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Title: Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

Journal Article · · Journal of Physical Chemistry. C
 [1];  [1];  [2];  [3];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Alfred Univ., Alfred, NY (United States)
  3. Michigan State Univ., East Lansing, MI (United States)
+ Show Author Affiliations

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.

Research Organization:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC04-94AL85000
OSTI ID:
1235297
Alternate ID(s):
OSTI ID: 1237461
Report Number(s):
SAND-2015-5572J; SAND-2015-2329J; 594962
Journal Information:
Journal of Physical Chemistry. C, Vol. 119, Issue 30; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 75 works
Citation information provided by
Web of Science

References (76)

Hydrodynamics in Clay Nanopores journal July 2011
The Use of Clay as an Engineered Barrier in Radioactive-Waste Management – A Review journal December 2013
Chapter 11.4 Clays and Nuclear Waste Management book January 2006
Interlayer structure and dynamics of Cl-bearing hydrotalcite: far infrared spectroscopy and molecular dynamics modeling journal February 2003
Solvent Structure, Dynamics, and Ion Mobility in Aqueous Solutions at 25 °C journal May 1998
Geometry and Dynamics of Intercalated Water in Na-Fluorhectorite Clay Hydrates journal January 2008
Molecular Modeling of the Tributyl Phosphate Complex of Europium Nitrate in the Clay Hectorite journal August 1998
On the Calculation of Diffusion Coefficients in Confined Fluids and Interfaces with an Application to the Liquid−Vapor Interface of Water † journal May 2004
In Situ 13 C and 23 Na Magic Angle Spinning NMR Investigation of Supercritical CO 2 Incorporation in Smectite–Natural Organic Matter Composites journal February 2014
Structural and dynamical relationships of Ca2+ and H2O in smectite/2H2O systems journal February 2014
The structural environments of cations adsorbed onto clays: 133Cs variable-temperature MAS NMR spectroscopic study of hectorite journal June 1990
Water and Halide Adsorption to Corrosion Surfaces: Molecular Simulations of Atmospheric Interactions with Aluminum Oxyhydroxide and Gold journal July 2008
Molecular Dynamics Modeling of Chloride Binding to the Surfaces of Calcium Hydroxide, Hydrated Calcium Aluminate, and Calcium Silicate Phases journal August 2002
Molecular Dynamics Studies of Interfacial Water at the Alumina Surface journal December 2010
Microscale effect of microvadose in shale reservoirs journal August 2014
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
YUCCA MOUNTAIN: Earth-Science Issues at a Geologic Repository for High-Level Nuclear Waste journal May 2004
NMR Studies on Dynamics of Water Intercalated in Clay Minerals journal July 1999
Structural and Dielectric Properties of Quartz−Water Interfaces journal November 2008
Molecular dynamics study of water and ions transport in nano-pore of layered structure: A case study of tobermorite journal September 2014
Molecular Dynamics Modeling of Ion Adsorption to the Basal Surfaces of Kaolinite journal April 2007
Adsorption-Desorption Processes in Subsurface Reactive Transport Modeling journal August 2007
Upscaling of Permeability of Porous Materials: First Insight into the Effect of Pore-Space Characteristics journal January 2010
Dynamics in Clays - Combining Neutron Scattering and Microscopic Simulation journal February 2010
Molecular Dynamics Simulations of the Dynamic and Energetic Properties of Alkali and Halide Ions Using Water-Model-Specific Ion Parameters journal October 2009
Structure, Energetics, and Dynamics of Water Adsorbed on the Muscovite (001) Surface:  A Molecular Dynamics Simulation journal August 2005
Hydration Properties and Interlayer Organization of Water and Ions in Synthetic Na-Smectite with Tetrahedral Layer Charge. Part 2. Toward a Precise Coupling between Molecular Simulations and Diffraction Data journal December 2010
Microscopic simulation of structure and dynamics of water and counterions in a monohydrated montmorillonite journal August 2002
The effect of surface-solute interactions on the transport of solutes through porous materials journal April 2009
Assessing conceptual models for subsurface reactive transport of inorganic contaminants journal January 2004
NMR studies and multi-scale modeling of the water and ionic mobilities within the porous networks limited by clay particles journal June 2005
Effects of substrate structure and composition on the structure, dynamics, and energetics of water at mineral surfaces: A molecular dynamics modeling study journal February 2006
Water Structure and Aqueous Uranyl(VI) Adsorption Equilibria onto External Surfaces of Beidellite, Montmorillonite, and Pyrophyllite:  Results from Molecular Simulations journal June 2006
Connecting the Molecular Scale to the Continuum Scale for Diffusion Processes in Smectite-Rich Porous Media journal March 2010
Animated molecular dynamics simulations of hydrated caesium-smectite interlayers journal September 2002
Temperature effects on alkaline earth metal ions adsorption on gibbsite: Approaches from macroscopic sorption experiments and molecular dynamics simulations journal June 2013
Experimental evaluation of mixed fluid reactions between supercritical carbon dioxide and NaCl brine: Relevance to the integrity of a geologic carbon repository journal April 2005
Modeling Sorption and Diffusion of Organic Sorbate in Hexadecyltrimethylammonium-Modified Clay Nanopores – A Molecular Dynamics Simulation Study journal February 2013
