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Title: Structure and reactivity of the calcite–water interface

Abstract

The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO2 partial pressure. Changes in pH have only a weak effect in non–equilibrium solutions. The surface structure of (104) faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ~4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 ± 0.05 Å above surface calcium ions and the second layer at 3.24 ± 0.06 Å above the surface associated with surface carbonate ions. A Basic Stern surface complexation model is developed to model observed zetapotentials, while only considering outer–sphere complexes of ions other than protons and hydroxide. The Basic Sternmore » SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results.« less

Authors:
 [1];  [2];  [1];  [3];  [1];  [4]
  1. Karlsruher Inst. für Technologie, Karlsruhe (Germany)
  2. Univ. of Alaskan, Fairbanks, AK (United States)
  3. Univ. of Chicago, IL (United States). GeoSoilEnviroCars
  4. Forschungszentrum Julich (Germany). Inst. für Energieforschung
Publication Date:
Research Org.:
Univ. of Chicago, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1509824
Grant/Contract Number:  
FG02-94ER14466; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Colloid and Interface Science
Additional Journal Information:
Journal Volume: 354; Journal Issue: 2; Journal ID: ISSN 0021-9797
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
58 GEOSCIENCES; Synchrotron radiation; Calcite; Zetapotential; Surface diffraction; Crystal truncation rod; Surface complexation model

Citation Formats

Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., and Bosbach, Dirk. Structure and reactivity of the calcite–water interface. United States: N. p., 2010. Web. doi:10.1016/j.jcis.2010.10.047.
Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., & Bosbach, Dirk. Structure and reactivity of the calcite–water interface. United States. https://doi.org/10.1016/j.jcis.2010.10.047
Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., and Bosbach, Dirk. Tue . "Structure and reactivity of the calcite–water interface". United States. https://doi.org/10.1016/j.jcis.2010.10.047. https://www.osti.gov/servlets/purl/1509824.
@article{osti_1509824,
title = {Structure and reactivity of the calcite–water interface},
author = {Heberling, Frank and Trainor, Thomas P. and Lützenkirchen, Johannes and Eng, Peter and Denecke, Melissa A. and Bosbach, Dirk},
abstractNote = {The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO2 partial pressure. Changes in pH have only a weak effect in non–equilibrium solutions. The surface structure of (104) faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ~4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 ± 0.05 Å above surface calcium ions and the second layer at 3.24 ± 0.06 Å above the surface associated with surface carbonate ions. A Basic Stern surface complexation model is developed to model observed zetapotentials, while only considering outer–sphere complexes of ions other than protons and hydroxide. The Basic Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results.},
doi = {10.1016/j.jcis.2010.10.047},
journal = {Journal of Colloid and Interface Science},
number = 2,
volume = 354,
place = {United States},
year = {Tue Oct 26 00:00:00 EDT 2010},
month = {Tue Oct 26 00:00:00 EDT 2010}
}

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Cited by: 212 works
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Figure 1 Figure 1: SEM picture of commercial calcite.

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Works referenced in this record:

The long-term fate of Cu2+, Zn2+, and Pb2+ adsorption complexes at the calcite surface: An X-ray absorption spectroscopy study
journal, June 2006

  • Elzinga, Evert J.; Rouff, Ashaki A.; Reeder, Richard J.
  • Geochimica et Cosmochimica Acta, Vol. 70, Issue 11
  • DOI: 10.1016/j.gca.2006.02.026

Spectroscopic investigation of U(VI) sorption at the calcite-water interface
journal, June 2004

  • Elzinga, Evert J.; Tait, C. Drew; Reeder, Richard J.
  • Geochimica et Cosmochimica Acta, Vol. 68, Issue 11
  • DOI: 10.1016/j.gca.2003.09.023

Laser and X-ray spectroscopic studies of uranium-calcite interface phenomena
journal, September 1997


