Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Binding Geometries of Silicate Species on Ferrihydrite Surfaces

Abstract

Silicate sorption on ferrihydrite surfaces, as monomers, oligomers, and polymers, strongly affects ferrihydrite crystallinity, thermodynamic stability, and surface reactivity. How these silicate species bind on ferrihydrite surfaces is, however, not well understood. We have determined silicate binding geometries using a combination of X-ray absorption spectroscopy (XAS), differential atomic pair distribution function (d-PDF) analysis, and density functional theory (DFT) calculations. Silicon K-edge absorption pre-edges and DFT-predicted energies indicate that silicate forms monomeric monodentate–mononuclear (MM) complexes at low silicate sorption loadings. With increasing silicate loading, the pre-edge peak shifts to higher energies, suggesting changes in the silicate binding geometry toward multidentate complexation. The d-PDF analysis determines the Si–Fe interatomic distance to be ~3.25 Å for the high-loading samples. The DFT calculations indicate that such distance corresponds to an oligomer in the bidentate–binuclear (BB) binding geometry. The transition of the silicate sorption geometry accompanied by polymerization can affect stability of ferrihydrite and its adsorption and redox reactivity and increase the degree of Si isotopic fractionation upon silicate sorption on Fe oxides. MM monomeric complexes and BB oligomeric complexes should be used for surface complexation models predicting silicate sorption on Fe oxide surfaces.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [5]; ORCiD logo [6]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Wyoming, Laramie, WY (United States)
  2. Univ. of Texas at El Paso, TX (United States)
  3. Umeå Univ. (Sweden)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Univ. of Saskatchewan, Saskatchewan (Canada)
  6. Huazhong Agricultural Univ., Wuhan (China)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCESFOREIGN
OSTI Identifier:
1424771
Resource Type:
Accepted Manuscript
Journal Name:
ACS Earth and Space Chemistry
Additional Journal Information:
Journal Volume: 2; Journal Issue: 2; Journal ID: ISSN 2472-3452
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Sorption; Oxides; Monomers; Silicon; Mathematical methods; silicate; ferrihydrite; binding geometry; polymerization; Si K-edge XANES spectroscopy; differential PDF analysis; DFT calculations

Citation Formats

Wang, Xiaoming, Kubicki, James D., Boily, Jean-François, Waychunas, Glenn A., Hu, Yongfeng, Feng, Xionghan, and Zhu, Mengqiang. Binding Geometries of Silicate Species on Ferrihydrite Surfaces. United States: N. p., 2018. Web. doi:10.1021/acsearthspacechem.7b00109.
Copy to clipboard
Wang, Xiaoming, Kubicki, James D., Boily, Jean-François, Waychunas, Glenn A., Hu, Yongfeng, Feng, Xionghan, & Zhu, Mengqiang. Binding Geometries of Silicate Species on Ferrihydrite Surfaces. United States. https://doi.org/10.1021/acsearthspacechem.7b00109
Copy to clipboard
Wang, Xiaoming, Kubicki, James D., Boily, Jean-François, Waychunas, Glenn A., Hu, Yongfeng, Feng, Xionghan, and Zhu, Mengqiang. Fri . "Binding Geometries of Silicate Species on Ferrihydrite Surfaces". United States. https://doi.org/10.1021/acsearthspacechem.7b00109. https://www.osti.gov/servlets/purl/1424771.
Copy to clipboard
@article{osti_1424771,
title = {Binding Geometries of Silicate Species on Ferrihydrite Surfaces},
author = {Wang, Xiaoming and Kubicki, James D. and Boily, Jean-François and Waychunas, Glenn A. and Hu, Yongfeng and Feng, Xionghan and Zhu, Mengqiang},
abstractNote = {Silicate sorption on ferrihydrite surfaces, as monomers, oligomers, and polymers, strongly affects ferrihydrite crystallinity, thermodynamic stability, and surface reactivity. How these silicate species bind on ferrihydrite surfaces is, however, not well understood. We have determined silicate binding geometries using a combination of X-ray absorption spectroscopy (XAS), differential atomic pair distribution function (d-PDF) analysis, and density functional theory (DFT) calculations. Silicon K-edge absorption pre-edges and DFT-predicted energies indicate that silicate forms monomeric monodentate–mononuclear (MM) complexes at low silicate sorption loadings. With increasing silicate loading, the pre-edge peak shifts to higher energies, suggesting changes in the silicate binding geometry toward multidentate complexation. The d-PDF analysis determines the Si–Fe interatomic distance to be ~3.25 Å for the high-loading samples. The DFT calculations indicate that such distance corresponds to an oligomer in the bidentate–binuclear (BB) binding geometry. The transition of the silicate sorption geometry accompanied by polymerization can affect stability of ferrihydrite and its adsorption and redox reactivity and increase the degree of Si isotopic fractionation upon silicate sorption on Fe oxides. MM monomeric complexes and BB oligomeric complexes should be used for surface complexation models predicting silicate sorption on Fe oxide surfaces.},
doi = {10.1021/acsearthspacechem.7b00109},
journal = {ACS Earth and Space Chemistry},
number = 2,
volume = 2,
place = {United States},
year = {Fri Jan 05 00:00:00 EST 2018},
month = {Fri Jan 05 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsearthspacechem.7b00109
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal

Figures / Tables:

Figure 1 Figure 1: Silicate sorption isotherms at pH 4, 7 and 10, respectively, and their fits with the Langmuir equation (Qe = Qmax*kL*C/(1 + kL*C), where Qe is the amount of silicate sorbed, Qmax is the maximum sorption capacity, C is the equilibrium concentration, and KL is a constant related tomore » the binding strength) (a), and silicate adsorption kinetics on ferrihydrite surfaces with 1 mM Si at pH 4 (b).« less
All figures and tables (7 total)
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A Structural Model for Natural Siliceous Ferrihydrite
journal, January 1992

Ferrihydrite: A review of structure, properties and occurrence in relation to soils
journal, January 1992

Composition and structural aspects of naturally occurring ferrihydrite
journal, February 2011

  • Cismasu, A. Cristina; Michel, F. Marc; Tcaciuc, A. Patricia
  • Comptes Rendus Geoscience, Vol. 343, Issue 2-3
  • DOI: 10.1016/j.crte.2010.11.001

A New Approach to Sampling Intact Fe Plaque Reveals Si-Induced Changes in Fe Mineral Composition and Shoot As in Rice
journal, December 2016

  • Amaral, Douglas C.; Lopes, Guilherme; Guilherme, Luiz R. G.
  • Environmental Science & Technology, Vol. 51, Issue 1
  • DOI: 10.1021/acs.est.6b03558

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

Properties of impurity-bearing ferrihydrite III. Effects of Si on the structure of 2-line ferrihydrite
journal, May 2014

  • Cismasu, A. Cristina; Michel, F. Marc; Tcaciuc, A. Patricia
  • Geochimica et Cosmochimica Acta, Vol. 133
  • DOI: 10.1016/j.gca.2014.02.018

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

Si Incorporation into Hematite by Heating Si−Ferrihydrite
journal, September 2002

  • Campbell, A. S.; Schwertmann, U.; Stanjek, H.
  • Langmuir, Vol. 18, Issue 21
  • DOI: 10.1021/la011741w

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

Effects of phosphate and silicate on the transformation of hydroxycarbonate green rust to ferric oxyhydroxides
journal, December 2015

Polymerization of Silicate on Hematite Surfaces and Its Influence on Arsenic Sorption
journal, December 2012

  • Christl, Iso; Brechbühl, Yves; Graf, Moritz
  • Environmental Science & Technology, Vol. 46, Issue 24
  • DOI: 10.1021/es303297m

Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: formation of carbonate green rust in the presence of phosphate
journal, July 2004

  • Kukkadapu, Ravi K.; Zachara, John M.; Fredrickson, James K.
  • Geochimica et Cosmochimica Acta, Vol. 68, Issue 13
  • DOI: 10.1016/j.gca.2003.12.024

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide
journal, February 2009

  • Delstanche, S.; Opfergelt, S.; Cardinal, D.
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 4
  • DOI: 10.1016/j.gca.2008.11.014

Assessing the role of silicate polymerization on metal oxyhydroxide surfaces using X-ray photoelectron spectroscopy
journal, June 2011

Silicic Acid Adsorption and Oligomerization at the Ferrihydrite−Water Interface: Interpretation of ATR-IR Spectra Based on a Model Surface Structure
journal, January 2010

  • Swedlund, Peter J.; Miskelly, Gordon M.; McQuillan, A. James
  • Langmuir, Vol. 26, Issue 5
  • DOI: 10.1021/la903160q

An attenuated total reflectance IR study of silicic acid adsorbed onto a ferric oxyhydroxide surface
journal, July 2009

  • Swedlund, Peter J.; Miskelly, Gordon M.; McQuillan, A. James
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 14
  • DOI: 10.1016/j.gca.2009.04.007

The Application of Raman Spectroscopy to Probe the Association of H4SiO4 with Iron Oxides
journal, August 2016

The Influence of Surface Structure on H 4 SiO 4 Oligomerization on Rutile and Amorphous TiO 2 Surfaces: An ATR-IR and Synchrotron XPS Study
journal, October 2012

  • Song, Yantao; Swedlund, Peter J.; McIntosh, Grant J.
  • Langmuir, Vol. 28, Issue 49
  • DOI: 10.1021/la3032623

Stability constants for silicate adsorbed to ferrihydrite
journal, September 1994

Modeling Silica Sorption to Iron Hydroxide
journal, February 2002

  • Davis, Christina C.; Chen, Hsiao-Wen; Edwards, Marc
  • Environmental Science & Technology, Vol. 36, Issue 4
  • DOI: 10.1021/es010996t

