DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Precipitation pathways for ferrihydrite formation in acidic solutions

Abstract

Iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV-vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+]=0.2M, 1.8

Authors:
 [1];  [2];  [3];  [4];  [5];  [5];  [3];  [6];  [7]
  1. Univ. of Wyoming, Laramie, WY (United States). Dept. of Ecosystem Science and Management; Lawrence Berkeley National Lab., Berkeley, CA (United States). Earth Sciences Division
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
  3. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Physics
  4. Univ. of Delaware, Newark, DE (United States). Dept. of Geological Sciences
  5. Univ. of California, Berkeley, CA (United States). Dept. of Earth and Planetary Science
  6. Univ. of California, Berkeley, CA (United States). Dept. of Earth and Planetary Science; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Danish Council for Independent Research (DFF)
OSTI Identifier:
1228832
Alternate Identifier(s):
OSTI ID: 1398140; OSTI ID: 1456925
Report Number(s):
BNL-108457-2015-JA
Journal ID: ISSN 0016-7037; R&D Project: LS001
Grant/Contract Number:  
SC00112704; AC02-05CH11231; EAR-1529937; AC02-98CH10886; AC02-06CH11357; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Geochimica et Cosmochimica Acta
Additional Journal Information:
Journal Volume: 172; Journal Issue: C; Journal ID: ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhu, Mengqiang, Khalid, Syed, Frandsen, Cathrine, Wallace, Adam F., Legg, Benjamin, Zhang, Hengzhong, Morup, Steen, Banfield, Jillian F., and Waychunas, Glenn A. Precipitation pathways for ferrihydrite formation in acidic solutions. United States: N. p., 2015. Web. doi:10.1016/j.gca.2015.09.015.
Zhu, Mengqiang, Khalid, Syed, Frandsen, Cathrine, Wallace, Adam F., Legg, Benjamin, Zhang, Hengzhong, Morup, Steen, Banfield, Jillian F., & Waychunas, Glenn A. Precipitation pathways for ferrihydrite formation in acidic solutions. United States. https://doi.org/10.1016/j.gca.2015.09.015
Zhu, Mengqiang, Khalid, Syed, Frandsen, Cathrine, Wallace, Adam F., Legg, Benjamin, Zhang, Hengzhong, Morup, Steen, Banfield, Jillian F., and Waychunas, Glenn A. Sat . "Precipitation pathways for ferrihydrite formation in acidic solutions". United States. https://doi.org/10.1016/j.gca.2015.09.015. https://www.osti.gov/servlets/purl/1228832.
@article{osti_1228832,
title = {Precipitation pathways for ferrihydrite formation in acidic solutions},
author = {Zhu, Mengqiang and Khalid, Syed and Frandsen, Cathrine and Wallace, Adam F. and Legg, Benjamin and Zhang, Hengzhong and Morup, Steen and Banfield, Jillian F. and Waychunas, Glenn A.},
abstractNote = {Iron oxides and oxyhydroxides form via Fe3+ hydrolysis and polymerization in many aqueous environments, but the pathway from Fe3+ monomers to oligomers and then to solid phase nuclei is unknown. In this work, using combined X-ray, UV-vis, and Mössbauer spectroscopic approaches, we were able to identify and quantify the long-time sought ferric speciation over time during ferric oxyhydroxide formation in partially-neutralized ferric nitrate solutions ([Fe3+]=0.2M, 1.8},
doi = {10.1016/j.gca.2015.09.015},
journal = {Geochimica et Cosmochimica Acta},
number = C,
volume = 172,
place = {United States},
year = {Sat Oct 03 00:00:00 EDT 2015},
month = {Sat Oct 03 00:00:00 EDT 2015}
}

Journal Article:

Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Neutron Pair Distribution Function Study of Two-Line Ferrihydrite
journal, December 2011

  • Harrington, Richard; Hausner, Douglas B.; Xu, Wenqian
  • Environmental Science & Technology, Vol. 45, Issue 23
  • DOI: 10.1021/es2020633

Dissimilatory Reduction and Transformation of Ferrihydrite-Humic Acid Coprecipitates
journal, November 2013

  • Shimizu, Masayuki; Zhou, Jihai; Schröder, Christian
  • Environmental Science & Technology, Vol. 47, Issue 23
  • DOI: 10.1021/es402812j

