Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

Taylor, Sandra D.; Cliff, John B.; Wietsma, Thomas W.; Rosso, Kevin M.

doi:10.1039/d4en01004c

Title: Facet-dependent growth and dissolution of hematite resulting from autocatalytic interactions with Fe(II) and oxalic acid

Journal Article · 24 January 2025 · Environmental Science: Nano

DOI: https://doi.org/10.1039/d4en01004c · OSTI ID:2510513

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Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

The ability to simultaneously monitor the flux of iron atoms within the solution and solid phases can provide considerable insight into mechanisms of iron oxide mineral transformations. The autocatalytic interaction between hematite and Fe(II)-oxalate has long been of interest for its environmental and industrial relevance. In this study we take advantage of iron isotopic labelling and mass-sensitive imaging at the single particle scale to determine how changes in solution composition correlate with the morphologic evolution of faceted, micrometer-sized hematite platelets. Net dissolution is confirmed through analyses of aqueous iron chemistry, as well as by quantitative atomic force microscopy. Isotopic mapping techniques show that Fe(II) readily adsorbs to (001) and (012) surfaces in the absence of oxalate, but when oxalate is present selective dissolution of the (001) surface prevails and Fe deposition via recrystallization is not observed. Comparison between particle microtopographies following reaction with Fe(II), oxalate, and Fe(II)-oxalate show substantially different behaviors, consistent with distinct mechanisms of interaction with hematite surfaces. The extensive characterization conducted on the coupled solution/solid dynamics in this system provides new insight for distinguishing crystal growth, dissolution, and recrystallization processes.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: Environmental Molecular Sciences Laboratory (EMSL); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-00OR22725; AC05-76RL01830

OSTI ID:: 2510513

Journal Information:: Environmental Science: Nano, Journal Name: Environmental Science: Nano Journal Issue: 3 Vol. 12; ISSN 2051-8153

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (34)