Effect of Ferrihydrite Crystallite Size on Phosphate Adsorption Reactivity
journal, August 2013

  • Wang, Xiaoming; Li, Wei; Harrington, Richard
  • Environmental Science & Technology, Vol. 47, Issue 18
  • DOI: 10.1021/es401301z

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

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

A graphical user-friendly interface for MCR-ALS: a new tool for multivariate curve resolution in MATLAB
journal, March 2005

  • Jaumot, Joaquim; Gargallo, Raimundo; de Juan, Anna
  • Chemometrics and Intelligent Laboratory Systems, Vol. 76, Issue 1
  • DOI: 10.1016/j.chemolab.2004.12.007

Singular value decomposition and least squares solutions
journal, April 1970

  • Golub, G. H.; Reinsch, C.
  • Numerische Mathematik, Vol. 14, Issue 5
  • DOI: 10.1007/BF02163027

Determination of the number of factors and the experimental error in a data matrix
journal, April 1977

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

Arsenic Adsorption onto Minerals: Connecting Experimental Observations with Density Functional Theory Calculations
journal, March 2014

  • Watts, Heath; Tribe, Lorena; Kubicki, James
  • Minerals, Vol. 4, Issue 2
  • DOI: 10.3390/min4020208

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Specific Adsorption of Silicate and Phosphate by Soils
journal, March 1972

Polymerization of Silicic Acid Adsorbed on Iron(III) Hydroxide
journal, April 1980

  • Yokoyama, Takushi; Nakazato, Tatsuo; Tarutani, Toshikazu
  • Bulletin of the Chemical Society of Japan, Vol. 53, Issue 4
  • DOI: 10.1246/bcsj.53.850

X-ray Absorption Spectroscopic Quantification and Speciation Modeling of Sulfate Adsorption on Ferrihydrite Surfaces
journal, July 2016

  • Gu, Chunhao; Wang, Zimeng; Kubicki, James D.
  • Environmental Science & Technology, Vol. 50, Issue 15
  • DOI: 10.1021/acs.est.6b00753

Speciation of Iron and Sulfate in Acid Waters:  Aqueous Clusters to Mineral Precipitates
journal, January 2005

  • Majzlan, Juraj; Myneni, Satish C. B.
  • Environmental Science & Technology, Vol. 39, Issue 1
  • DOI: 10.1021/es049664p

Silicon K-edge XANES spectra of silicate minerals
journal, March 1995

  • Li, Dien; Bancroft, G. M.; Fleet, M. E.
  • Physics and Chemistry of Minerals, Vol. 22, Issue 2
  • DOI: 10.1007/BF00202471

Structural change of orthorhombic- I tridymite with temperature: A study based on second-order thermal-vibrational parameters
journal, January 1986

  • Kihara, Kuniaki; Matsumoto, Takeo; Imamura, Moritaka
  • Zeitschrift für Kristallographie, Vol. 177, Issue 1-2
  • DOI: 10.1524/zkri.1986.177.1-2.27

Short range order at the amorphous TiO2–water interface probed by silicic acid adsorption and interfacial oligomerization: An ATR-IR and 29Si MAS-NMR study
journal, February 2012

  • Swedlund, Peter J.; Song, Yantao; Zujovic, Zoran D.
  • Journal of Colloid and Interface Science, Vol. 368, Issue 1
  • DOI: 10.1016/j.jcis.2011.10.073

Adsorption and surface complex modeling of silicates on maghemite in aqueous suspensions
journal, February 2010

  • Jolsterå, Rickard; Gunneriusson, Lars; Forsling, Willis
  • Journal of Colloid and Interface Science, Vol. 342, Issue 2
  • DOI: 10.1016/j.jcis.2009.10.080

Soil Incorporation of Silica-Rich Rice Husk Decreases Inorganic Arsenic in Rice Grain
journal, May 2016

  • Seyfferth, Angelia L.; Morris, Andrew H.; Gill, Rattandeep
  • Journal of Agricultural and Food Chemistry, Vol. 64, Issue 19
  • DOI: 10.1021/acs.jafc.6b01201
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    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

    Phosphate Sorption Speciation and Precipitation Mechanisms on Amorphous Aluminum Hydroxide
    journal, March 2019

    Carbonate Adsorption to Ferrihydrite: Competitive Interaction with Phosphate for Use in Soil Systems
    journal, December 2018

      Sort by:
      [ × clear filter / sort ]

      Figures / Tables found in this record:

      Figure 1 (p. 11)figure
      Figure 2 (p. 12)figure
      Figure 3 (p. 14)figure
      Figure 4 (p. 17)figure
      Figure 5 (p. 18)figure
      Figure 6 (p. 20)figure
      Figure 7 (p. 23)figure
        [ × clear filter / sort ]
        Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

        Similar Records in DOE PAGES and OSTI.GOV collections: