Engineered Clay Barriers

(1)

Developments

Clay

Natural and

Engineered Clay

Barriers

Edited

_by

Christophe

Tournassat

Water, Environment and

_{Ecotechnology}

Division, French

Geological

Survey

(BRGM),

Orleans,

France

Earth Sciences

_Division,

Lawrence

_Berkeley

National

_Laboratory,

Berkeley,

CA, USA

Carl

I. Steefel

Earth Sciences

_Division,

Lawrence

_Berkeley

National

_Laboratory,

Berkeley,

CA, USA

Ian C.

_Bourg

Department

of Civil and Environmental

_Engineering,

Princeton

_University,

Princeton, NJ, USA

Earth Sciences

_Division,

Lawrence

_Berkeley

National

_Laboratory,

Berkeley,

CA, USA

FaYza

_Bergaya

Centrede Recherche sur la Matiere

Divisee,

Centre National de la

Recherche

_{Scientifique (CNRS), Orleans,}

France

AMSTERDAM•BOSTON• HEIDELBERG•LONDON•NEW YORK•OXFORD

(2)

List of Contributors xi

Acknowledgments

xiii

Introduction 1

1. Surface

_Properties

of

_Clay

Minerals 5

Christophe

Tournassat, Ian C. _Bourg, Carl I.Steefeland

Fa'fza_Bergaya

1.1 From Sheetsto

_Clay

Mineral Layers 6 1.1.1 Structure of

_Clay

Mineral _Layers 6

1.1.2 _Layer

_Charge

and

Charge Compensation

Mechanisms 8

1.1.3 _Aspect Ratio and

Morphology

of

_Clay

Mineral

Particles 8

1.2 From _Layersto Particles and

_Aggregates

9 1.2.1 _Layer

_Stacking

and

_Hydration

9 1.2.2

_{Mixed-Layer Clay}

Minerals 10 1.2.3 Particle SSA 10

1.2.4 Nature of theExternal Basal Surfaces of

_Clay

Mineral Particles 13

1.2.5

_Charge

Balanceatthe Scale ofa

Clay

Mineral Particle 15 1.2.6 From Particlesto _Aggregatesand Porous Media 15 1.3 Surface

_Properties

of Basal Surfaces 17

1.3.1 Cation

Exchange

and Cation

_{Exchange Capacity}

17

1.3.2 Protonation and

_{Deprotonation}

of

_Oxygen

Atoms

on Basal Surfaces 19

1.3.3 Electrostatic Potential, Cation Condensation, and

Anion Exclusion 19

1.4 Surface

_Properties

of

_Edges

23 1.4.1 Structureof

_Edges

23 1.4.2

_{Protonation/Deprotonation,}

Edge

Surface

Charge,

and Electrostatic Potential 23

1.4.3 Surface

_{Complexation,}

Cation andAnion

_Exchange

24 1.5 _Summary 25

References 25

(3)

2.

_Adsorption

of

_Inorganic

and

_Organic

Solutes

by Clay

Minerals 33

Mikhail Borisover and JamesA. Davis

2.1 Introduction 34

2.2

_Clay

Minerals and Surface Functional _Croups 34

2.3

_Inorganic

Solute _{Adsorption—Desorption}Mechanisms 35 2.3.1

_{Interlayer Adsorption}

36

2.3.2

_Edge

Site

_Adsorption

37

2.3.3 Surface

_{Precipitation}

and Metal Substitution

Reactions inthe

_Clay

Mineral Layer 45 2.4

_Organic

Solute

_Adsorption

Mechanisms 46

2.4.1

_Adsorption

of _Organic Molecules

_{by Clay}

Mineral

Surfaces 46

2.4.2

_Adsorption

of

_Charged

_{Organic Species}

_{by Clay}

Mineral Surfaces 52

2.5 Interactions of

_Clay

Mineral Surfaces in Soils and Sediments with NOM and Natural Nanoparticles of

Other Minerals 55

2.6

_Adsorption

Processeson

Clays

in Natural and

Engineered

Environments 56 2.6.1 Interactionsof Metal and MetalloidIonswith

Clays

in Natural and

_Engineered

Environments 57 2.6.2 Interactionsof

_{Organic Compounds}

with

_Clays

in

Natural and

_Engineered

Environments 59

2.7

_Summary

62

References 64

3. Chemical Conditions in

_Clay-Rocks

71

Christophe

Tournassat,Agnes Vinsot, Eric C. Gaucher and Scott Altmann

3.1 Introduction 72

3.2

_{Clay-Rock Mineralogy,}

WaterContent and _Porosity 73 3.3 _{Investigation}Methods for Pore-Water Chemical