Neptunium(V) adsorption to calcite
journal, December 2008


Neptunium(V) Coprecipitation with Calcite
journal, January 2008

  • Heberling, Frank; Denecke, Melissa A.; Bosbach, Dirk
  • Environmental Science & Technology, Vol. 42, Issue 2
  • DOI: 10.1021/es071790g

Uranyl Incorporation into Calcite and Aragonite:  XAFS and Luminescence Studies
journal, February 2000

  • Reeder, Richard J.; Nugent, Melissa; Lamble, Geraldine M.
  • Environmental Science & Technology, Vol. 34, Issue 4
  • DOI: 10.1021/es990981j

A Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) Study of the Interaction of Trivalent Actinides (Cm(III)) with Calcite
journal, May 2002

  • Stumpf, Thorsten; Fanghänel, Thomas
  • Journal of Colloid and Interface Science, Vol. 249, Issue 1
  • DOI: 10.1006/jcis.2002.8251

Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite
journal, March 1996


Eu(III), Sm(III), Np(V), Pu(V), and Pu(IV) sorption to calcite
journal, January 2005


Partitioning of rare earth elements (REEs) between calcite and seawater solutions at 25°C and 1 atm, and high dissolved REE concentrations
journal, February 1995


Relationship between surface structure, growth mechanism, and trace element incorporation in calcite
journal, February 1995


Theoretical surface morphology of {011¯2} acute rhombohedron of calcite
journal, February 2008


Surface speciation of calcite observed in situ by high-resolution X-ray reflectivity
journal, April 2000


Three-dimensional structure of the calcite–water interface by surface X-ray scattering
journal, December 2004


Crystalline Order of a Water/Glycine Film Coadsorbed on the (104) Calcite Surface
journal, April 2007

  • Magdans, Uta; Torrelles, Xavier; Angermund, Klaus
  • Langmuir, Vol. 23, Issue 9
  • DOI: 10.1021/la0636659

The {1 0 4} cleavage rhombohedron of calcite: theoretical equilibrium properties
journal, October 2000


Free Energy of Adsorption of Water and Metal Ions on the {101̄4} Calcite Surface
journal, August 2004

  • Kerisit, Sebastien; Parker, Stephen C.
  • Journal of the American Chemical Society, Vol. 126, Issue 32
  • DOI: 10.1021/ja0487776

Atomistic simulation of the free energies of dissolution of ions from flat and stepped calcite surfaces
journal, August 2006


Theoretical Insights into the Hydrated (10.4) Calcite Surface: Structure, Energetics, and Bonding Relationships
journal, June 2009

  • Villegas-Jiménez, Adrián; Mucci, Alfonso; Whitehead, Michael A.
  • Langmuir, Vol. 25, Issue 12
  • DOI: 10.1021/la803652x

Derivation of an Accurate Force-Field for Simulating the Growth of Calcium Carbonate from Aqueous Solution: A New Model for the Calcite−Water Interface
journal, February 2010

  • Raiteri, Paolo; Gale, Julian D.; Quigley, David
  • The Journal of Physical Chemistry C, Vol. 114, Issue 13
  • DOI: 10.1021/jp910977a

The zero point of charge of calcite
journal, August 1967


Surface charge of MnCO3and FeCO3
journal, August 1990


Surface Speciation Models of Calcite and Dolomite/Aqueous Solution Interfaces and Their Spectroscopic Evaluation
journal, March 2000

  • Pokrovsky, O. S.; Mielczarski, J. A.; Barres, O.
  • Langmuir, Vol. 16, Issue 6
  • DOI: 10.1021/la980905e

Surface Chemistry and Dissolution Kinetics of Divalent Metal Carbonates
journal, February 2002

  • Pokrovsky, O. S.; Schott, J.
  • Environmental Science & Technology, Vol. 36, Issue 3
  • DOI: 10.1021/es010925u

Defining reactive sites on hydrated mineral surfaces: Rhombohedral carbonate minerals
journal, August 2009

  • Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S.
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 15, p. 4326-4345
  • DOI: 10.1016/j.gca.2009.04.036

