Tracking Initial Fe(II)-Driven Ferrihydrite Transformations: A Mössbauer Spectroscopy and Isotope Investigation

Latta, Drew; Rosso, Kevin M.; Scherer, Michelle M.

doi:10.1021/acsearthspacechem.2c00291

Title: Tracking Initial Fe(II)-Driven Ferrihydrite Transformations: A Mössbauer Spectroscopy and Isotope Investigation

Journal Article · Thu Sep 28 00:00:00 EDT 2023 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.2c00291· OSTI ID:2006901

^[1];

^[2];

^[1]

Department of Civil and Environmental Engineering/IIHR, The University of Iowa, Iowa City, Iowa 52242, United States
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99345, United States

Transformation of nanocrystalline ferrihydrite to more stable microcrystalline Fe(III) oxides is rapidly accelerated under reducing conditions with aqueous Fe(II) present. While the major steps of Fe(II)-catalyzed ferrihydrite transformation are known, processes in the initial phase that lead to nucleation and the growth of product minerals remain unclear. To track ferrihydrite–Fe(II) interactions during this initial phase, we used Fe isotopes, Mössbauer spectroscopy, and extractions to monitor the structural, magnetic, and isotope composition changes of ferrihydrite within ~30 min of Fe(II) exposure. We observed rapid isotope mixing between aqueous Fe(II) and ferrihydrite during this initial lag phase. Our findings from Mössbauer spectroscopy indicate that a more magnetically ordered Fe(III) phase initially forms that is distinct from ferrihydrite and bulk crystalline transformation products. The signature of this phase is consistent with the early stage emergence of lepidocrocite-like lamellae observed in previous transmission electron microscopy studies. Its signature is furthermore removed by xylenol extraction of Fe(III), the same approach used to identify a chemically labile form of Fe(III) resulting from Fe(II) contact that is correlated to the ultimate emergence of crystalline product phases detectable by X-ray diffraction. Our work indicates that the mineralogical changes in the initial lag phase of Fh transformation initiated by Fe(II)–Fh electron transfer are critical to understanding ferrihydrite behavior in soils and sediments, particularly with regard to metal uptake and release.

View Journal Article

Cite

Export

Save

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

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

Grant/Contract Number:: AC05-76RL01830; FWP 56674

OSTI ID:: 2006901

Alternate ID(s):: OSTI ID: 2007385; OSTI ID: 2203511

Report Number(s):: PNNL-SA-190780

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Vol. 7 Journal Issue: 10; ISSN 2472-3452

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (65)