Effect of phosphate, silicate, and Ca on Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water studied by X-ray absorption spectroscopy
journal, January 2010

  • Voegelin, Andreas; Kaegi, Ralf; Frommer, Jakob
  • Geochimica et Cosmochimica Acta, Vol. 74, Issue 1
  • DOI: 10.1016/j.gca.2009.09.020

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy
journal, October 2003


Dynamic Fe-precipitate formation induced by Fe(II) oxidation in aerated phosphate-containing water
journal, September 2013

  • Voegelin, Andreas; Senn, Anna-Caterina; Kaegi, Ralf
  • Geochimica et Cosmochimica Acta, Vol. 117
  • DOI: 10.1016/j.gca.2013.04.022

Early Stage Formation of Iron Oxyhydroxides during Neutralization of Simulated Acid Mine Drainage Solutions
journal, July 2012

  • Zhu, Mengqiang; Legg, Benjamin; Zhang, Hengzhong
  • Environmental Science & Technology, Vol. 46, Issue 15
  • DOI: 10.1021/es301268g

Iron speciation in natural hyperacid water investigated by Mössbauer spectroscopy
journal, November 2009

  • Bender Koch, C.; Rasmussen, H. K.; Mørup, S.
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 74, Issue 4
  • DOI: 10.1016/j.saa.2009.08.038

Aqueous formation and manipulation of the iron-oxo Keggin ion
journal, February 2015


The influence of crystallinity on magnetic ordering in natural ferrihydrites
journal, June 1988


Structure and Mechanisms of Formation of FeOOH(NO 3 ) Oligomers in the Early Stages of Hydrolysis
journal, June 1997

  • Rose, Jérôme; Manceau, Alain; Masion, Armand
  • Langmuir, Vol. 13, Issue 12
  • DOI: 10.1021/la962079k

Chromatographic Separation and Characterization of Hydrolyzed Cr(III) Species
journal, July 2002

  • Friese, J. I.; Ritherdon, B.; Clark, S. B.
  • Analytical Chemistry, Vol. 74, Issue 13
  • DOI: 10.1021/ac0109772

Environmentally Abundant Anions Influence the Nucleation, Growth, Ostwald Ripening, and Aggregation of Hydrous Fe(III) Oxides
journal, May 2012

  • Hu, Yandi; Lee, Byeongdu; Bell, Christopher
  • Langmuir, Vol. 28, Issue 20
  • DOI: 10.1021/la300791w

Structure of Sulfate Adsorption Complexes on Ferrihydrite
journal, October 2013

  • Zhu, Mengqiang; Northrup, Paul; Shi, Chenyang
  • Environmental Science & Technology Letters, Vol. 1, Issue 1
  • DOI: 10.1021/ez400052r

Characterization of Decaaqua-mu-oxodi-iron(III) by Mössbauer and Vibrational Spectroscopy.
journal, January 1975


Molecular Dynamics Simulation Study of the Early Stages of Nucleation of Iron Oxyhydroxide Nanoparticles in Aqueous Solutions
journal, August 2015

  • Zhang, Hengzhong; Waychunas, Glenn A.; Banfield, Jillian F.
  • The Journal of Physical Chemistry B, Vol. 119, Issue 33
  • DOI: 10.1021/acs.jpcb.5b03801

Kinetics of Hydrolysis and Precipitation of Ferric Iron in Seawater
journal, September 2003

  • Rose, Andrew L.; Waite, T. David
  • Environmental Science & Technology, Vol. 37, Issue 17
  • DOI: 10.1021/es034102b

Reconciling kinetic and equilibrium observations of iron(III) solubility in aqueous solutions with a polymer-based model
journal, December 2007


Sulfate Local Coordination Environment in Schwertmannite
journal, August 2015

  • Wang, Xiaoming; Gu, Chunhao; Feng, Xionghan
  • Environmental Science & Technology, Vol. 49, Issue 17
  • DOI: 10.1021/acs.est.5b02660

Fe(III) Nucleation in the Presence of Bivalent Cations and Oxyanions Leads to Subnanoscale 7 Å Polymers
journal, October 2014

  • van Genuchten, Case M.; Gadgil, Ashok J.; Peña, Jasquelin
  • Environmental Science & Technology, Vol. 48, Issue 20
  • DOI: 10.1021/es503281a