Toward a conceptual model of the calcite surface: hydration, hydrolysis, and surface potential
journal, October 1999


Charge determination at calcium salt/aqueous solution interface
journal, January 1979

  • Foxall, Thomas; Peterson, Gordon C.; Rendall, Henry M.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
  • DOI: 10.1039/f19797501034

A Surface Structural Approach to Ion Adsorption: The Charge Distribution (CD) Model
journal, May 1996

  • Hiemstra, T.; Van Riemsdijk, W. H.
  • Journal of Colloid and Interface Science, Vol. 179, Issue 2
  • DOI: 10.1006/jcis.1996.0242

Nagra/PSI Chemical Thermodynamic Data Base 01/01
journal, January 2002


Angle calculations for a `4S+2D' six-circle diffractometer
journal, August 1999


Improved data acquisition in grazing-incidence X-ray scattering experiments using a pixel detector
journal, June 2005

  • Schlepütz, C. M.; Herger, R.; Willmott, P. R.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 61, Issue 4
  • DOI: 10.1107/S0108767305014790

ROD : a program for surface X-ray crystallography
journal, April 2000


Calculation of crystal truncation rod structure factors for arbitrary rational surface terminations
journal, November 2002

  • Trainor, Thomas P.; Eng, Peter J.; Robinson, Ian K.
  • Journal of Applied Crystallography, Vol. 35, Issue 6
  • DOI: 10.1107/S0021889802013985

Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

  • Brown, I. D.; Altermatt, D.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4
  • DOI: 10.1107/S0108768185002063

UCODE, a computer code for universal inverse modeling
journal, May 1999


Crystal truncation rods and surface roughness
journal, March 1986


An atomic force microscopy study of calcite dissolution in saline solutions: The role of magnesium ions
journal, June 2009

  • Ruiz-Agudo, E.; Putnis, C. V.; Jiménez-López, C.
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 11
  • DOI: 10.1016/j.gca.2009.03.016

Intrinsic Proton Affinity of Reactive Surface Groups of Metal (Hydr)oxides: The Bond Valence Principle
journal, December 1996

  • Hiemstra, T.; Venema, P.; Riemsdijk, W. H. Van
  • Journal of Colloid and Interface Science, Vol. 184, Issue 2
  • DOI: 10.1006/jcis.1996.0666

The calcite/water interface
journal, September 2007

  • Eriksson, Rasmus; Merta, Juha; Rosenholm, Jarl B.
  • Journal of Colloid and Interface Science, Vol. 313, Issue 1
  • DOI: 10.1016/j.jcis.2007.04.034

Interfacial Charging Phenomena of Aluminum (Hydr)oxides
journal, August 1999


A macroscopic water structure based model for describing charging phenomena at inert hydrophobic surfaces in aqueous electrolyte solutions
journal, January 2008

  • Lützenkirchen, Johannes; Preočanin, Tajana; Kallay, Nikola
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 32
  • DOI: 10.1039/b807395c

Kinetics of calcite growth: surface processes and relationships to macroscopic rate laws
journal, July 2000


Nanoscale phenomena during the growth of solid solutions on calcite {101¯4} surfaces
journal, January 2006


Charged Barite−Aqueous Solution Interface:  Surface Potential and Atomically Resolved Visualization
journal, November 2003

  • Bokern, D. G.; Hunter, K. A.; McGrath, K. M.
  • Langmuir, Vol. 19, Issue 24
  • DOI: 10.1021/la0269255

Works referencing / citing this record:

Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite–water interface
journal, January 2012

  • Wolthers, M.; Di Tommaso, D.; Du, Z.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 43
  • DOI: 10.1039/c2cp42290e

Evolution of calcite surface reconstruction and interface adsorption of calcite-CO 2 with temperature
journal, November 2018


On Permeability Prediction From Complex Conductivity Measurements Using Polarization Magnitude and Relaxation Time
journal, May 2018

  • Robinson, Judith; Slater, Lee; Weller, Andreas
  • Water Resources Research, Vol. 54, Issue 5
  • DOI: 10.1002/2017wr022034