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
Fe3O4 and γ-Fe2O3 nanoparticles for the adsorption of Co2+ from aqueous solution Uheida, Abdusalam; Salazar-Alvarez, German; Björkman, Eva Journal of Colloid and Interface Science, Vol. 298, Issue 2 https://doi.org/10.1016/j.jcis.2005.12.057	journal	June 2006
Roles of Hydration and Magnetism on the Structure of Ferrihydrite from First Principles Sassi, Michel; Rosso, Kevin M. ACS Earth and Space Chemistry, Vol. 3, Issue 1 https://doi.org/10.1021/acsearthspacechem.8b00138	journal	November 2018
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
Redox potential measurements and Mössbauer spectrometry of FeII adsorbed onto FeIII (oxyhydr)oxides Silvester, Ewen; Charlet, Laurent; Tournassat, Christophe Geochimica et Cosmochimica Acta, Vol. 69, Issue 20 https://doi.org/10.1016/j.gca.2005.06.013	journal	October 2005
Spectrophotometric determination of iron(II) with 1,10-phenanthroline in the presence of large amounts of iron(III) Tamura, Hiroki; Goto, Katsumi; Yotsuyanagi, Takao Talanta, Vol. 21, Issue 4 https://doi.org/10.1016/0039-9140(74)80012-3	journal	April 1974
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
An 57Fe Mössbauer effect study of poorly crystalline γ-FeOOH De Grave, E.; Persoons, R. M.; Chambaere, D. G. Physics and Chemistry of Minerals, Vol. 13, Issue 1 https://doi.org/10.1007/BF00307313	journal	January 1986
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
Dissimilatory microbial iron reduction release DOC (dissolved organic carbon) from carbon-ferrihydrite association Pan, Weinan; Kan, Jinjun; Inamdar, Shreeram Soil Biology and Biochemistry, Vol. 103 https://doi.org/10.1016/j.soilbio.2016.08.026	journal	December 2016
Ab initio thermodynamics reveals the nanocomposite structure of ferrihydrite Sassi, Michel; Chaka, Anne M.; Rosso, Kevin M. Communications Chemistry, Vol. 4, Issue 1 https://doi.org/10.1038/s42004-021-00562-7	journal	September 2021
Impact of Organic Carbon Electron Donors on Microbial Community Development under Iron- and Sulfate-Reducing Conditions Kwon, Man Jae; O’Loughlin, Edward J.; Boyanov, Maxim I. PLOS ONE, Vol. 11, Issue 1 https://doi.org/10.1371/journal.pone.0146689	journal	January 2016
The Iron Oxides Cornell, R. M.; Schwertmann, U. https://doi.org/10.1002/3527602097	book	July 2003
Fe(II)-induced phase transformation of ferrihydrite: The inhibition effects and stabilization of divalent metal cations Liu, Chengshuai; Zhu, Zhenke; Li, Fangbai Chemical Geology, Vol. 444 https://doi.org/10.1016/j.chemgeo.2016.10.002	journal	December 2016
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
A Closer Look at Fe(II) Passivation of Goethite Notini, Luiza; Latta, Drew E.; Neumann, Anke ACS Earth and Space Chemistry, Vol. 3, Issue 12 https://doi.org/10.1021/acsearthspacechem.9b00224	journal	October 2019
Extended Voigt-based analytic lineshape method for determining N-dimensional correlated hyperfine parameter distributions in Mössbauer spectroscopy Lagarec, K.; Rancourt, D. G. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 129, Issue 2 https://doi.org/10.1016/S0168-583X(97)00284-X	journal	July 1997
Stabilization of Ferrihydrite and Lepidocrocite by Silicate during Fe(II)-Catalyzed Mineral Transformation: Impact on Particle Morphology and Silicate Distribution Schulz, Katrin; ThomasArrigo, Laurel K.; Kaegi, Ralf Environmental Science & Technology, Vol. 56, Issue 9 https://doi.org/10.1021/acs.est.1c08789	journal	April 2022
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
Magnetic properties of ferrihydrite nanoparticles doped with Ni, Mo, and Ir Punnoose, A.; Phanthavady, T.; Seehra, M. S. Physical Review B, Vol. 69, Issue 5 https://doi.org/10.1103/PhysRevB.69.054425	journal	February 2004
Coexisting Goethite Promotes Fe(II)-Catalyzed Transformation of Ferrihydrite to Goethite Notini, Luiza; ThomasArrigo, Laurel K.; Kaegi, Ralf Environmental Science & Technology, Vol. 56, Issue 17 https://doi.org/10.1021/acs.est.2c03925	journal	August 2022
Magnetic properties of synthetic six-line ferrihydrite nanoparticles Guyodo, Yohan; Banerjee, Subir K.; Lee Penn, R. Physics of the Earth and Planetary Interiors, Vol. 154, Issue 3-4 https://doi.org/10.1016/j.pepi.2005.05.009	journal	March 2006
Susceptibility of Goethite to Fe ²⁺ -Catalyzed Recrystallization over Time Joshi, Prachi; Fantle, Matthew S.; Larese-Casanova, Philip Environmental Science & Technology, Vol. 51, Issue 20 https://doi.org/10.1021/acs.est.7b02603	journal	September 2017
Further insights into the Fe( ii ) reduction of 2-line ferrihydrite: a semi in situ and in situ TEM study Gomez, Mario Alberto; Jiang, Ruonan; Song, Miao Nanoscale Advances, Vol. 2, Issue 10 https://doi.org/10.1039/D0NA00643B	journal	January 2020