In Situ Structural Characterization of Ferric Iron Dimers in Aqueous Solutions: Identification of μ-Oxo Species
journal, May 2013

  • Zhu, Mengqiang; Puls, Brendan W.; Frandsen, Cathrine
  • Inorganic Chemistry, Vol. 52, Issue 12
  • DOI: 10.1021/ic302053w

Nucleation and Growth Mechanisms of Fe Oxyhydroxide in the Presence of PO 4 Ions. 1. Fe K-Edge EXAFS Study
journal, January 1996

  • Rose, Jérôme; Manceau, Alain; Bottero, Jean-Yves
  • Langmuir, Vol. 12, Issue 26
  • DOI: 10.1021/la9606299

Formation and secondary mineralization of ferrihydrite in the presence of silicate and Mn(II)
journal, November 2015


On the Crystal Structure of Some Basic Aluminium Salts.
journal, January 1960


Formation Mechanism of the Ga 13 Keggin Ion:  A Combined EXAFS and NMR Study
journal, June 2000

  • Michot, Laurent J.; Montargès-Pelletier, Emmanuelle; Lartiges, Bruno S.
  • Journal of the American Chemical Society, Vol. 122, Issue 25
  • DOI: 10.1021/ja9941429

Speciation of Fe in Fe-modified zeolite catalysts
journal, August 2010


From Fe(III) Ions to Ferrihydrite and then to Hematite
journal, January 1999

  • Schwertmann, Udo; Friedl, Josef; Stanjek, Helge
  • Journal of Colloid and Interface Science, Vol. 209, Issue 1
  • DOI: 10.1006/jcis.1998.5899

Homopolynuclear and heteropolynuclear Rh(III) aqua ions – a review
journal, July 2004


Direct Observation of Tetrahedrally Coordinated Fe(III) in Ferrihydrite
journal, March 2012

  • Peak, Derek; Regier, Tom
  • Environmental Science & Technology, Vol. 46, Issue 6
  • DOI: 10.1021/es203816x

Hydrolysis of inorganic iron(III) salts
journal, February 1984


Nucleation and Growth Mechanisms of Iron Oxyhydroxides in the Presence of PO 4 Ions. 4. Structure of the Aggregates
journal, July 1997

  • Masion, Armand; Rose, Jérôme; Bottero, Jean-Yves
  • Langmuir, Vol. 13, Issue 14
  • DOI: 10.1021/la970041h

Size-Dependent Bandgap of Nanogoethite
journal, August 2011

  • Zhang, Hengzhong; Bayne, Meredith; Fernando, Sandra
  • The Journal of Physical Chemistry C, Vol. 115, Issue 36
  • DOI: 10.1021/jp205192a

The Mössbauer spectrum of “well”-crystallized ferrihydrite
journal, September 1988


A disordered nanoparticle model for 6-line ferrihydrite
journal, August 2013

  • Gilbert, B.; Erbs, J. J.; Penn, R. L.
  • American Mineralogist, Vol. 98, Issue 8-9
  • DOI: 10.2138/am.2013.4421

Removing Arsenic from Synthetic Groundwater with Iron Electrocoagulation: An Fe and As K-Edge EXAFS Study
journal, December 2011

  • van Genuchten, Case M.; Addy, Susan E. A.; Peña, Jasquelin
  • Environmental Science & Technology, Vol. 46, Issue 2
  • DOI: 10.1021/es201913a

Iron oxides: From molecular clusters to solid. A nice example of chemical versatility
journal, June 2006

  • Jolivet, Jean-Pierre; Tronc, Elisabeth; Chanéac, Corinne
  • Comptes Rendus Geoscience, Vol. 338, Issue 6-7
  • DOI: 10.1016/j.crte.2006.04.014

Iron(III) Hydrolysis and Solubility at 25 °C
journal, September 2007

  • Stefánsson, Andri
  • Environmental Science & Technology, Vol. 41, Issue 17
  • DOI: 10.1021/es070174h

Kinetics of Fe(III) precipitation in aqueous solutions at pH 6.0–9.5 and 25°C
journal, February 2006

  • Pham, A. Ninh; Rose, Andrew L.; Feitz, Andrew J.
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 3
  • DOI: 10.1016/j.gca.2005.10.018