High-precision SIMS oxygen, sulfur and iron stable isotope analyses of geological materials: accuracy, surface topography and crystal orientation Kita, N. T.; Huberty, J. M.; Kozdon, R. Surface and Interface Analysis, Vol. 43, Issue 1-2 https://doi.org/10.1002/sia.3424	journal	May 2010
Catalytic dissoluion of iron(III)(hydr)oxides by oxalic acid in the presence of Fe(II) Suter, D.; Siffert, C.; Sulzberger, B. Naturwissenschaften, Vol. 75, Issue 11 https://doi.org/10.1007/BF00377723	journal	November 1988
Analysis of Three-dimensional Atom-probe Data by the Proximity Histogram Hellman, Olof C.; Vandenbroucke, Justin A.; Rüsing, Järg Microscopy and Microanalysis, Vol. 6, Issue 05 https://doi.org/10.1007/S100050010051	journal	September 2000
The coordination chemistry of weathering: II. Dissolution of Fe(III) oxides Zinder, Bettina; Furrer, Gerhard; Stumm, Werner Geochimica et Cosmochimica Acta, Vol. 50, Issue 9 https://doi.org/10.1016/0016-7037(86)90244-9	journal	September 1986
Preparation of well-defined colloidal particles by thermal decomposition of metal chelates. I. Iron oxides Sapieszko, Ronald S.; Matijević, Egon Journal of Colloid and Interface Science, Vol. 74, Issue 2 https://doi.org/10.1016/0021-9797(80)90210-6	journal	April 1980
Interactions of metal hydrous oxides with chelating agents Chang, Han-Chyen; Matijević, Egon Journal of Colloid and Interface Science, Vol. 92, Issue 2 https://doi.org/10.1016/0021-9797(83)90169-8	journal	April 1983
Interactions of metal hydrous oxides with chelating agents Torres, Roberto; Blesa, Miguel A.; Matijević, Egon Journal of Colloid and Interface Science, Vol. 131, Issue 2 https://doi.org/10.1016/0021-9797(89)90199-9	journal	September 1989
Interactions of metal hydrous oxides with chelating agents Torres, Roberto; Blesa, Miguel A.; Matijević, Egon Journal of Colloid and Interface Science, Vol. 134, Issue 2 https://doi.org/10.1016/0021-9797(90)90157-J	journal	February 1990
The role of oxalate in accelerating the reductive dissolution of hematite (α-Fe2O3) by ascorbate Banwart, Steven; Davies, Simon; Stumm, Werner Colloids and Surfaces, Vol. 39, Issue 2 https://doi.org/10.1016/0166-6622(89)80281-1	journal	January 1989
Mechanisms of dissolution of iron oxides in aqueous oxalic acid solutions Panias, D.; Taxiarchou, M.; Paspaliaris, I. Hydrometallurgy, Vol. 42, Issue 2 https://doi.org/10.1016/0304-386X(95)00104-O	journal	September 1996
Dissolution of hematite in acidic oxalate solutions: the effect of ferrous ions addition Panias, D.; Taxiarchou, M.; Douni, I. Hydrometallurgy, Vol. 43, Issue 1-3 https://doi.org/10.1016/0304-386X(96)00004-7	journal	November 1996
Surface complexation and dissolution of hematite by C 1 -C 6 dicarboxylic acids at pH = 5.0 Duckworth, Owen W.; Martin, Scot T. Geochimica et Cosmochimica Acta, Vol. 65, Issue 23 https://doi.org/10.1016/S0016-7037(01)00696-2	journal	December 2001
Dissolution of hematite in acidic oxalate solutions Taxiarchou, M.; Panias, D.; Douni, I. Hydrometallurgy, Vol. 44, Issue 3 https://doi.org/10.1016/S0304-386X(96)00075-8	journal	March 1997
Colorimetric ferrozine-based assay for the quantitation of iron in cultured cells Riemer, Jan; Hoepken, Hans Hermann; Czerwinska, Hania Analytical Biochemistry, Vol. 331, Issue 2 https://doi.org/10.1016/j.ab.2004.03.049	journal	August 2004
Crystal orientation effects in δ18O for magnetite and hematite by SIMS Huberty, Jason M.; Kita, Noriko T.; Kozdon, Reinhard Chemical Geology, Vol. 276, Issue 3-4 https://doi.org/10.1016/j.chemgeo.2010.06.012	journal	September 2010
Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH Catalano, Jeffrey G.; Fenter, Paul; Park, Changyong Geochimica et Cosmochimica Acta, Vol. 74, Issue 5 https://doi.org/10.1016/j.gca.2009.12.018	journal	March 2010
A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect Taylor, S. D.; Marcano, M. C.; Becker, U. Geochimica et Cosmochimica Acta, Vol. 197 https://doi.org/10.1016/j.gca.2016.10.022	journal	January 2017
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
Structure and reactivity of the hydrated hematite (0001) surface Trainor, Thomas P.; Chaka, Anne M.; Eng, Peter J. Surface Science, Vol. 573, Issue 2 https://doi.org/10.1016/j.susc.2004.09.040	journal	December 2004
Fe(II) Redox Chemistry in the Environment Huang, Jianzhi; Jones, Adele; Waite, T. David Chemical Reviews, Vol. 121, Issue 13 https://doi.org/10.1021/acs.chemrev.0c01286	journal	June 2021
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
Ascorbate Induced Facet Dependent Reductive Dissolution of Hematite Nanocrystals Huang, Xiaopeng; Hou, Xiaojing; Song, Fahui The Journal of Physical Chemistry C, Vol. 121, Issue 2 https://doi.org/10.1021/acs.jpcc.6b09281	journal	January 2017
Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides Taylor, S. D.; Becker, U.; Rosso, K. M. The Journal of Physical Chemistry C, Vol. 121, Issue 36 https://doi.org/10.1021/acs.jpcc.7b06893	journal	September 2017
Pb ²⁺ –Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite Yuan, Ke; De Andrade, Vincent; Feng, Zhange The Journal of Physical Chemistry C, Vol. 122, Issue 4 https://doi.org/10.1021/acs.jpcc.7b11682	journal	January 2018
Resolving Iron(II) Sorption and Oxidative Growth on Hematite (001) Using Atom Probe Tomography Taylor, Sandra D.; Liu, Jia; Arey, Bruce W. The Journal of Physical Chemistry C, Vol. 122, Issue 7 https://doi.org/10.1021/acs.jpcc.7b11989	journal	February 2018
Energetics and the Role of Defects in Fe(II)-Catalyzed Goethite Recrystallization from Molecular Simulations Zarzycki, Piotr; Rosso, Kevin M. ACS Earth and Space Chemistry, Vol. 3, Issue 2 https://doi.org/10.1021/acsearthspacechem.8b00175	journal	January 2019
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
Fe(II) Sorption on Hematite: New Insights Based on Spectroscopic Measurements Larese-Casanova, Philip; Scherer, Michelle M. Environmental Science & Technology, Vol. 41, Issue 2 https://doi.org/10.1021/es0617035	journal	January 2007
Connecting Observations of Hematite (α-Fe ₂ O ₃ ) Growth Catalyzed by Fe(II) Rosso, Kevin M.; Yanina, Svetlana V.; Gorski, Christopher A. Environmental Science & Technology, Vol. 44, Issue 1 https://doi.org/10.1021/es901882a	journal	January 2010
Light-induced dissolution of hematite in the presence of oxalate. A case study Siffert, Christophe.; Sulzberger, Barbara. Langmuir, Vol. 7, Issue 8 https://doi.org/10.1021/la00056a014	journal	August 1991
Difference in anisotropic etching characteristics of alkaline and copper based acid solutions for single-crystalline Si Chen, Wei; Liu, Yaoping; Yang, Lixia Scientific Reports, Vol. 8, Issue 1 https://doi.org/10.1038/s41598-018-21877-x	journal	February 2018
Visualizing the iron atom exchange front in the Fe(II)-catalyzed recrystallization of goethite by atom probe tomography Taylor, Sandra D.; Liu, Jia; Zhang, Xin Proceedings of the National Academy of Sciences, Vol. 116, Issue 8 https://doi.org/10.1073/pnas.1816620116	journal	February 2019
Linked Reactivity at Mineral-Water Interfaces Through Bulk Crystal Conduction Yanina, S. V.; Rosso, K. M. Science, Vol. 320, Issue 5873 https://doi.org/10.1126/science.1154833	journal	March 2008
Origin of undulated growth steps on hematite crystals from Sasazawa, Japan. Taijing, Lu; Sunagawa, I. Mineralogical Journal, Vol. 13, Issue 7 https://doi.org/10.2465/minerj.13.409	journal	January 1987

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