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
Redox Reactions of Reduced Flavin Mononucleotide (FMN), Riboflavin (RBF), and Anthraquinone-2,6-disulfonate (AQDS) with Ferrihydrite and Lepidocrocite Shi, Zhi; Zachara, John M.; Shi, Liang Environmental Science & Technology, Vol. 46, Issue 21 https://doi.org/10.1021/es301544b	journal	October 2012
Release of arsenic associated with the reduction and transformation of iron oxides Pedersen, Hanne D.; Postma, Dieke; Jakobsen, Rasmus Geochimica et Cosmochimica Acta, Vol. 70, Issue 16 https://doi.org/10.1016/j.gca.2006.06.1370	journal	August 2006
From Fe(III) Ions to Ferrihydrite and then to Hematite Schwertmann, Udo; Friedl, Josef; Stanjek, Helge Journal of Colloid and Interface Science, Vol. 209, Issue 1 https://doi.org/10.1006/jcis.1998.5899	journal	January 1999
Interparticle interactions in composites of nanoparticles of ferrimagnetic (γ-Fe2O3) and antiferromagnetic (CoO,NiO) materials Frandsen, C.; Ostenfeld, C.; Xu, M. Physical Review B, Vol. 70, Issue 13 https://doi.org/10.1103/PhysRevB.70.134416	journal	October 2004
Hexahydro-1,3,5-trinitro-1,3,5-triazine Transformation by Biologically Reduced Ferrihydrite: Evolution of Fe Mineralogy, Surface Area, and Reaction Rates Williams, Aaron G. B.; Gregory, Kelvin B.; Parkin, Gene F. Environmental Science & Technology, Vol. 39, Issue 14 https://doi.org/10.1021/es0490525	journal	July 2005
Effects of Zwitterionic Buffers on Sorption of Ferrous Iron at Goethite and Its Oxidation by CCl ₄ Buchholz, Anke; Laskov, Christine; Haderlein, Stefan B. Environmental Science & Technology, Vol. 45, Issue 8 https://doi.org/10.1021/es103172c	journal	April 2011
Arsenic Effects and Behavior in Association with the Fe(II)-Catalyzed Transformation of Schwertmannite Burton, Edward D.; Johnston, Scott G.; Watling, Kym Environmental Science & Technology, Vol. 44, Issue 6 https://doi.org/10.1021/es903424h	journal	February 2010
Electron Mobility and Trapping in Ferrihydrite Nanoparticles Soltis, Jennifer A.; Schwartzberg, Adam M.; Zarzycki, Piotr ACS Earth and Space Chemistry, Vol. 1, Issue 4 https://doi.org/10.1021/acsearthspacechem.7b00030	journal	May 2017
High crystallinity Si-ferrihydrite: An insight into its Néel temperature and size dependence of magnetic properties Berquó, Thelma S.; Banerjee, Subir K.; Ford, Robert G. Journal of Geophysical Research, Vol. 112, Issue B2 https://doi.org/10.1029/2006JB004583	journal	January 2007
Transformation of ferric hydroxide into spinel by iron(II) adsorption Tronc, Elisabeth; Belleville, Philippe; Jolivet, Jean Pierre Langmuir, Vol. 8, Issue 1 https://doi.org/10.1021/la00037a057	journal	January 1992
The effect of silica and natural organic matter on the Fe(II)-catalysed transformation and reactivity of Fe(III) minerals Jones, Adele M.; Collins, Richard N.; Rose, Jerome Geochimica et Cosmochimica Acta, Vol. 73, Issue 15 https://doi.org/10.1016/j.gca.2009.04.025	journal	August 2009
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
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
Effects of crystallite size on the structure and magnetism of ferrihydrite Wang, Xiaoming; Zhu, Mengqiang; Koopal, Luuk K. Environmental Science: Nano, Vol. 3, Issue 1 https://doi.org/10.1039/C5EN00191A	journal	January 2016
Labile Fe(III) supersaturation controls nucleation and properties of product phases from Fe(II)-catalyzed ferrihydrite transformation Sheng, Anxu; Liu, Juan; Li, Xiaoxu Geochimica et Cosmochimica Acta, Vol. 309 https://doi.org/10.1016/j.gca.2021.06.027	journal	September 2021
Transformation of Two-Line Ferrihydrite to Goethite and Hematite as a Function of pH and Temperature Das, Soumya; Hendry, M. Jim; Essilfie-Dughan, Joseph Environmental Science & Technology, Vol. 45, Issue 1 https://doi.org/10.1021/es101903y	journal	January 2011
Formation of goethite from ferrihydrite at physiological pH under the influence of cysteine Cornell, R. M.; Schneider, W. Polyhedron, Vol. 8, Issue 2 https://doi.org/10.1016/S0277-5387(00)86496-7	journal	January 1989
Effects of magnetic interactions in antiferromagnetic ferrihydrite particles Berquó, Thelma S.; Erbs, Jasmine J.; Lindquist, Anna Journal of Physics: Condensed Matter, Vol. 21, Issue 17 https://doi.org/10.1088/0953-8984/21/17/176005	journal	April 2009
Mediated Electrochemical Reduction of Iron (Oxyhydr-)Oxides under Defined Thermodynamic Boundary Conditions Aeppli, Meret; Voegelin, Andreas; Gorski, Christopher A. Environmental Science & Technology, Vol. 52, Issue 2 https://doi.org/10.1021/acs.est.7b04411	journal	December 2017