Supercritical fluid behavior at nanoscale interfaces: Implications for CO 2 sequestration in geologic formations journal March 2010
Anisotropy of Water Dynamics in Clays: Insights from Molecular Simulations for Experimental QENS Analysis journal July 2013
Alkali Metal and H 2 O Dynamics at the Smectite/Water Interface journal October 2011
Hydration, Swelling, Interlayer Structure, and Hydrogen Bonding in Organolayered Double Hydroxides:  Insights from Molecular Dynamics Simulation of Citrate-Intercalated Hydrotalcite journal March 2006
Molecular Models of Hydroxide, Oxyhydroxide, and Clay Phases and the Development of a General Force Field journal January 2004
Microscopic Simulations of Interlayer Structure and Dynamics in Bihydrated Heteroionic Montmorillonites journal February 2003
Toward Modeling Clay Mineral Nanoparticles: The Edge Surfaces of Pyrophyllite and Their Interaction with Water journal November 2014
Surface geochemistry of the clay minerals journal March 1999
A Thermodynamic Understanding of Clay-Swelling Inhibition by Potassium Ions journal September 2006
Change of Free Energy during Adsorption of a Molecule journal December 2003
Molecular modeling of water structure in nano-pores between brucite (001) surfaces journal August 2004
Molecular models and simulations of layered materials journal January 2009
Overview of scientific investigations at Yucca Mountain—the potential repository for high-level nuclear waste journal May 1999
How Electrostatics Influences Hydrodynamic Boundary Conditions: Poiseuille and Electro-osmostic Flows in Clay Nanopores. journal January 2013
Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite journal February 2014
Dissolution and Precipitation of Clay Minerals under Geologic CO 2 Sequestration Conditions: CO 2 −Brine−Phlogopite Interactions journal August 2010
Effects of thermodynamic ensembles and mineral surfaces on interfacial water structure journal January 2012
Diffusion of Water in Clays on the Microscopic Scale:  Modeling and Experiment journal February 2006
Multiblock Pore-Scale Modeling and Upscaling of Reactive Transport: Application to Carbon Sequestration journal August 2012
Structure, Energetics, and Dynamics of Smectite Clay Interlayer Hydration: Molecular Dynamics and Metadynamics Investigation of Na-Hectorite journal March 2013
Multinuclear NMR study of the structure and micro-dynamics of counterions and water molecules within clay colloids journal June 2009
Mineralogy, morphology, and textural relationships in coatings on quartz grains in sediments in a quartz-sand aquifer journal June 2011
Adsorption Isotherms of Water on Mica: Redistribution and Film Growth journal January 2009
Structure and dynamics of water at a clay surface from molecular dynamics simulation journal January 2008
Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl–CaCl2) solutions journal August 2011
H 2 O and Cation Structure and Dynamics in Expandable Clays:  2 H and 39 K NMR Investigations of Hectorite journal March 2008
An ab Initio and Classical Molecular Dynamics Investigation of the Structural and Vibrational Properties of Talc and Pyrophyllite journal August 2007
Kinetic effects in predicting adsorption using the GCMC method – using CO 2 adsorption on ZIFs as an example journal January 2014
Alcohol and Thiol Adsorption on (Oxy)hydroxide and Carbon Surfaces: Molecular Dynamics Simulation and Desorption Experiments journal December 2012
Molecular Dynamics Simulations of Water and Sodium Diffusion in Smectite Interlayer Nanopores as a Function of Pore Size and Temperature journal December 2013
Effects of layer-charge distribution on the thermodynamic and microscopic properties of Cs-smectite journal April 2008
Temperature effect in a montmorillonite clay at low hydration—microscopic simulation journal September 2004
Molecular dynamics simulation of uranyl(vi) adsorption equilibria onto an external montmorillonite surface journal January 2005
Morphology, Genesis, and Distribution of Nanometer-Scale Pores in Siliceous Mudstones of the Mississippian Barnett Shale journal November 2009
Molecular dynamics simulations of the orthoclase (001)- and (010)-water interfaces journal March 2008
Water Dynamics in Hectorite Clays: Infuence of Temperature Studied by Coupling Neutron Spin Echo and Molecular Dynamics journal April 2011
Diffusion of Na and Cs in montmorillonite journal April 2008
Geochemical Processes Controlling Migration of Tank Wastes in Hanford's Vadose Zone journal January 2007

Cited By (6)

Classical Polarizable Force Field to Study Hydrated Hectorite: Optimization on DFT Calculations and Validation against XRD Data journal May 2018
Surface microstructure engenders unusual hydrophobicity in phyllosilicates journal January 2018
Hydrogen bonds at silica–CO 2 saturated water interface under geologic sequestration conditions journal July 2016
Hydrogen bonds at silica–CO2 saturated water interface under geologic sequestration conditions text January 2016
Hydrogen bonds at silica–CO2 saturated water interface under geologic sequestration conditions text January 2016
Atomistic Structure of Mineral Nano-aggregates from Simulated Compaction and Dewatering journal November 2017

Figures / Tables (10)

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Table 2(p. 22)table Table 2
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Figure 6(p. 24)figure Figure 6
Table 4(p. 25)table Table 4

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