Composition

Characterization 75 3.3.1 In Situ

_Techniques:

Piezometers and Instrumented

Boreholes 75

3.3.2 Pore-Water Extraction from Core

_{Samples by}

Squeezing 78 3.3.3 Alternative

_Techniques

79

3.3.4

_Examples

of Pore-Water

_Compositions

80 3.3.5 Indirect Characterization ofPore-Water

_Chemistry

80 3.4

_Modeling

Pore-Water

_Composition

86

3.4.1

_{Modeling Hypotheses,}

_Strategies,and

(4)

3.4.2

_Modeling

the Pore-Water_Composition in Pristine

Rock 91

3.4.3 Additional Model Controls 92

3.4.4

_Significance

ofPore-Water _Composition 92 3.5 Conclusion:Achievements and Future

_Challenges

93

References 93

4. Dissolution Kinetics of

_Clay

Minerals 101

JordiCama andJiwchar Ganor

4.1 Introduction 102

4.2 Theoretical

_{Background: Clay}

Mineral Dissolution

Kinetics 103

4.2.1

_{pH Dependence}

105

4.2.2 T

_Dependence

107 4.2.3

_{Catalytic/inhibitor}

Effect 107

4.2.4 Effect ofDeviationfrom

_Equilibrium

(ACrEffect) 108 4.2.5 Surface Area and Surface

_Reactivity

109 4.2.6 Ionic

_Strength

Effect 109

4.3

_{Experimental Methodology}

109

4.3.1

_{Aqueous Chemistry:}

Chemical Reactors 110 4.3.2 Solid

_Sample

Surface

_Topography:

_{AFM, VSI, PSI,}

and LCM-DIM 111

4.4 Kaolinite 112

4.4.1 _pH andT

_Dependence

113 4.4.2 EffectofDeviation from

_Equilibrium

(ACr Effect) 115 4.4.3

_{Catalytic/Inhibition}

Effect 116 4.4.4 Ionic

_Strength

Effect 117 4.4.5 Surface Area Effect 117

4.5 Smectite 118

4.5.1

_pH

andT

_Dependence

118 4.5.2 Effect ofDeviation from

_Equilibrium

_(ACrEffect) 121

4.5.3

_{Catalytic/Inhibition}

Effect 122 4.5.4 Ionic

_Strength

Effect 124

4.5.5 SurfaceArea Effect 124

4.6 Micas 127 4.6.1 lllite 127 4.6.2 Muscovite 129 4.6.3 Biotite 132 4.6.4

_Phlogopite

136 4.7 Vermiculite 137 4.8 Chlorite 137

4.9

_Summary

and Conclusions 141

Appendix

143

(5)

5.

_Stability

of

_Clay

Barriers Under

Chemical

Perturbations

155 Olivier Bildstein andFrancis Claret

5.2

_Perturbing

the

_{Physicochemical}

Conditions inthe

Subsurface: Desaturation and Oxidation 157 5.3

_Introducing

Allochthonous Solid Materials in the

Geological

Environment 160

5.3.1

_{Concrete/Clay}

Interactions 160 5.3.2 Steel Corrosion in

_Clay

165 5.4 Chemical Perturbations dueto Allochthonous Gas 170 5.4.1 H2

Injection/Production

171 5.4.2

_Injection

ofC02 172 5.5 Conclusion: What Is Known andWhat Needsto Be

Improved

175

References 176

6.

Self-Diffusion

of Water and Ions in

_Clay

Barriers

189

Ian C. _Bourgand

_Christophe

Tournassat

6.2 _MacroscopicScale Diffusion Coefficients: Definition

and Measurement 191 6.2.1 Fickian

_Expressions

191 6.2.2

_{Experimental Techniques}

192

6.2.3

_{Experimental Challenges}

195

6.3

_Conceptual

Models ofDaand De 197 6.4 _SummaryofMeasured _Daand _DeValues 199

6.4.1 Parametersthat Influence Diffusion in

_Clay

Barriers 199

6.4.2

_Compilation

of Diffusion Data 201

6.4.3 WaterDiffusion 207 6.4.4 Anion Diffusion 209

6.4.5 Cation Diffusion 211

6.5 Future Research Opportunities 216

References 217

7. Gas

Transfer

_{Through Clay}

Barriers 227 A.

_{Amann-Hildenbrand,}

B.M. _{Krooss, J.}

_Harrington,

R. Cuss,

C.

_Davy,

F.

