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

Title: A structural coarse-grained model for clays using simple iterative Boltzmann inversion

Abstract

Cesium-137 is a crucial byproduct of nuclear energy generation and is environmentally threatening due to its long half-life and affinity for naturally occurring micaceous clays. Current experimental observations of illite and phlogopite mica indicate that Cs+ is capable of exchanging with K+ bound in the anhydrous interlayers of layered silicates, forming sharp exchange fronts, leading to interstratification of Cs- and K-illite. We introduce here a coarse-grained (CG) model of the anhydrous illite interlayer developed using iterative Boltzmann inversion that qualitatively and quantitatively reproduces features of a previously proposed feedback mechanism of ion exchange. The CG model represents a 70-fold speedup over all-atom models of clay systems and predicts interlayer expansion for K-illite near ion exchange fronts. Contrary to the longstanding theory that ion exchange in a neighboring layer increases the binding of K in lattice counterion sites leading to interstratification, we find that the presence of neighboring exchanged layers leads to short-range structural relaxations that increase basal spacing and decrease cohesion of the neighboring K-illite layers. We also provide evidence that the formation of alternating Cs- and K-illite interlayers (i.e., ordered interstratification) is both thermodynamically and mechanically favorable compared to exchange in adjacent interlayers.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [3]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1532325
Alternate Identifier(s):
OSTI ID: 1421881
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schaettle, Karl, Ruiz Pestana, Luis, Head-Gordon, Teresa, and Lammers, Laura Nielsen. A structural coarse-grained model for clays using simple iterative Boltzmann inversion. United States: N. p., 2018. Web. doi:10.1063/1.5011817.
Copy to clipboard
Schaettle, Karl, Ruiz Pestana, Luis, Head-Gordon, Teresa, & Lammers, Laura Nielsen. A structural coarse-grained model for clays using simple iterative Boltzmann inversion. United States. https://doi.org/10.1063/1.5011817
Copy to clipboard
Schaettle, Karl, Ruiz Pestana, Luis, Head-Gordon, Teresa, and Lammers, Laura Nielsen. Tue . "A structural coarse-grained model for clays using simple iterative Boltzmann inversion". United States. https://doi.org/10.1063/1.5011817. https://www.osti.gov/servlets/purl/1532325.
Copy to clipboard
@article{osti_1532325,
title = {A structural coarse-grained model for clays using simple iterative Boltzmann inversion},
author = {Schaettle, Karl and Ruiz Pestana, Luis and Head-Gordon, Teresa and Lammers, Laura Nielsen},
abstractNote = {Cesium-137 is a crucial byproduct of nuclear energy generation and is environmentally threatening due to its long half-life and affinity for naturally occurring micaceous clays. Current experimental observations of illite and phlogopite mica indicate that Cs+ is capable of exchanging with K+ bound in the anhydrous interlayers of layered silicates, forming sharp exchange fronts, leading to interstratification of Cs- and K-illite. We introduce here a coarse-grained (CG) model of the anhydrous illite interlayer developed using iterative Boltzmann inversion that qualitatively and quantitatively reproduces features of a previously proposed feedback mechanism of ion exchange. The CG model represents a 70-fold speedup over all-atom models of clay systems and predicts interlayer expansion for K-illite near ion exchange fronts. Contrary to the longstanding theory that ion exchange in a neighboring layer increases the binding of K in lattice counterion sites leading to interstratification, we find that the presence of neighboring exchanged layers leads to short-range structural relaxations that increase basal spacing and decrease cohesion of the neighboring K-illite layers. We also provide evidence that the formation of alternating Cs- and K-illite interlayers (i.e., ordered interstratification) is both thermodynamically and mechanically favorable compared to exchange in adjacent interlayers.},
doi = {10.1063/1.5011817},
journal = {Journal of Chemical Physics},
number = 22,
volume = 148,
place = {United States},
year = {Tue Feb 20 00:00:00 EST 2018},
month = {Tue Feb 20 00:00:00 EST 2018}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5011817
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Comparison of the probability distribution of bond distances and bond angles for the ClayFF (solid) and ClayCG model (dotted). (a) Distribution of bond distances for the O-O CG bond; (b) Distribution of bond angles for the O-O-O 60 degree angle type bond.
All figures and tables (9 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:

Multiscale modeling of swelling clays: A computational and experimental approach
journal, June 2009

  • Katti, Dinesh R.; Matar, Mohamed I.; Katti, Kalpana S.
  • KSCE Journal of Civil Engineering, Vol. 13, Issue 4
  • DOI: 10.1007/s12205-009-0243-0

Acid−Base Properties of 2:1 Clays. I. Modeling the Role of Electrostatics
journal, June 2010

  • Delhorme, Maxime; Labbez, Christophe; Caillet, Céline
  • Langmuir, Vol. 26, Issue 12
  • DOI: 10.1021/la100069g

Uptake of Cesium and Strontium Ions by Artificially Altered Phlogopite
journal, April 2014