Kinetics of ferric oxyhydroxide precipitation
journal, August 1993


Competing Fe(II)-Induced Mineralization Pathways of Ferrihydrite
journal, September 2005

  • Hansel, Colleen M.; Benner, Shawn G.; Fendorf, Scott
  • Environmental Science & Technology, Vol. 39, Issue 18
  • DOI: 10.1021/es050666z

Iron oxide chemistry. From molecular clusters to extended solid networks
journal, January 2004

  • Jolivet, Jean-Pierre; Chanéac, Corinne; Tronc, Elisabeth
  • Chem. Commun., Issue 5
  • DOI: 10.1039/B304532N

Surface and mineral structure of ferrihydrite
journal, March 2013


Utilization of crown ethers to stabilize the dinuclear μ-oxo bridged iron(iii) aqua ion, [(H2O)5Fe(μ-O)Fe(OH2)5]4+
journal, January 2002

  • Junk, Peter C.; McCool, Brian J.; Moubaraki, Boujemaa
  • Journal of the Chemical Society, Dalton Transactions, Issue 6
  • DOI: 10.1039/b105691n

Structural relationships between colloidal solutions and hydroxide gels of iron(III) nitrate
journal, January 1977


Hydrolysis of Iron(III)…Chaotic Olation Versus Nucleation
journal, March 1984


Partial hydrolysis of ferric nitrate salt. Structural investigation by dynamic light scattering and small-angle x-ray scattering
journal, July 1991

  • Bottero, Jean Yves.; Tchoubar, D.; Arnaud, M.
  • Langmuir, Vol. 7, Issue 7
  • DOI: 10.1021/la00055a013

Composition and Structure of Polynuclear Chromium(III) Hydroxo Complexes
journal, November 2009

  • Torapava, Natallia; Radkevich, Artsiom; Davydov, Dmitri
  • Inorganic Chemistry, Vol. 48, Issue 21
  • DOI: 10.1021/ic901539g

Minerals as Molecules-Use of Aqueous Oxide and Hydroxide Clusters to Understand Geochemical Reactions
journal, April 2009

  • Casey, William H.; Rustad, James R.; Spiccia, Leone
  • Chemistry - A European Journal, Vol. 15, Issue 18
  • DOI: 10.1002/chem.200802636

Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism
journal, February 2010

  • Michel, F. M.; Barron, V.; Torrent, J.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 7
  • DOI: 10.1073/pnas.0910170107

Structure of Fe(III) precipitates generated by the electrolytic dissolution of Fe(0) in the presence of groundwater ions
journal, February 2014

  • van Genuchten, Case M.; Peña, Jasquelin; Amrose, Susan E.
  • Geochimica et Cosmochimica Acta, Vol. 127
  • DOI: 10.1016/j.gca.2013.11.044

New Reaction Path in the Dissociation of the Fe 2 (μ-OH) 2 (H 2 O) 8 4+ Complex
journal, February 1999

  • Lente, Gábor; Fábián, István
  • Inorganic Chemistry, Vol. 38, Issue 3
  • DOI: 10.1021/ic980813c

The Structure of Ferrihydrite, a Nanocrystalline Material
journal, June 2007


Structure and mechanisms of formation of iron oxide hydroxide (chloride) polymers
journal, January 1994

  • Bottero, Jean Yves; Manceau, Alain; Villieras, Frederic
  • Langmuir, Vol. 10, Issue 1
  • DOI: 10.1021/la00013a046

Basic concepts of the crystallization from aqueous solutions: The example of aluminum oxy(hydroxi)des and aluminosilicates
journal, February 2011

  • Jolivet, Jean-Pierre; Chanéac, Corinne; Chiche, David
  • Comptes Rendus Geoscience, Vol. 343, Issue 2-3
  • DOI: 10.1016/j.crte.2010.12.006

Formation of iron(III) hydroxides from homogeneous solutions
journal, June 1997


The structure of an iron core analog of ferritin
journal, June 1968

  • Brady, G. W.; Kurkjian, C. R.; Lyden, E. F. X.
  • Biochemistry, Vol. 7, Issue 6
  • DOI: 10.1021/bi00846a022

Mössbauer spectroscopic studies of the magnetic hyperfine interaction in the ferric hexaquo complex in frozen aqueous solution
journal, January 1977


Quick extended x-ray absorption fine structure instrument with millisecond time scale, optimized for in situ applications
journal, January 2010