_Skoczylas,

E. _JacopsandN. Maes

7A Introduction 228

7.2 Diffusive

_Transport

of Gas in Solution 230 7.2.1 Theoretical

_Background

230 7.2.2 Literature Review 232

7.3 Advective Flow 235

7.3.1 Theoretical

_Background

235 7.3.2 Literature Review 241

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7.4 _Experiments 245 7.4.1 Diffusion

_Experiments

245 7.4.2 Two-Phase Flow

_Experiments

246 7.4.3

_Examples

247 7.5 Final Remarks and Conclusions 257

Symbols

and Abbreviations 258

References 259

8.

_{Semipermeable}

Membrane

_Properties

and

Chemomechanical

_Coupling

in

_Clay

Barriers 269

Julio Gonqalves,Pierre M.

_Adler,

_{Philippe Cosenza,}

Aliaksei Pazdniakou and Ghislain de

_Marsily

Table of Notation 270

8.2

_Transport

Processes in

_Clay-Rock

Formations 274 8.2.1 Reevaluation of _Darcy's Lawfor

_Clay-Rocks

274 8.2.2

_Experimental

Evidence for aLimited

Validity

of

Darcy's

Law in

_Clay-Rocks

276 8.2.3 Standard

_{Hydrogeological Approach: Nondiagonal}

Terms areAssumed

Negligible

279

8.2.4 When

_Off-Diagonal

Terms Are Not

_Negligible:

Formalism and

_Experimental

Evidence 287 8.2.5 _Importanceof

_Coupled

Terms in

_{Transport Equations}

296 8.3 PredictiveModels for

_{Hydrodynamical Coupling}

Terms

Using

Continuous and/or Granular Media

_Physics

300 8.3.1 Chemical OsmoticModels 300 8.3.2 Electroosmosis 302 8.3.3 Thermoosmosis: From Molecular

_Concepts

to a

Macroscopic

Model 306 8.4

_{Coupled Hydro-Chemo-Mechanical}

Behavior in

Clay-Rocks

308 8.4.1 Surface Forcesand _Disjunction Pressure 308 8.4.2

_Implication

of the

_Disjunction

Pressure Term for

the

_Storativity:

The Electrochemical

_Specific

StorageCoefficient 311

8.5 Conclusion 319

References 320

9.

_{Coupled Thermo-Hydro-Mechanical}

Behavior of

Natural and

_{Engineered Clay}

Barriers 329

Jonny Rutqvist

9.2 THM Behavior of Buffer and Backfill Material 333

9.3 THM Behavior of

_Clay

HostRocks 343 9.4

_Coupled

THM Evolution of

_Engineered

and Natural

_Clay

Barriers in aNuclearWasteRepository 346

9.5 Links ofTHM to

_Geochemistry

350 9.6

_Concluding

Remarks 352

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10.

_{Transport Properties through}

_Partially

Saturated

Charged

Membranes and

_Geophysical

_Approaches

357

A. Revil

10.2 Notations 359

10.3 Electrokinetic Phenomena withoutFiltration 360

10.3.1

_Summary

of the

_Theory

360 10.3.2

_Application

to Electrical

_Conductivity

365 10.3.3

_Application

tothe

_Streaming

Potential

Coupling

Coefficient 366 10.3.4

_Application

totheElectroosmotic

_Permeability

371

10.4 Filtration

_Efficiency

372 10.4.1

_Summary

of the

_Theory

373 10.4.2 Determination of the Osmotic

_Efficiency

374 10.4.3 Filtration

_Efficiency

inSaturated Conditions 377

10.4.4 Filtration

_Efficiency

in Unsaturated Conditions 379

10.4.5 DiffusionCoefficient 380

10.5 Useof

_Geophysical

Methods 382

10.5.1 The Self-Potential Method 382 10.5.2 The DirectCurrent (DC)

Resistivity

Method 383

10.5.3 The Induced PolarizationMethod 383

10.6 Conclusions 384

Glossary

384

Appendix

A:

_{Cation-Dependent}

CEC 386

Appendix B: Osmotic Pressure with theDonnan and

Revil Models 387

Appendix

C: Osmotic Coefficient, Reverse _Osmosis,

and Salt

_Diffusivity

391

References 394

11.

_{Upscaling Strategies}

for

_{Modeling Clay-Rock}

Properties

399

Virginie

MarryandBenjamin

Rotenberg

11.2 From theAtomic Scale tothe Mesoscale 400

11.2.1

_Interlayer

Porosity 400

11.2.2

_Clay

Mineral Particle in Contactwith a Reservoir 403

11.3 From the _Mesoscopicto the

_Macroscopic

Scale 406

11.3.1

_{Representative Elementary}

Volume 407 11.3.2

_Upscaling

from the Particle and PoreScales

tothe

_Sample

Scale 408

11.4 Conclusion 411

References 411

Summary

and

_Perspective

419