectroscopic studies of sulfate complexation at the goethite-water interface Persson, Per; Lövgren, Lars Geochimica et Cosmochimica Acta, Vol. 60, Issue 15 https://doi.org/10.1016/0016-7037(96)00124-X	journal	August 1996
Effect of Solution and Solid-Phase Conditions on the Fe(II)-Accelerated Transformation of Ferrihydrite to Lepidocrocite and Goethite Boland, Daniel D.; Collins, Richard N.; Miller, Christopher J. Environmental Science & Technology, Vol. 48, Issue 10 https://doi.org/10.1021/es4043275	journal	April 2014
Spectroscopic studies of Pb(II)-sulfate interactions at the goethite-water interface Elzinga, E. J.; Peak, D.; Sparks, D. L. Geochimica et Cosmochimica Acta, Vol. 65, Issue 14 https://doi.org/10.1016/S0016-7037(01)00595-6	journal	July 2001
Influence of Coprecipitated Organic Matter on Fe ²⁺ _(aq) -Catalyzed Transformation of Ferrihydrite: Implications for Carbon Dynamics Chen, Chunmei; Kukkadapu, Ravi; Sparks, Donald L. Environmental Science & Technology, Vol. 49, Issue 18 https://doi.org/10.1021/acs.est.5b02448	journal	July 2015
Crystal Shape Engineering Lovette, Michael A.; Browning, Andrea Robben; Griffin, Derek W. Industrial & Engineering Chemistry Research, Vol. 47, Issue 24 https://doi.org/10.1021/ie800900f	journal	December 2008
Ligand effect on the adsorption of heavy metals: The sulfate ? Cadmium ? Goethite case Hoins, Ulrich; Charlet, Laurent; Sticher, Hans Water, Air, & Soil Pollution, Vol. 68, Issue 1-2 https://doi.org/10.1007/BF00479406	journal	May 1993
Spectroscopic Evidence for Fe(II)−Fe(III) Electron Transfer at the Iron Oxide−Water Interface Williams, Aaron G. B.; Scherer, Michelle M. Environmental Science & Technology, Vol. 38, Issue 18 https://doi.org/10.1021/es049373g	journal	September 2004
The surface chemistry of goethite (alpha FeOOH) in major ion seawater Balistrieri, L. S.; Murray, J. W. American Journal of Science, Vol. 281, Issue 6 https://doi.org/10.2475/ajs.281.6.788	journal	June 1981
Transmission Electron Microscopy of Synthetic 2- and 6-Line Ferrihydrite Janney, Dawn E. Clays and Clay Minerals, Vol. 48, Issue 1 https://doi.org/10.1346/CCMN.2000.0480114	journal	January 2000
The Role of Defects in Fe(II)–Goethite Electron Transfer Notini, Luiza; Latta, Drew E.; Neumann, Anke Environmental Science & Technology, Vol. 52, Issue 5 https://doi.org/10.1021/acs.est.7b05772	journal	February 2018
Redox characterization of the Fe(II)-catalyzed transformation of ferrihydrite to goethite Jones, Adele M.; Collins, Richard N.; Waite, T. David Geochimica et Cosmochimica Acta, Vol. 218 https://doi.org/10.1016/j.gca.2017.09.024	journal	December 2017

Similar Records

Further insights into the Fe( ii ) reduction of 2-line ferrihydrite: a semi in situ and in situ TEM study

Journal Article · Tue Oct 13 00:00:00 EDT 2020 · Nanoscale Advances · OSTI ID:1699508

Gomez, Mario Alberto; Jiang, Ruonan; Song, Miao; +7 more

Labile Fe(III) supersaturation controls nucleation and properties of product phases from Fe(II)-catalyzed ferrihydrite transformation

Journal Article · Mon Jun 28 00:00:00 EDT 2021 · Geochimica et Cosmochimica Acta · OSTI ID:1699508

Sheng, Anxu; Liu, Juan; Li, Xiaoxu; +6 more

Citrate Controls Fe(II)-Catalyzed Transformation of Ferrihydrite by Complexation of the Labile Fe(III) Intermediate

Journal Article · Tue Jun 16 00:00:00 EDT 2020 · Environmental Science & Technology · OSTI ID:1699508

Sheng, Anxu; Li, Xiaoxu; Arai, Yuji; +3 more

Related Subjects

54 ENVIRONMENTAL SCIENCES

Title: Nanoscale observations of Fe(ii)-induced ferrihydrite transformation

Citation Formats

References (62)

Similar Records

Related Subjects