Natural organic matter inhibits Ni stabilization during Fe(II)-catalyzed ferrihydrite transformation Zhou, Zhe; Latta, Drew E.; Scherer, Michelle M. Science of The Total Environment, Vol. 755 https://doi.org/10.1016/j.scitotenv.2020.142612	journal	February 2021
Ferrihydrite: A review of structure, properties and occurrence in relation to soils Childs, Cyril W. Zeitschrift für Pflanzenernährung und Bodenkunde, Vol. 155, Issue 5 https://doi.org/10.1002/jpln.19921550515	journal	January 1992
Fe(II)-Catalyzed Recrystallization of Goethite Revisited Handler, Robert M.; Frierdich, Andrew J.; Johnson, Clark M. Environmental Science & Technology, Vol. 48, Issue 19 https://doi.org/10.1021/es503084u	journal	September 2014
Effect of organic C on stable Fe isotope fractionation and isotope exchange kinetics between aqueous Fe(II) and ferrihydrite at neutral pH Chanda, Piyali; Zhou, Zhe; Latta, Drew E. Chemical Geology, Vol. 531 https://doi.org/10.1016/j.chemgeo.2019.119344	journal	January 2020
Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism Michel, F. M.; Barron, V.; Torrent, J. Proceedings of the National Academy of Sciences, Vol. 107, Issue 7 https://doi.org/10.1073/pnas.0910170107	journal	February 2010
Structure and composition of natural ferrihydrite nano-colloids in anoxic groundwater Engel, Maya; Noël, Vincent; Pierce, Samuel Water Research, Vol. 238 https://doi.org/10.1016/j.watres.2023.119990	journal	June 2023
Formation of green rust via mineralogical transformation of ferric oxides (ferrihydrite, goethite and hematite) Usman, M.; Hanna, K.; Abdelmoula, M. Applied Clay Science, Vol. 64 https://doi.org/10.1016/j.clay.2011.10.008	journal	August 2012
Impact of Zn substitution on Fe(II)-induced ferrihydrite transformation pathways Yan, Jinshu; Frierdich, Andrew J.; Catalano, Jeffrey G. Geochimica et Cosmochimica Acta, Vol. 320 https://doi.org/10.1016/j.gca.2022.01.014	journal	March 2022
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
Kinetics of Fe(II)-Catalyzed Transformation of 6-line Ferrihydrite under Anaerobic Flow Conditions Yang, Li; Steefel, Carl I.; Marcus, Matthew A. Environmental Science & Technology, Vol. 44, Issue 14 https://doi.org/10.1021/es1007565	journal	July 2010
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
AQDS and Redox-Active NOM Enables Microbial Fe(III)-Mineral Reduction at cm-Scales Bai, Yuge; Mellage, Adrian; Cirpka, Olaf A. Environmental Science & Technology, Vol. 54, Issue 7 https://doi.org/10.1021/acs.est.9b07134	journal	February 2020
Effect of Amorphous Fe(III) Oxide Transformation on the Fe(II)-Mediated Reduction of U(VI) Boland, Daniel D.; Collins, Richard N.; Payne, Timothy E. Environmental Science & Technology, Vol. 45, Issue 4 https://doi.org/10.1021/es101848a	journal	February 2011
Magnetism of iron oxide based core-shell nanoparticles from interface mixing with enhanced spin-orbit coupling Skoropata, E.; Desautels, R. D.; Chi, C. -C. Physical Review B, Vol. 89, Issue 2 https://doi.org/10.1103/PhysRevB.89.024410	journal	January 2014
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
Stable mineral recrystallization in low temperature aqueous systems: A critical review Gorski, Christopher A.; Fantle, Matthew S. Geochimica et Cosmochimica Acta, Vol. 198 https://doi.org/10.1016/j.gca.2016.11.013	journal	February 2017
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
Phosphate Imposed Limitations on Biological Reduction and Alteration of Ferrihydrite Borch, Thomas; Masue, Yoko; Kukkadapu, Ravi K. Environmental Science & Technology, Vol. 41, Issue 1 https://doi.org/10.1021/es060695p	journal	January 2007
Changes in Crystallinity and Tracer-Isotope Distribution of Goethite during Fe(II)-Accelerated Recrystallization Southall, Scarlett C.; Micklethwaite, Steven; Wilson, Siobhan A. ACS Earth and Space Chemistry, Vol. 2, Issue 12 https://doi.org/10.1021/acsearthspacechem.8b00100	journal	November 2018
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

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:2006901

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:2006901

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:2006901

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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Fe(II)−Fe(III) interfacial electron transfer
ferrihydrite transformation
recrystallization
dissolution−reprecipitation
induction period
lag phase
labile Fe(III)
dissolution
extraction
isotopes
phase transition
solution chemistry

Title: Tracking Initial Fe(II)-Driven Ferrihydrite Transformations: A Mössbauer Spectroscopy and Isotope Investigation

Citation Formats

References (65)

Similar Records

Related Subjects