  • Khalid, S.; Caliebe, W.; Siddons, P.
  • Review of Scientific Instruments, Vol. 81, Issue 1
  • DOI: 10.1063/1.3276679

New insight into the structure of nanocrystalline ferrihydrite: EXAFS evidence for tetrahedrally coordinated iron(III)
journal, May 2011

  • Maillot, Fabien; Morin, Guillaume; Wang, Yuheng
  • Geochimica et Cosmochimica Acta, Vol. 75, Issue 10
  • DOI: 10.1016/j.gca.2011.03.011

Nucleation and Growth Mechanisms of Fe Oxyhydroxide in the Presence of PO 4 Ions. 2. P K-Edge EXAFS Study
journal, March 1997

  • Rose, Jérôme; Flank, Anne-Marie; Masion, Armand
  • Langmuir, Vol. 13, Issue 6
  • DOI: 10.1021/la961039d

Al30: A Giant Aluminum Polycation
journal, February 2000


Supramolecular Complexation of Polynuclear Aqua Ions: A Crown Ether Adduct of aμ-Oxo-Bridged Iron(III) Aqua Dimer
journal, August 1999


Nucleation and Growth Mechanisms of Iron Oxyhydroxides in the Presence of PO4 Ions. 3. Speciation of Fe by Small Angle X-ray Scattering
journal, July 1997

  • Masion, Armand; Rose, Jérôme; Bottero, Jean-Yves
  • Langmuir, Vol. 13, Issue 14
  • DOI: 10.1021/la962015+

Works referencing / citing this record:

Composition-Dependent Sorptive Fractionation of Anthropogenic Dissolved Organic Matter by Fe(III)-Montmorillonite
journal, March 2018


The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid
journal, April 2018

  • Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W.
  • Angewandte Chemie International Edition, Vol. 57, Issue 21
  • DOI: 10.1002/anie.201802915

Condensed ferric dimers for green photocatalytic synthesis of nylon precursors
journal, January 2019

  • Ide, Yusuke; Tominaka, Satoshi; Yoneno, Yumi
  • Chemical Science, Vol. 10, Issue 27
  • DOI: 10.1039/c9sc01253b

Direct Evidence for Ferrous Ion Oxidation and Incorporation in the Absence of Oxidants by Dps from Marinobacter hydrocarbonoclasticus
journal, December 2018

  • Penas, Daniela; Pereira, Alice S.; Tavares, Pedro
  • Angewandte Chemie, Vol. 131, Issue 4
  • DOI: 10.1002/ange.201809584

Evolution of the reactive surface area of ferrihydrite: time, pH, and temperature dependency of growth by Ostwald ripening
journal, January 2019

  • Hiemstra, Tjisse; Mendez, Juan C.; Li, Jiayu
  • Environmental Science: Nano, Vol. 6, Issue 3
  • DOI: 10.1039/c8en01198b

Iron speciation in iron–organic matter nanoaggregates: a kinetic approach coupling Quick-EXAFS and MCR-ALS chemometrics
journal, January 2019

  • Vantelon, Delphine; Davranche, Mélanie; Marsac, Rémi
  • Environmental Science: Nano, Vol. 6, Issue 8
  • DOI: 10.1039/c9en00210c

Direct Evidence for Ferrous Ion Oxidation and Incorporation in the Absence of Oxidants by Dps from Marinobacter hydrocarbonoclasticus
journal, January 2019

  • Penas, Daniela; Pereira, Alice S.; Tavares, Pedro
  • Angewandte Chemie International Edition, Vol. 58, Issue 4
  • DOI: 10.1002/anie.201809584

The Role of Bi 3+ in Promoting and Stabilizing Iron Oxo Clusters in Strong Acid
journal, April 2018

  • Sadeghi, Omid; Amiri, Mehran; Reinheimer, Eric W.
  • Angewandte Chemie, Vol. 130, Issue 21
  • DOI: 10.1002/ange.201802915

Iron Aquo Complex as an Efficient and Selective Homogeneous Photocatalyst for Organic Synthetic Reactions
journal, October 2018

  • Iqbal, Muhammad Faisal; Tominaka, Satoshi; Peng, Wenqin
  • ChemCatChem, Vol. 10, Issue 20
  • DOI: 10.1002/cctc.201801360