  • Tamura, Kenji; Kogure, Toshihiro; Watanabe, Yujiro
  • Environmental Science & Technology, Vol. 48, Issue 10
  • DOI: 10.1021/es4052654

Molecular Models of Cesium and Rubidium Adsorption on Weathered Micaceous Minerals
journal, May 2015

  • Zaunbrecher, Laura K.; Cygan, Randall T.; Elliott, W. Crawford
  • The Journal of Physical Chemistry A, Vol. 119, Issue 22
  • DOI: 10.1021/jp512824k

Experimental and modelling studies of caesium sorption on illite
journal, October 1999

  • Poinssot, Christophe; Baeyens, Bart; Bradbury, Michael H.
  • Geochimica et Cosmochimica Acta, Vol. 63, Issue 19-20
  • DOI: 10.1016/s0016-7037(99)00246-x

Kinetics of cesium sorption on illite
journal, March 1992

XRD and HRTEM Evidence for Fixation of Cesium Ions in Vermiculite Clay
journal, April 2012

  • Kogure, Toshihiro; Morimoto, Kazuya; Tamura, Kenji
  • Chemistry Letters, Vol. 41, Issue 4
  • DOI: 10.1246/cl.2012.380

Half-life measurements at the National Institute of Standards and Technology
journal, January 2002

Multilevel Summation Method for Electrostatic Force Evaluation
journal, January 2015

  • Hardy, David J.; Wu, Zhe; Phillips, James C.
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 2
  • DOI: 10.1021/ct5009075

Predicted spatio-temporal dynamics of radiocesium deposited onto forests following the Fukushima nuclear accident
journal, September 2013

  • Hashimoto, Shoji; Matsuura, Toshiya; Nanko, Kazuki
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02564

Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995

Characterization of the frayed edge site of micaceous minerals in soil clays influenced by different pedogenetic conditions in Japan and northern Thailand
journal, August 2008

Direct Exchange Mechanism for Interlayer Ions in Non-Swelling Clays
journal, December 2016

  • Ruiz Pestana, Luis; Kolluri, Kedarnath; Head-Gordon, Teresa
  • Environmental Science & Technology, Vol. 51, Issue 1
  • DOI: 10.1021/acs.est.6b04747

Global transition path search for dislocation formation in Ge on Si(001)
journal, August 2016

Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima
journal, February 2016

  • Mukai, Hiroki; Hirose, Atsushi; Motai, Satoko
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep21543

Caesium incorporation and retention in illite interlayers
journal, May 2015

A uniqueness theorem for fluid pair correlation functions
journal, September 1974

Diffusion of Ions in Bentonite and Vermiculite1
journal, January 1961

Cs–sorption in weathered biotite from Fukushima granitic soil
journal, January 2015

  • Kikuchi, Ryosuke; Mukai, Hiroki; Kuramata, Chisaki
  • Journal of Mineralogical and Petrological Sciences, Vol. 110, Issue 3
  • DOI: 10.2465/jmps.141218

Selective Sorption and Fixation of Cations by Clay Minerals: A Review
journal, January 1972

On the driving force of cation exchange in clays: Insights from combined microcalorimetry experiments and molecular simulation
journal, July 2009

  • Rotenberg, Benjamin; Morel, Jean-Pierre; Marry, Virginie
  • Geochimica et Cosmochimica Acta, Vol. 73, Issue 14
  • DOI: 10.1016/j.gca.2009.04.012

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Connecting the Molecular Scale to the Continuum Scale for Diffusion Processes in Smectite-Rich Porous Media
journal, March 2010

  • Bourg, Ian C.; Sposito, Garrison
  • Environmental Science & Technology, Vol. 44, Issue 6
  • DOI: 10.1021/es903645a

Sorption of cesium on illite: Non-equilibrium behaviour and reversibility
journal, February 1991

Representability problems for coarse-grained water potentials
journal, April 2007

  • Johnson, Margaret E.; Head-Gordon, Teresa; Louis, Ard A.
  • The Journal of Chemical Physics, Vol. 126, Issue 14
  • DOI: 10.1063/1.2715953

Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field
journal, January 2004

  • Cygan, Randall T.; Liang, Jian-Jie; Kalinichev, Andrey G.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 4
  • DOI: 10.1021/jp0363287

Multilevel summation of electrostatic potentials using graphics processing units
journal, March 2009

Cesium adsorption and distribution onto crushed granite under different physicochemical conditions
journal, January 2009

An Ion Diffusion Model in Semi-Permeable Clay Materials
journal, August 2007

  • Liu, Chongxuan
  • Environmental Science & Technology, Vol. 41, Issue 15
  • DOI: 10.1021/es0624117

Interstratified Clays as Fundamental Particles
journal, August 1984

Mechanism of Strong Affinity of Clay Minerals to Radioactive Cesium: First-Principles Calculation Study for Adsorption of Cesium at Frayed Edge Sites in Muscovite
journal, March 2013