Zeta potential in oil-water-carbonate systems and its impact on oil recovery during controlled salinity water-flooding
journal, November 2016

  • Jackson, Matthew D.; Al-Mahrouqi, Dawoud; Vinogradov, Jan
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep37363

Zeta potential of porous rocks in contact with mixtures of monovalent and divalent electrolytes
journal, March 2019

  • Thanh, Luong Duy; Sprik, Rudolf; Nguyen, Xuan Ca
  • Geophysical Prospecting, Vol. 67, Issue 5
  • DOI: 10.1111/1365-2478.12759

Response of Non-Polar Oil Component on Low Salinity Effect in Carbonate Reservoirs: Adhesion Force Measurement Using Atomic Force Microscopy
journal, December 2019

  • Maskari, Nasser S. Al; Sari, Ahmad; Hossain, Md Mofazzal
  • Energies, Vol. 13, Issue 1
  • DOI: 10.3390/en13010077

Low Salinity Waterflooding in Carbonate Reservoirs: Review of Interfacial Mechanisms
journal, May 2018

  • Derkani, Maryam; Fletcher, Ashleigh; Abdallah, Wael
  • Colloids and Interfaces, Vol. 2, Issue 2
  • DOI: 10.3390/colloids2020020

Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy
journal, July 2014


Impact of Initial Wettability and Injection Brine Chemistry on Mechanical Behaviour of Kansas Chalk
journal, March 2019

  • Sachdeva, Jaspreet S.; Nermoen, Anders; Korsnes, Reidar I.
  • Transport in Porous Media, Vol. 128, Issue 2
  • DOI: 10.1007/s11242-019-01269-z

Nucleation in confinement generates long-range repulsion between rough calcite surfaces
journal, June 2019

  • Dziadkowiec, Joanna; Zareeipolgardani, Bahareh; Dysthe, Dag Kristian
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-019-45163-6

Electrokinetic Characterization of Natural Stones Coated with Nanocomposites for the Protection of Cultural Heritage
journal, September 2018

  • Roveri, Marco; Raneri, Simona; Bianchi, Sabrina
  • Applied Sciences, Vol. 8, Issue 9
  • DOI: 10.3390/app8091694

Surface chemistry considerations in the flotation of rare-earth and other semisoluble salt minerals
journal, February 2013

  • Zhang, X.; Du, H.; Wang, X.
  • Mining, Metallurgy & Exploration, Vol. 30, Issue 1
  • DOI: 10.1007/bf03402338

Optimizing a flow-through X-ray transmission cell for studies of temporal and spatial variations of ion distributions at mineral–water interfaces
journal, November 2012

  • Lee, Sang Soo; Fenter, Paul; Park, Changyong
  • Journal of Synchrotron Radiation, Vol. 20, Issue 1
  • DOI: 10.1107/s0909049512041568

Nucleation in Confinement Generates Long-range Repulsion between Rough Calcite Surfaces
text, January 2019


Reconsidering Calcium Dehydration as the Rate-Determining Step in Calcium Mineral Growth
journal, October 2019

  • Koskamp, Janou A.; Ruiz-Hernandez, Sergio E.; Di Tommaso, Devis
  • The Journal of Physical Chemistry C, Vol. 123, Issue 44
  • DOI: 10.1021/acs.jpcc.9b06403

Nucleation in confinement generates long-range repulsion between rough calcite surfaces
journal, June 2019

  • Dziadkowiec, Joanna; Zareeipolgardani, Bahareh; Dysthe, Dag Kristian
  • Scientific Reports, Vol. 9, Issue 1
  • DOI: 10.1038/s41598-019-45163-6

Novel Approach to Study the Impact of Asphaltene Properties on Low Salinity Flooding
conference, October 2020

  • Hassan, Saleh F.; Yutkin, Maxim P.; Kamireddy, Sirisha
  • Day 2 Tue, October 27, 2020
  • DOI: 10.2118/201747-ms