  • Okumura, Masahiko; Nakamura, Hiroki; Machida, Masahiko
  • Journal of the Physical Society of Japan, Vol. 82, Issue 3
  • DOI: 10.7566/jpsj.82.033802

Retention of potentially mobile radiocesium in forest surface soils affected by the Fukushima nuclear accident
journal, December 2012

  • Koarashi, Jun; Moriya, Koichi; Atarashi-Andoh, Mariko
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep01005

A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions
journal, September 2006

  • Liu, Xian-Dong; Lu, Xian-Cai
  • Angewandte Chemie International Edition, Vol. 45, Issue 38
  • DOI: 10.1002/anie.200601740

Thermodynamic Study of Na-K-Ca Exchange Reactions in Vermiculite
journal, January 1984

Finite-size effects in molecular dynamics simulations: Static structure factor and compressibility. I. Theoretical method
journal, March 1996

Beware of density dependent pair potentials
journal, September 2002

The Cs/K Exchange in Muscovite Interlayers: An Ab Initio Treatment
journal, January 2001

Preferential adsorption of 137Cs to micaceous minerals in contaminated freshwater sediment
journal, April 1976

  • Francis, C. W.; Brinkley, F. S.
  • Nature, Vol. 260, Issue 5551
  • DOI: 10.1038/260511a0

Coarse-Grained Protein Models and Their Applications
journal, June 2016

Mesoscale properties of clay aggregates from potential of mean force representation of interactions between nanoplatelets
journal, April 2014

  • Ebrahimi, Davoud; Whittle, Andrew J.; Pellenq, Roland J. -M.
  • The Journal of Chemical Physics, Vol. 140, Issue 15
  • DOI: 10.1063/1.4870932

Salt exclusion in charged porous media: a coarse-graining strategy in the case of montmorillonite clays
journal, January 2009

  • Jardat, Marie; Dufrêche, Jean-François; Marry, Virginie
  • Physical Chemistry Chemical Physics, Vol. 11, Issue 12
  • DOI: 10.1039/b818055e

First-principles study of illite–smectite and implications for clay mineral systems
journal, November 2002

Potassium Release from Muscovite as Influenced by Particle Size*
journal, January 1969

Molecular Dynamics Simulations of Structural and Mechanical Properties of Muscovite: Pressure and Temperature Effects
journal, July 2012

  • Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 28
  • DOI: 10.1021/jp303143s

Mesoscale simulation of clay aggregate formation and mechanical properties
journal, June 2016

  • Ebrahimi, Davoud; Pellenq, Roland J. -M.; Whittle, Andrew J.
  • Granular Matter, Vol. 18, Issue 3
  • DOI: 10.1007/s10035-016-0655-8

A pair potential for liquid rubidium from the pair correlation function
journal, February 1973

Identification of the actual cesium-adsorbing materials in the contaminated Fukushima soil
journal, March 2016

Ca-K Exchange Reaction and Interstratification in Montmorillonite
journal, January 1979

Hydration Energy Determines Isovalent Cation Exchange Selectivity by Clay Minerals
journal, January 2006

  • Teppen, Brian J.; Miller, David M.
  • Soil Science Society of America Journal, Vol. 70, Issue 1
  • DOI: 10.2136/sssaj2004.0212

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22
  • DOI: 10.1063/1.1323224

Selective and irreversible adsorption mechanism of cesium on illite
journal, October 2017

Diffusion and retention behaviour of Cs in illite-added compacted montmorillonite
journal, May 2016

Direct observation of cesium at the interlayer region in phlogopite mica
journal, November 2013

Water Dynamics in Hectorite Clays: Infuence of Temperature Studied by Coupling Neutron Spin Echo and Molecular Dynamics
journal, April 2011

  • Marry, Virginie; Dubois, Emmanuelle; Malikova, Natalie
  • Environmental Science & Technology, Vol. 45, Issue 7
  • DOI: 10.1021/es1031932

A space–time-ensemble parallel nudged elastic band algorithm for molecular kinetics simulation
journal, February 2008

VMD: Visual molecular dynamics
journal, February 1996

Vibrational Spectroscopy and Dynamics of Water
journal, April 2016

Multiscale micromechanical modeling of polymer/clay nanocomposites and the effective clay particle
journal, January 2004

Mechanism of Exfoliation and Prediction of Materials Properties of Clay–Polymer Nanocomposites from Multiscale Modeling
journal, November 2015

Multilevel Summation Method for Electrostatic Force Evaluation
journal, January 2015

A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions
journal, September 2006

Global transition path search for dislocation formation in Ge on Si(001)
text, January 2016

    Sort by:
    [ × clear filter / sort ]

    Figures / Tables found in this record:

    Figure 1 (p. 10)figure
    Figure 2 (p. 10)figure
    Figure 3 (p. 11)figure
    Table 1 (p. 12)table
    Figure 4 (p. 13)figure
    Table 2 (p. 13)table
    Figure 5 (p. 14)figure
    Table 3 (p. 15)table
    Figure 6 (p. 16)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: